Expanding the Chemistry of Rhenium Metal–Metal Bonded Fluoro Complexes: Facile Preparation and Characterization of Paddlewheel Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Balasekaran, Samundeeswari Mariappan; Sattelberger, Alfred P.; Hagenbach, Adelheid

Quadruply bonded rhenium(III) dimers with the stoichiometry Re 2L 4F 2 (1, L = hexahydro-2H-pyrimido[1,2a]pyrimidinate (hpp –); 2, L = diphenyl formamidinate (dpf –)) were prepared from the solid-state melt reactions (SSMRs) between (NH 4) 2[Re 2F 8]·2H 2O and HL. Then those compounds were characterized in the solid state by single-crystal X-ray diffraction and in solution by UV–visible spectroscopy and cyclic voltammetry. The compound [Re 2(hpp) 4F 2]PF 6 (3) was prepared from the one-electron oxidation of Re 2(hpp) 4F 2 with [Cp 2Fe]PF 6. Compounds 1–3 are isostructural with the corresponding chloro derivatives. In summation, compound 1 undergoesmore » two one-electron oxidations. Comparison with its higher halogen homologues reveals that Re 2(hpp) 4F 2 (1) is more easily oxidized than its chloro and bromo analogues.« less

Role of Dynamically Frustrated Bond Disorder in a Li + Superionic Solid Electrolyte

DOE PAGES

Adelstein, Nicole; Wood, Brandon C.

2016-09-16

Inorganic lithium solid electrolytes are critical components in next-generation solid-state batteries, yet the fundamental nature of the cation-anion interactions and their relevance for ionic conductivity in these materials remains enigmatic. Here, we employ first-principles molecular dynamics simulations to explore the interplay between chemistry, structure, and functionality of a highly conductive Li + solid electrolyte, Li3InBr6. Using local-orbital projections to dynamically track the evolution of the electronic charge density, the simulations reveal rapid, correlated fluctuations between cation-anion interactions with different degrees of directional covalent character. These chemical bond dynamics are shown to correlate with Li + mobility, and are enabled thermallymore » by intrinsic frustration between the preferred geometries of chemical bonding and lattice symmetry. We suggest that the fluctuating chemical environment from the polarizable anions functions similar to a solvent, contributing to the superionic behavior of Li 3InBr 6 by temporarily stabilizing configurations favorable for migrating Li +. The generality of these conclusions for understanding solid electrolytes and key factors governing the superionic phase transition is discussed.« less

Density Functionals of Chemical Bonding

PubMed Central

Putz, Mihai V.

2008-01-01

The behavior of electrons in general many-electronic systems throughout the density functionals of energy is reviewed. The basic physico-chemical concepts of density functional theory are employed to highlight the energy role in chemical structure while its extended influence in electronic localization function helps in chemical bonding understanding. In this context the energy functionals accompanied by electronic localization functions may provide a comprehensive description of the global-local levels electronic structures in general and of chemical bonds in special. Becke-Edgecombe and author’s Markovian electronic localization functions are discussed at atomic, molecular and solid state levels. Then, the analytical survey of the main workable kinetic, exchange, and correlation density functionals within local and gradient density approximations is undertaken. The hierarchy of various energy functionals is formulated by employing both the parabolic and statistical correlation degree of them with the electronegativity and chemical hardness indices by means of quantitative structure-property relationship (QSPR) analysis for basic atomic and molecular systems. PMID:19325846

A Comprehensive Study on the Electronic State of Hydrogen in α-Phase PdH(D)x-Does a Chemical Bond Between Pd and H(D) Exist?

PubMed

Dekura, Shun; Kobayashi, Hirokazu; Ikeda, Ryuichi; Maesato, Mitsuhiko; Yoshino, Haruka; Ohba, Masaaki; Ishimoto, Takayoshi; Kawaguchi, Shogo; Kubota, Yoshiki; Yoshioka, Satoru; Matsumura, Syo; Sugiyama, Takeharu; Kitagawa, Hiroshi

2018-06-12

The palladium(Pd)-hydrogen(H) system is one of the most famous hydrogen storage systems. Although there has been much research on β-phase PdH(D)x, we comprehensively investigated the nature of the interaction between Pd and H(D) in α-phase PdH(D)x (x < 0.03 at 303 K), and revealed the existence of Pd-H(D) chemical bond for the first time, by various in situ experimental techniques and first-principles theoretical calculations. The lattice expansion by H(D) dissolution in the α-phase lattice suggests the existence of interaction between Pd and H(D). The decrease of magnetic susceptibility and the increase of electrical resistivity indicate that the electronic states are changed by the H(D) dissolution in the α phase. In situ solid-state 1H and 2H NMR results and first-principles theoretical calculations revealed that a Pd-H(D) chemical bond exists in the α phase, but the bonding character of the Pd-H(D) chemical bond in the α phase is quite different from that in the β phase; the nature of the Pd-H(D) chemical bond in the α phase is a localized covalent bond whereas that in the β phase is a metallic bond. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser-Induced Modification Of Energy Bands Of Transparent Solids

NASA Astrophysics Data System (ADS)

Gruzdev, Vitaly

2010-10-01

Laser-induced variations of electron energy bands of transparent solids significantly affect the initial stages of laser-induced ablation (LIA) influencing rates of ionization and light absorption by conduction-band electrons. We analyze fast variations with characteristic duration in femto-second time domain that include: 1) switching electron functions from bonding to anti-bonding configuration due to laser-induced ionization; 2) laser-driven oscillations of electrons in quasi-momentum space; and 3) direct distortion of the inter-atomic potential by electric field of laser radiation. Among those effects, the latter two have zero delay and reversibly modify band structure taking place from the beginning of laser action. They are of special interest due to their strong influence on the initial stage and threshold of laser ablation. The oscillations modify the electron-energy bands by adding pondermotive potential. The direct action of radiation's electric field leads to high-frequency Franz-Keldysh effect (FKE) spreading the allowed electron states into the forbidden-energy bands. FKE provides decrease of the effective band gap while the electron oscillations lead either to monotonous increase or oscillatory variations of the gap. We analyze the competition between those two opposite trends and their role in initiating LIA.

Structure and bonding in beta-HMX-characterization of a trans-annular N...N interaction.

PubMed

Zhurova, Elizabeth A; Zhurov, Vladimir V; Pinkerton, A Alan

2007-11-14

Chemical bonding in the beta-phase of the 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) crystal based on the experimental electron density obtained from X-ray diffraction data at 20 K, and solid state theoretical calculations, has been analyzed in terms of the quantum theory of atoms in molecules. Features of the intra- and intermolecular bond critical points and the oxygen atom lone-pair locations are discussed. An unusual N...N bonding interaction across the 8-membered ring has been discovered and characterized. Hydrogen bonding, O...O and O...C intermolecular interactions are reported. Atomic charges and features of the electrostatic potential are discussed.

Effect of processing route for preparation of mullite from kaolinite and alumina

NASA Astrophysics Data System (ADS)

Behera, Pallavi Suhasinee; Bhattacharyya, Sunipa

2018-05-01

In current work, two different types of mullite ceramic powder were prepared using kaolinite and alumina by solid state and chemical precipitation route. The phases, bond types and microstructural evolution of the mullite powders were investigated by X-ray diffraction, infrared analysis, and field emission scanning electron microscopy to study the mullitisation behavior. The solid state method evident a pure mullite phase formation at 1550 °C. In case of chemical precipitation route small amount of alumina peak was noticed along with major phase of mullite which was also clearly apprehended from FESEM micrographs and IR spectra. Densification was more for the samples prepared by solid state process which may be correlated to the delayed mullitization process in chemical precipitation route.

Probing the oxygen environment in UO(2)(2+) by solid-state 17O nuclear magnetic resonance spectroscopy and relativistic density functional calculations.

PubMed

Cho, Herman; de Jong, Wibe A; Soderquist, Chuck Z

2010-02-28

A combined theoretical and solid-state (17)O nuclear magnetic resonance (NMR) study of the electronic structure of the uranyl ion UO(2)(2+) in (NH(4))(4)UO(2)(CO(3))(3) and rutherfordine (UO(2)CO(3)) is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens and the latter exemplifying a uranyl environment without hydrogens. Relativistic density functional calculations reveal unique features of the U-O covalent bond, including the finding of (17)O chemical shift anisotropies that are among the largest for oxygen ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state (17)O NMR measurements in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the (17)O echo signal of U (17)O(2)(2+).

Electronic structure studies of a clock-reconstructed Al/Pd(1 0 0) surface alloy

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Tainter, Craig J.

We have employed solid-state Fenske-Hall band structure calculations to examine the electronic structure of Al/Pd(1 0 0), a surface alloy that undergoes a reconstruction, or rearrangement, of the atoms in the top few surface layers. Surface alloys are materials that consist primarily of a single elemental metal, but which have a bimetallic surface composition that is only a few atomic layers in thickness. The results of this study indicate that reconstruction into a clock configuration simultaneously optimizes the intralayer bonding within the surface plane and the bonding between the first and second atomic layers. These results also allow us to examine the fundamental relationship between the electronic and physical structures of this reconstructed surface alloy.

13C and 19F solid-state NMR and X-ray crystallographic study of halogen-bonded frameworks featuring nitrogen-containing heterocycles.

PubMed

Szell, Patrick M J; Gabriel, Shaina A; Gill, Russell D D; Wan, Shirley Y H; Gabidullin, Bulat; Bryce, David L

2017-03-01

Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals formed between two fluorinated halogen-bond donors (1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene) and several nitrogen-containing heterocycles (acridine, 1,10-phenanthroline, 2,3,5,6-tetramethylpyrazine, and hexamethylenetetramine). New structures are reported for the following three cocrystals, all in the P2 1 /c space group: acridine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 13 H 9 N, 1,10-phenanthroline-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 12 H 8 N 2 , and 2,3,5,6-tetramethylpyrazine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C 6 F 3 I 3 ·C 8 H 12 N 2 . 13 C and 19 F solid-state magic-angle spinning (MAS) NMR is shown to be a convenient method to characterize the structural features of the halogen-bond donor and acceptor, with chemical shifts attributable to cocrystal formation observed in the spectra of both nuclides. Cross polarization (CP) from 19 F to 13 C results in improved spectral sensitivity in characterizing the perfluorinated halogen-bond donor when compared to conventional 1 H CP. Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of magnetic shielding constants, along with optimization of the XRD structures, provide a final set of structures in best agreement with the experimental 13 C and 19 F chemical shifts. Data for carbons bonded to iodine remain outliers due to well-known relativistic effects.

Solid-phase synthesis of self-assembling multivalent π-conjugated peptides

DOE PAGES

Sanders, Allix M.; Kale, Tejaswini S.; Katz, Howard E.; ...

2017-02-07

Here, we present a completely solid-phase synthetic strategy to create three- and four-fold peptide-appended π-electron molecules, where the multivalent oligopeptide presentation is dictated by the symmetries of reactive handles placed on discotic π-conjugated cores. Carboxylic acid and anhydride groups were viable amidation and imidation partners, respectively, and oligomeric π-electron discotic cores were prepared through Pd-catalyzed cross-couplings. Due to intermolecular hydrogen bonding between the three or four peptide axes, these π-peptide hybrids self-assemble into robust one-dimensional nanostructures with high aspect ratios in aqueous solution. The preparation of these systems via solid-phase methods will be detailed along with their self-assembly properties, asmore » revealed by steady-state spectroscopy and transmission electron microscopy and electrical characterization using field-effect transistor measurements.« less

79/81Br nuclear quadrupole resonance spectroscopic characterization of halogen bonds in supramolecular assemblies† †Electronic supplementary information (ESI) available: 13C SSNMR spectra, powder X-ray diffractograms. See DOI: 10.1039/c8sc01094c

PubMed Central

Cerreia Vioglio, P.; Szell, P. M. J.; Chierotti, M. R.; Gobetto, R.

2018-01-01

Despite the applicability of solid-state NMR to study the halogen bond, the direct NMR detection of 79/81Br covalently bonded to carbon remains impractical due to extremely large spectral widths, even at ultra-high magnetic fields. In contrast, nuclear quadrupole resonance (NQR) offers comparatively sharp resonances. Here, we demonstrate the abilities of 79/81Br NQR to characterize the electronic changes in the C–Br···N halogen bonding motifs found in supramolecular assemblies constructed from 1,4-dibromotetrafluorobenzene and nitrogen-containing heterocycles. An increase in the bromine quadrupolar coupling constant is observed, which correlates linearly with the halogen bond distance (dBr···N). Notably, 79/81Br NQR is able to distinguish between two symmetry-independent halogen bonds in the same crystal structure. This approach offers a rapid and reliable indication for the occurrence of a halogen bond, with experimental times limited only by the observation of 79/81Br NQR resonances. PMID:29899948

Porous electronic current collector bodies for electrochemical cell configurations

DOEpatents

Pollack, William; Reichner, Philip

1989-01-01

A high-temperature, solid electrolyte electrochemical cell configuration is made comprising a plurality of elongated electrochemical cells 1, having inner electrodes 3, outer electrodes 6 and solid electrolyte 4 therebetween, the cells being electronically connected in series and parallel by flexible, porous, fibrous strips 7, where the strips contain flexible, electronically conductive fibers bonded together and coated with a refractory oxide, and where the oxide coating is effective to prevent additional bonding of fibers during electrochemical cell operation at high temperatures.

Spectral analysis and DFT computations of the hydrogen bonded complex between 2,6-diaminopyridine with 2,6-dichloro-4-nitrophenol in different solvents

NASA Astrophysics Data System (ADS)

Al-Ahmary, Khairia M.; Soliman, Saied M.; Habeeb, Moustafa M.; Al-Obidan, Areej H.

2017-09-01

New hydrogen bonded complex between 2,6-dichloro-4-nitrophenol (DCNP), proton donor with the proton acceptor 2,6-diaminopyridine (DAP) has been synthesized and characterized in solution and solid state by different spectroscopic techniques. Electronic spectra were used to identify the novel proton transfer complex through appearance of new absorption bands in acetonitrile (CH3CN), methanol (CH3OH) and mixture composed from 1:1 methanol and acetonitrile (AN-Me). The complex stoichiometry was determined to be 1:1 by job's method and photometric titrations. The formation constant was determined by applying minimum-maximum absorbances method where it reached high values confirming the complex high stability. A spectroscopic method for determining DAP was presented and validated statistically. The solid complex was characterized by elemental analysis, infrared and 1H NMR studies where the hydrogen bonded reaction occurs between the phenolic OH with the pyridine ring nitrogen as well as one amino group of DNP. The density functional theory DFT (B3LYP) method has been used to energy optimization of the reactants and complex in the ground state using two basis sets 6-31G(d) and 6-31 G+(d,p). The first one led to energy optimized structure through bifurcated hydrogen bond between OH of DCNP with the ring nitrogen and one amino group of DAP with optimization energy -1998.7 Hartree. The second one gave an optimized structure thought hydrogen bonding between OH and one amino group with lowered optimization energy -2018.1 Hartree. Hence, the experimental results will be simulated with the most stable one at DFT/B3LYB 6-31G+ (d,p). The most reactive electrophilic and nucleophilic sites of DCNP and DAP were predicted using the molecular electrostatic potential. The theoretical electronic spectra in the gas phase and the investigated solvents were calculated at TD-DFT/B3LYP 6-31G+ (d,p) and compared with measured electronic spectra where a satisfactory results have been obtained. An important aim of this work is analysis of the interaction energies between the filled natural bond orbitals (NBOs) and the empty ones in order to shed the light on the ease of electron delocalization among bonds in the novel hydrogen bonded complex.

Organometallic benzylidene anilines: donor-acceptor features in NCN-pincer Pt(ii) complexes with a 4-(E)-[(4-R-phenyl)imino]methyl substituent.

PubMed

Batema, Guido D; Lutz, Martin; Spek, Anthony L; van Walree, Cornelis A; van Klink, Gerard P M; van Koten, Gerard

2014-08-28

A series of organometallic 4,4'-substituted benzylidene aniline complexes 4-ClPt-3,5-(CH2NMe2)2C6H2CH[double bond, length as m-dash]NC6H4R'-4', abbreviated as PtCl[NCN(CH[double bond, length as m-dash]NC6H4R'-4')-4], with R' = NMe2, Me, H, Cl, CN (, respectively), was synthesized via a Schiff-base condensation reaction involving reaction of PtCl[NCN(CH[double bond, length as m-dash]O)-4] () with the appropriate 4-R'-substituted aniline derivative () in toluene. The resulting arylplatinum(ii) products were obtained in 75-88% yield. Notably, product was also obtained in 68% yield from a reaction in the solid state by grinding solid with aniline . The structures of , , and in the solid state (single crystal X-ray diffraction) showed a non-planar geometry, in particular for compound . The electronic interaction between the donor benzylidene fragment PtCl(NCN-CH) and the para-R' aniline substituent through the azomethine bridge was studied with NMR and UV/Vis spectroscopy. Linear correlations were found between the azomethine (1)H, the (195)Pt NMR and various (13)C NMR chemical shifts, and the substituent parameters σF and σR of R' at the aniline site. In common with organic benzylidene anilines, the azomethine (1)H NMR chemical shift showed anomalous substituent behavior. The (195)Pt NMR chemical shift of the platinum center can be used as a probe for the electronic properties of the delocalized π-system of the benzylidene aniline framework, to which it is connected. The dual substituent parameter treatment of the azomethine (13)C NMR shift gave important insight into the unique behaviour of the Pt-pincer group as a substituent. Inductively, it is a very strong electron-withdrawing group, whereas mesomerically it behaves like a very strong electron donating group.

X-ray electron density investigation of chemical bonding in van der Waals materials

NASA Astrophysics Data System (ADS)

Kasai, Hidetaka; Tolborg, Kasper; Sist, Mattia; Zhang, Jiawei; Hathwar, Venkatesha R.; Filsø, Mette Ø.; Cenedese, Simone; Sugimoto, Kunihisa; Overgaard, Jacob; Nishibori, Eiji; Iversen, Bo B.

2018-03-01

Van der Waals (vdW) solids have attracted great attention ever since the discovery of graphene, with the essential feature being the weak chemical bonding across the vdW gap. The nature of these weak interactions is decisive for many extraordinary properties, but it is a strong challenge for current theory to accurately model long-range electron correlations. Here we use synchrotron X-ray diffraction data to precisely determine the electron density in the archetypal vdW solid, TiS2, and compare the results with density functional theory calculations. Quantitative agreement is observed for the chemical bonding description in the covalent TiS2 slabs, but significant differences are identified for the interactions across the gap, with experiment revealing more electron deformation than theory. The present data provide an experimental benchmark for testing theoretical models of weak chemical bonding.

Unusually short chalcogen bonds involving organoselenium: insights into the Se-N bond cleavage mechanism of the antioxidant ebselen and analogues.

PubMed

Thomas, Sajesh P; Satheeshkumar, K; Mugesh, Govindasamy; Guru Row, T N

2015-04-27

Structural studies on the polymorphs of the organoselenium antioxidant ebselen and its derivative show the potential of organic selenium to form unusually short Se⋅⋅⋅O chalcogen bonds that lead to conserved supramolecular recognition units. Se⋅⋅⋅O interactions observed in these polymorphs are the shortest such chalcogen bonds known for organoselenium compounds. The FTIR spectral evolution characteristics of this interaction from solution state to solid crystalline state further validates the robustness of this class of supramolecular recognition units. The strength and electronic nature of the Se⋅⋅⋅O chalcogen bonds were explored using high-resolution X-ray charge density analysis and atons-in-molecules (AIM) theoretical analysis. A charge density study unravels the strong electrostatic nature of Se⋅⋅⋅O chalcogen bonding and soft-metal-like behavior of organoselenium. An analysis of the charge density around Se-N and Se-C covalent bonds in conjunction with the Se⋅⋅⋅O chalcogen bonding modes in ebselen and its analogues provides insights into the mechanism of drug action in this class of organoselenium antioxidants. The potential role of the intermolecular Se⋅⋅⋅O chalcogen bonding in forming the intermediate supramolecular assembly that leads to the bond cleavage mechanism has been proposed in terms of electron density topological parameters in a series of molecular complexes of ebselen with reactive oxygen species (ROS). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of nano-LaF3 on the friction and wear behaviors of PTFE-based bonded solid lubricating coatings under different lubrication conditions

NASA Astrophysics Data System (ADS)

Jia, Yulong; Wan, Hongqi; Chen, Lei; Zhou, Huidi; Chen, Jianmin

2016-09-01

Influence of nanometer lanthanum fluoride (nano-LaF3) on the tribological behaviors of polytetrafluoroethylene (PTFE) bonded solid lubricating coatings were investigated using a ring-on-block friction-wear tester under dry friction and RP-3 jet fuel lubrication conditions. The worn surfaces and transfer films formed on the counterpart steel rings were observed by scanning electron microscope (SEM) and optical microscope (OM), respectively. The microstructures of the nano-LaF3 modified coatings and the distribution states of nano-LaF3 were studied by field-emission scanning electron microscope (FESEM) and transmission electron microscopy (TEM), respectively. The results show that incorporation of nano-LaF3 improves the microhardness and the friction-reduced and anti-wear abilities of PTFE bonded solid lubricating coatings. The wear life of the modified coating is about 6 times longer than that of the coating without nano-LaF3 filler at a relatively low applied load (200 N) and rotary speed (1000 rev/min) under dry friction condition. The friction coefficient and wear life of the modified coating decrease with increase of applied load under dry friction, but the friction coefficient has hardly any variation and wear life decreases under RP-3 jet fuel lubrication condition. In addition, the friction coefficient of the modified coating reduces with the rotary speed increasing under dry sliding but has little change under RP-3 lubrication, the wear life increases firstly and then decreases. The results indicated that the wear failure mechanism is dominated by applied load, which plays an important role in guidance of application of nano-LaF3 modified PTFE bonded coating under different working environment.

Isothermal Fourier transform infrared microspectrosopic studies on the stability kinetics of solid-state intramolecular cyclization of aspartame sweetener.

PubMed

Cheng, Y D; Lin, S Y

2000-03-01

A novel Fourier transform infrared (FT-IR) microspectrophotometer equipped with differential scanning calorimetry (DSC) was used to investigate the kinetics of intramolecular cyclization of aspartame (APM) sweetener in the solid state under isothermal conditions. The thermal-dependent changes in the peak intensity of IR spectra at 1543, 1283, and 1259 cm(-1) were examined to explore the reaction. The results support that the intramolecular cyclization process in APM proceeded in three steps: the methoxyl group of ester was first thermolyzed to release methanol, then an acyl cation was attacked by the lone pair of electrons available on nitrogen by an S(N)1 pathway, and finally ring-closure occurred. The intramolecular cyclization of APM determined by this microscopic FT-IR/DSC system was found to follow zero-order kinetics after a brief induction period. The bond cleavage energy (259.38 kJ/mol) of thermolysis for the leaving group of -OCH(3), the bond conversion energy (328.88 kJ/mol) for the amide II NH band to DKP NH band, and the CN bond formation energy (326.93 kJ/mol) of cyclization for the DKP in the APM molecule were also calculated from the Arrhenius equation. The total activation energy of the DKP formation via intramolecular cyclization was 261.33 kJ/mol, calculated by the above summation of the bond energy of cleavage, conversion, and formation, which was near to the value determined by the DSC or TGA method. This indicates that the microscopic FT-IR/DSC system is useful as a potential tool not only to investigate the degradation mechanism of drugs in the solid state but also to directly predict the bond energy of the reaction.

Probing hydrogen bonding in cocrystals and amorphous dispersions using (14)N-(1)H HMQC solid-state NMR.

PubMed

Tatton, Andrew S; Pham, Tran N; Vogt, Frederick G; Iuga, Dinu; Edwards, Andrew J; Brown, Steven P

2013-03-04

Cocrystals and amorphous solid dispersions have generated interest in the pharmaceutical industry as an alternative to more established solid delivery forms. The identification of intermolecular hydrogen bonding interactions in a nicotinamide palmitic acid cocrystal and a 50% w/w acetaminophen-polyvinylpyrrolidone solid dispersion are reported using advanced solid-state magic-angle spinning (MAS) NMR methods. The application of a novel (14)N-(1)H HMQC experiment, where coherence transfer is achieved via through-space couplings, is shown to identify specific hydrogen bonding motifs. Additionally, (1)H isotropic chemical shifts and (14)N electric field gradient (EFG) parameters, both accessible from (14)N-(1)H HMQC experiments, are shown to be sensitive to changes in hydrogen bonding geometry. Numerous indicators of molecular association are accessible from this experiment, including NH cross-peaks occurring from intermolecular hydrogen bonds and changes in proton chemical shifts or electric field gradient parameters. First-principles calculations using the GIPAW approach that yield accurate estimates of isotropic chemical shifts, and EFG parameters were used to assist in assignment. It is envisaged that (14)N-(1)H HMQC solid state NMR experiments could become a valuable screening technique of solid delivery forms in the pharmaceutical industry.

Preparation and characterization of azithromycin--Aerosil 200 solid dispersions with enhanced physical stability.

PubMed

Li, Xuechao; Peng, Huanhuan; Tian, Bin; Gou, Jingxin; Yao, Qing; Tao, Xiaoguang; He, Haibing; Zhang, Yu; Tang, Xing; Cai, Cuifang

2015-01-01

The main purpose of this study was to investigate the feasibility of azithromycin (AZI)--Aerosil 200 solid dispersions specifically with high stability under accelerated condition (40 °C/75% RH). Ball milling (BM) and hot-melt extrusion (HME) were used to prepare AZI solid dispersions. The physical properties of solid dispersions were evaluated by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). For solid dispersions prepared with both methods, no crystalline of AZI was detected (except for AZI: Aerosil 200=75:25) by DSC or PXRD, indicating the amorphous state of AZI in solid dispersions. The FT-IR results demonstrated the loss of crystallization water and the formation of hydrogen bonds between Aerosil 200 and AZI during the preparation of solid dispersions. After 4 weeks storage under accelerated condition, the degree of crystallinity of AZI increased in solid dispersions prepared by BM, whereas for solid dispersions containing AZI, Aerosil 200 and glyceryl behenate (GB) prepared by HME, no crystalline of AZI was identified. This high stability can be attributed to the hydrophobic properties of GB and the presence of hydrogen bonds. Based on the above results, it is inferred the protection of hydrogen bonds between AZI and Aerosil 200 formed during preparation process effectively inhibited the recrystallization of AZI and improved the physical stability of amorphous AZI in the presence of Aerosil 200. Copyright © 2015 Elsevier B.V. All rights reserved.

Electronegativity estimation of electronic polarizabilities of semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Keyan; Xue, Dongfeng, E-mail: dfxue@chem.dlut.edu.cn

2010-03-15

On the basis of the viewpoint of structure-property relationship in solid state matters, we proposed some useful relations to quantitatively calculate the electronic polarizabilities of binary and ternary chalcopyrite semiconductors, by using electronegativity and principal quantum number. The calculated electronic polarizabilities are in good agreement with reported values in the literature. Both electronegativity and principal quantum number can effectively reflect the detailed chemical bonding behaviors of constituent atoms in these semiconductors, which determines the magnitude of their electronic polarizabilities. The present work provides a useful guide to compositionally design novel semiconductor materials, and further explore advanced electro-optic devices.

Solubility Enhancement of a Poorly Water Soluble Drug by Forming Solid Dispersions using Mechanochemical Activation

PubMed Central

Rojas-Oviedo, I.; Retchkiman-Corona, B.; Quirino-Barreda, C. T.; Cárdenas, J.; Schabes-Retchkiman, P. S.

2012-01-01

Mechanochemical activation is a practical cogrinding operation used to obtain a solid dispersion of a poorly water soluble drug through changes in the solid state molecular aggregation of drug-carrier mixtures and the formation of noncovalent interactions (hydrogen bonds) between two crystalline solids such as a soluble carrier, lactose, and a poorly soluble drug, indomethacin, in order to improve its solubility and dissolution rate. Samples of indomethacin and a physical mixture with a weight ratio of 1:1 of indomethacin and lactose were ground using a high speed vibrating ball mill. Particle size was determined by electron microscopy, the reduction of crystallinity was determined by calorimetry and transmission electron microscopy, infrared spectroscopy was used to find evidence of any interactions between the drug and the carrier and the determination of apparent solubility allowed for the corroboration of changes in solubility. Before grinding, scanning electron microscopy showed the drug and lactose to have an average particle size of around 50 and 30 μm, respectively. After high speed grinding, indomethacin and the mixture had a reduced average particle size of around 5 and 2 μm, respectively, showing a morphological change. The ground mixture produced a solid dispersion that had a loss of crystallinity that reached 81% after 30 min of grinding while the drug solubility of indomethacin within the solid dispersion increased by 2.76 fold as compared to the pure drug. Drug activation due to hydrogen bonds between the carboxylic group of the drug and the hydroxyl group of lactose as well as the decrease in crystallinity of the solid dispersion and the reduction of the particle size led to a better water solubility of indomethacin. PMID:23798775

Ambient Mechanochemical Solid-State Reactions of Carbon Nanotubes and Their Reactions via Covalent Coordinate Bond in Solution

NASA Astrophysics Data System (ADS)

Kabbani, Mohamad A.

In its first part, this thesis deals with ambient mechanochemical solid-state reactions of differently functionalized multiple walled carbon nanotubes (MWCNTs) while in its second part it investigates the cross-linking reactions of CNTs in solution via covalent coordinate bonds with transitions metals and carboxylate groups decorating their surfaces. In the first part a series of mechanochemical reactions involving different reactive functionalities on the CNTs such as COOH/OH, COOH/NH2 and COCl/OH were performed. The solid-state unzipping of CNTs leading to graphene formation was confirmed using spectroscopic, thermal and electron microscopy techniques. The non-grapheme products were established using in-situ quadruple mass spectroscopy. The experimental results were confirmed by theoretical simulation calculations using the 'hot spots' protocol. The kinetics of the reaction between MWCNT-COOH and MWCNT-OH was monitored using variable temperature Raman spectroscopy. The low activation energy was discussed in terms of hydrogen bond mediated proton transfer mechanism. The second part involves the reaction of MWCNTII COOH with Zn (II) and Cu (II) to form CNT metal-organic frame (MOFs) products that were tested for their effective use as counter-electrodes in dyes sensitized solar cells (DSSC). The thesis concludes by the study of the room temperature reaction between the functionalized graphenes, GOH and G'-COOH followed by the application of compressive loads. The 3D solid graphene pellet product ( 0.6gm/cc) is conductive and reflective with a 35MPa ultimate strength as compared to 10MPa strength of graphite electrode ( 2.2gm/cc).

Ultrafast laser-induced modifications of energy bands of non-metal crystals

NASA Astrophysics Data System (ADS)

Gruzdev, Vitaly

2009-10-01

Ultrafast laser-induced variations of electron energy bands of transparent solids significantly influence ionization and conduction-band electron absorption driving the initial stage of laser-induced damage (LID). The mechanisms of the variations are attributed to changing electron functions from bonding to anti-bonding configuration via laser-induced ionization; laser-driven electron oscillations in quasi-momentum space; and direct distortion of the inter-atomic potential by electric field of laser radiation. The ionization results in the band-structure modification via accumulation of broken chemical bonds between atoms and provides significant contribution to the overall modification only when enough excited electrons are accumulated in the conduction band. The oscillations are associated with modification of electron energy by pondermotive potential of the oscillations. The direct action of radiation's electric field leads to specific high-frequency Franz-Keldysh effect (FKE) spreading the allowed electron states into the bands of forbidden energy. Those processes determine the effective band gap that is a laser-driven energy gap between the modified electron energy bands. Among those mechanisms, the latter two provide reversible band-structure modification that takes place from the beginning of the ionization and are, therefore, of special interest due to their strong influence on the initial stage of the ionization. The pondermotive potential results either in monotonous increase or oscillatory variations of the effective band gap that has been taken into account in some ionization models. The classical FKE provides decrease of the band gap. We analyzing the competition between those two opposite trends of the effective-band-gap variations and discuss applications of those effects for considerations of the laser-induced damage and its threshold in transparent solids.

Chemical activation of molecules by metals: Experimental studies of electron distributions and bonding

NASA Astrophysics Data System (ADS)

Lichtenberg, Dennis L.

During this period some important breakthroughs were accomplished in understanding the relationships between molecular ionization energies and bond energies in transition metal complexes, in understanding the electronic factors of carbon-hydrogen bond activation by transition metals, in characterizing small molecule bonding interactions with transition metals, and in investigating intermolecular interactions in thin films of transition metal complexes. The formal relationship between measured molecular ionization energies and thermodynamic bond dissociation energies was developed into a single equation which unifies the treatment of covalent bonds, ionic bonds, and partially ionic bonds. The relationship was used to clarify the fundamental thermodynamic information relating to metal-hydrogen, metal-alkyl, and metal-metal bond energies. The ionization energies were also used to correlate the rates of carbonyl substitution reactions of (eta(sup 5)-C5H4X)Rh(CO)2 complexes, and to reveal the factors that control the stability of the transition state. The investigations of the fundamental interactions of C-H sigma and sigma* orbitals metals were continued with study of eta(sup 3)-1-methylallyl metal complexes. Direct observation and measurement of the stabilization energy provided by the agostic interaction of the C-H bond with the metal was obtained. The ability to observe the electronic effects of intermolecular interactions by comparing the ionizations of metal complexes in the gas phase with the ionizations of thin solid organometallic films prepared in ultra-high vacuum was established. Most significantly, the scanning tunneling microscope imaging of these thin films was accomplished.

Electronic structures of anatase (TiO2)1-x(TaON)x solid solutions: a first-principles study.

PubMed

Dang, Wenqiang; Chen, Hungru; Umezawa, Naoto; Zhang, Junying

2015-07-21

Sensitizing wide band gap photo-functional materials under visible-light irradiation is an important task for efficient solar energy conversion. Although nitrogen doping into anatase TiO2 has been extensively studied for this purpose, it is hard to increase the nitrogen content in anatase TiO2 because of the aliovalent nitrogen substituted for oxygen, leading to the formation of secondary phases or defects that hamper the migration of photoexcited charge carriers. In this paper, electronic structures of (TiO2)1-x(TaON)x (0 ≤ x ≤ 1) solid solutions, in which the stoichiometry is satisfied with the co-substitution of Ti for Ta along with O for N, are investigated within the anatase crystal structure using first-principles calculations. Our computational results show that the solid solutions have substantially narrower band gaps than TiO2, without introducing any localized energy states in the forbidden gap. In addition, in comparison with the pristine TiO2, the solid solution has a direct band gap when the content of TaON exceeds 0.25, which is advantageous to light absorption. The valence band maximum (VBM) of the solid solutions, which is mainly composed of N 2p states hybridized with O 2p, Ti 3d or Ta 5d orbitals, is higher in energy than that of pristine anatase TiO2 consisting of non-bonding O 2p states. On the other hand, incorporating TaON into TiO2 causes the formation of d-d bonding states through π interactions and substantially lowers the conduction band minimum (CBM) because of the shortened distance between some metal atoms. As a result, the anatase (TiO2)1-x(TaON)x is expected to become a promising visible-light absorber. In addition, some atomic configurations are found to possess exceptionally narrow band gaps.

Silver flip chip interconnect technology and solid state bonding

NASA Astrophysics Data System (ADS)

Sha, Chu-Hsuan

In this dissertation, fluxless transient liquid phase (TLP) bonding and solid state bonding between thermal expansion mismatch materials have been developed using Ag-In binary systems, pure Au, Ag, and Cu-Ag composite. In contrast to the conventional soldering process, fluxless bonding technique eliminates any corrosion and contamination problems caused by flux. Without flux, it is possible to fabricate high quality joints in large bonding areas where the flux is difficult to clean entirely. High quality joints are crucial to bonding thermal expansion mismatch materials since shear stress develops in the bonded pair. Stress concentration at voids in joints could increases breakage probability. In addition, intermetallic compound (IMC) formation between solder and underbump metallurgy (UBM) is essential for interconnect joint formation in conventional soldering process. However, the interface between IMC and solder is shown to be the weak interface that tends to break first during thermal cycling and drop tests. In our solid state bonding technique, there is no IMC involved in the bonding between Au to Au, Ag and Cu, and Ag and Au. All the reliability issues related to IMC or IMC growth is not our concern. To sum up, ductile bonding media, such as Ag or Au, and proper metallic layered structure are utilized in this research to produce high quality joints. The research starts with developing a low temperature fluxless bonding process using electroplated Ag/In/Ag multilayer structures between Si chip and 304 stainless steel (304SS) substrate. Because the outer thin Ag layer effectively protects inner In layer from oxidation, In layer dissolves Ag layer and joints to Ag layer on the to-be-bonded Si chip when temperature reaches the reflow temperature of 166ºC. Joints consist of mainly Ag-rich Ag-In solid solution and Ag2In. Using this fluxless bonding technique, two 304SS substrates can be bonded together as well. From the high magnification SEM images taken at cross-section, there is no void or gap observed. The new bonding technique presented should be valuable in packaging high power electronic devices for high temperature operations. It should also be useful to bond two 304SS parts together at low bonding temperature of 190ºC. Solid state bonding technique is then introduced to bond semiconductor chips, such as Si, to common substrates, such as Cu or alumina, using pure Ag and Au at a temperature matching the typical reflow temperature used in packaging industries, 260°C. In bonding, we realize the possibilities of solid state bonding of Au to Au, Au to Ag, and Ag to Cu. The idea comes from that Cu, Ag, and Au are located in the same column on periodic table, meaning that they have similar electronic configuration. They therefore have a better chance to share electrons. Also, the crystal lattice of Cu, Ag, and Au is the same, face-centered cubic. In the project, the detailed bonding mechanism is beyond the scope and here we determine the bonding by the experimental result. Ag is chosen as the joint material because of its superior physical properties. It has the highest electrical and thermal conductivities among all metals. It has low yield strength and is relatively ductile. Au is considered as well because its excellent ductility and fatigue resistance. Thus, the Ag or Au joints can deform to accommodate the shear strain caused by CTE mismatch between Si and Cu. Ag and Au have melting temperatures higher than 950°C, so the pure Ag or Au joints are expected to sustain in high operating temperature. The resulting joints do not contain any intermetallic compound. Thus, all reliability issues associated with intermetallic growth in commonly used solder joints do not exist anymore. We finally move to the applications of solid state Ag bonding in flip chip interconnects design. At present, nearly all large-scale integrated circuit (IC) chips are packaged with flip-chip technology. This means that the chip is flipped over and the active (front) side is connected to the package using a large number of tiny solder joints, which provide mechanical support, electrical connection, and heat conduction. For chip-to-package level interconnects, a challenge is the severe mismatch in coefficient of thermal expansion (CTE) between chips and package substrates. The interconnect material thus needs to be compliant to deal with the CTE mismatch. At present, nearly all flip-chip interconnects in electronic industries are made of lead-free Sn-based solders. Soft solders are chosen due to high ductility, low yield strength, relatively low melting temperature, and reasonably good electrical and thermal conductivities. In the never ending scaling down trend, more and more transistors are placed on the same Si chip size. This results in larger pin-out numbers and smaller solder joints. According to International Technology Roadmap for Semiconductors (ITRS), by 2018, the pitch in flip-chip interconnects will become smaller than 70mum for high performance applications. Two problems occur. The first is increase in shear strain. The aspect ratio of flip-chip joints is constrained to 0.7 because it goes through molten phase in the reflow process. Therefore, smaller joints become shorter as well, resulting in larger shear strain arising from CTE mismatch between Si chips and package substrates. The second is increase in stress in the joints. Since intermetallic (IMC) thickness in the joint does not scale down with joint size, ratio of IMC thickness to joint height increases. This further enlarges the shear stress because the IMC does not deform as the soft solder does to accommodate CTE mismatch. In this research, the smallest dimension we achieve for Ag flip chip interconnect joint is 15mum in diameter. The ten advantages of Ag flip chip interconnect technology can be identified as (a) High electrical conductivity, 7.7 times of that of Pb-free solders, (b) High thermal conductivity, 5.2 times of that of Pb-free solders, (c) Completely fluxless, (d) No IMCs; all reliability issues associated with IMC and IMC growth do not exist, (e) Ag is very ductile and can manage CTE mismatch between chips and packages, (f) Ag joints can sustain at very high operation temperature because Ag has high melting temperature of 961°C, (g) No molten phase involved; the bump can better keep its shape and geometry, (h) No molten phase involved; bridging of adjacent bumps is less likely to occur, i. Aspect ratio of bumps can be made greater than 1, (j) The size of the bumps is only limited by the lithographic process. Cu-Ag composite flip chip interconnect joints is developed based on three reasons. The first is lower material cost. The second is to strengthen the columns because the yield strength of Cu is 6 times of that of Ag. The third is to avoid possible Ag migration between Ag electrodes under voltage at temperatures above 250°C. This Cu-Ag composite design presents a solution in the path to the scale down roadmap.

Strain engineering of van der Waals heterostructures.

PubMed

Vermeulen, Paul A; Mulder, Jefta; Momand, Jamo; Kooi, Bart J

2018-01-18

Modifying the strain state of solids allows control over a plethora of functional properties. The weak interlayer bonding in van der Waals (vdWaals) materials such as graphene, hBN, MoS 2 , and Bi 2 Te 3 might seem to exclude strain engineering, since strain would immediately relax at the vdWaals interfaces. Here we present direct observations of the contrary by showing growth of vdWaals heterostructures with persistent in-plane strains up to 5% and we show that strain relaxation follows a not yet reported process distinctly different from strain relaxation in three-dimensionally bonded (3D) materials. For this, 2D bonded Bi 2 Te 3 -Sb 2 Te 3 and 2D/3D bonded Bi 2 Te 3 -GeTe multilayered films are grown using Pulsed Laser Deposition (PLD) and their structure is monitored in situ using Reflective High Energy Electron Diffraction (RHEED) and post situ analysis is performed using Transmission Electron Microscopy (TEM). Strain relaxation is modeled and found to solely depend on the layer being grown and its initial strain. This insight demonstrates that strain engineering of 2D bonded heterostructures obeys different rules than hold for epitaxial 3D materials and opens the door to precise tuning of the strain state of the individual layers to optimize functional performance of vdWaals heterostructures.

Quantum entanglement and quantum information in biological systems (DNA)

NASA Astrophysics Data System (ADS)

Hubač, Ivan; Švec, Miloslav; Wilson, Stephen

2017-12-01

Recent studies of DNA show that the hydrogen bonds between given base pairs can be treated as diabatic systems with spin-orbit coupling. For solid state systems strong diabaticity and spin-orbit coupling the possibility of forming Majorana fermions has been discussed. We analyze the hydrogen bonds in the base pairs in DNA from this perspective. Our analysis is based on a quasiparticle supersymmetric transformation which couples electronic and vibrational motion and includes normal coordinates and the corresponding momenta. We define qubits formed by Majorana fermions in the hydrogen bonds and also discuss the entangled states in base pairs. Quantum information and quantum entropy are introduced. In addition to the well-known classical information connected with the DNA base pairs, we also consider quantum information and show that the classical and quantum information are closely connected.

1,2,4,5-Benzenetetracarboxylic acid: a versatile hydrogen bonding template for controlling the regioselective topochemical synthesis of head-to-tail photodimers from stilbazole derivatives.

PubMed

Ortega, Gabriela; Hernández, Jesús; González, Teresa; Dorta, Romano; Briceño, Alexander

2018-05-16

The crystal engineering of hydrogen bonded organic assemblies based on 1,2,4,5-benzenetetracarboxylic acid (H4bta) and stilbazole derivatives (1-10) is exploited to provide regio-controlled [2 + 2] photocycloadditions in the solid state. Single crystal X-ray diffraction analyses have revealed that all the arrays are built-up from the self-assembly of the (H2bta)2- dianion with two stilbazolium cations via O-HO- and N+-HO- charge-assisted H-bonding synthons: (4-Hstilbazolium+)2(H2bta2-). The dianion displays an interesting diversity of H-bonding motifs. Such structural flexibility allowed us to obtain four structure-types defined by the preferential formation of intramolecular or intermolecular hydrogen bonds between carboxylate-carboxylic groups. In these ionic assemblies two predominant structural H-bonding patterns were observed. The first pattern is characterised by the formation of intramolecular H-bonds in the dianion, leading to discrete assemblies based on ternary arrays. The second hydrogen pattern consists of 2-D hydrogen networks built-up from the self-assembly of anions via intermolecular H-bonds that are linked to the cations. Two additional examples, in which the dianion is self-assembled in two types of ribbons, were also observed. Another supramolecular feature predominant in all these arrays is the stacking of the cations in a head-to-tail fashion, which is controlled via cation-π interactions. These arrays are photoactive in the solid state upon UV-irradiation leading to the regioselective synthesis of rctt-cyclobutane head-to-tail-isomers in high to quantitative yield. In this work, the template tolerance either to steric or electronic effects by changing the number or positions of the supramolecular interactions exerted by distinctive functional groups was also explored. In addition, assemblies bearing 2-chloro (7 and 8) and 3-chloro-4-stilbazole (1 and 9) crystallize in two different crystalline forms, leading to novel examples of supramolecular isomers with similar solid state reactivity.

Metallic-covalent bonding conversion and thermoelectric properties of Al-based icosahedral quasicrystals and approximants.

PubMed

Takagiwa, Yoshiki; Kimura, Kaoru

2014-08-01

In this article, we review the characteristic features of icosahedral cluster solids, metallic-covalent bonding conversion (MCBC), and the thermoelectric properties of Al-based icosahedral quasicrystals and approximants. MCBC is clearly distinguishable from and closely related to the well-known metal-insulator transition. This unique bonding conversion has been experimentally verified in 1/1-AlReSi and 1/0-Al 12 Re approximants by the maximum entropy method and Rietveld refinement for powder x-ray diffraction data, and is caused by a central atom inside the icosahedral clusters. This helps to understand pseudogap formation in the vicinity of the Fermi energy and establish a guiding principle for tuning the thermoelectric properties. From the electron density distribution analysis, rigid heavy clusters weakly bonded with glue atoms are observed in the 1/1-AlReSi approximant crystal, whose physical properties are close to icosahedral Al-Pd-TM (TM: Re, Mn) quasicrystals. They are considered to be an intermediate state among the three typical solids: metals, covalently bonded networks (semiconductor), and molecular solids. Using the above picture and detailed effective mass analysis, we propose a guiding principle of weakly bonded rigid heavy clusters to increase the thermoelectric figure of merit ( ZT ) by optimizing the bond strengths of intra- and inter-icosahedral clusters. Through element substitutions that mainly weaken the inter-cluster bonds, a dramatic increase of ZT from less than 0.01 to 0.26 was achieved. To further increase ZT , materials should form a real gap to obtain a higher Seebeck coefficient.

Thinking Like a Chemist: Intuition in Thermoelectric Materials.

PubMed

Zeier, Wolfgang G; Zevalkink, Alex; Gibbs, Zachary M; Hautier, Geoffroy; Kanatzidis, Mercouri G; Snyder, G Jeffrey

2016-06-06

The coupled transport properties required to create an efficient thermoelectric material necessitates a thorough understanding of the relationship between the chemistry and physics in a solid. We approach thermoelectric material design using the chemical intuition provided by molecular orbital diagrams, tight binding theory, and a classic understanding of bond strength. Concepts such as electronegativity, band width, orbital overlap, bond energy, and bond length are used to explain trends in electronic properties such as the magnitude and temperature dependence of band gap, carrier effective mass, and band degeneracy and convergence. The lattice thermal conductivity is discussed in relation to the crystal structure and bond strength, with emphasis on the importance of bond length. We provide an overview of how symmetry and bonding strength affect electron and phonon transport in solids, and how altering these properties may be used in strategies to improve thermoelectric performance. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An experimental and theoretical study of a hydrogen-bonded complex: O-phenylenediamine with 2,6-pyridinedicarboxylic acid

NASA Astrophysics Data System (ADS)

Ghasemi, Khaled; Rezvani, Ali Reza; Habibi-Khorassani, Sayyed Mostafa; Shahraki, Mehdi; Shokrollahi, Ardeshir; Moghimi, Abolghasem; Tamandani, Halimeh Kord; Gavahi, Sara

2015-11-01

The hydrogen-bonded complex, [(OPDH)+(dipicH)-.H2O], between o-phenylenediamine (OPD) and 2,6-pyridinedicarboxylic acid (dipicH2) has been characterized in water by the 1H, 13C NMR and IR spectroscopies. The crystal structure showed that the edge to face C-H⋯π and C-O⋯π stacking interactions between the dipicH2 and OPD rings play an extra significant role in the formation of the hydrogen-bonded complex and supported the H-bonding interactions. The proton transfer also investigated theoretically in gas phase and thermodynamic parameters such as ΔH‡, ΔG‡, ΔS‡ were calculated for this process. Moreover, intramolecular hydrogen-bonding interaction has been recognized by calculating the electron density ρ(r) and Laplacian ∇2ρ(r) at the bond critical point (BCP) using Atoms-In-Molecule (AIM) method and also the interaction between electron acceptor (σ*) of OH with the lone pair of the nitrogen atom as an electron donor using Natural Bond Orbital (NBO) analysis. In addition, the protonation constants of dipicH2 and OPD and the equilibrium constants for the dipic-OPD (1:1) proton transfer system were obtained by the potentiometric pH titration method using the Hyperquad 2008 program. The stoichiometry of the proton transfer species in the solution confirmed the solid state result.

Mechanisms of H{sub 2}O desorption from amorphous solid water by 157-nm irradiation: An experimental and theoretical study

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeSimone, Alice J.; Crowell, Vernon D.; Sherrill, C. David

2013-10-28

The photodesorption of water molecules from amorphous solid water (ASW) by 157-nm irradiation has been examined using resonance-enhanced multiphoton ionization. The rotational temperature has been determined, by comparison with simulations, to be 425 ± 75 K. The time-of-flight spectrum of H{sub 2}O (v= 0) has been fit with a Maxwell-Boltzmann distribution with a translational temperature of 700 ± 200 K (0.12 ± 0.03 eV). H{sup +} and OH{sup +} fragment ions have been detected with non-resonant multiphoton ionization, indicating vibrationally excited parent water molecules with translational energies of 0.24 ± 0.08 eV. The cross section for water removal from ASWmore » by 7.9-eV photons near 100 K is (6.9 ± 1.8) × 10{sup −20} cm{sup 2} for >10 L H{sub 2}O exposure. Electronic structure computations have also probed the excited states of water and the mechanisms of desorption. Calculated electron attachment and detachment densities show that exciton delocalization leads to a dipole reversal state in the first singlet excited state of a model system of hexagonal water ice. Ab Initio Molecular Dynamics simulations show possible desorption of a photo-excited water molecule from this cluster, though the non-hydrogen bonded OH bond is stretched significantly before desorption. Potential energy curves of this OH stretch in the electronic excited state show a barrier to dissociation, lending credence to the dipole reversal mechanism.« less

Fluxless Bonding Processes Using Silver-Indium System for High Temperature Electronics and Silver Flip-Chip Interconnect Technology

NASA Astrophysics Data System (ADS)

Wu, Yuan-Yun

In this dissertation, fluxless silver (Ag)-indium (In) binary system bonding and Ag solid-state bonding are used between different bonded pairs which have large thermal expansion coefficient (CTE) mismatch and flip-chip interconnect bonding application. In contrast to the conventional soldering process, fluxless bonding technique eliminates contamination and reliability problems caused by flux to fabricate high quality joints. There are two section are reported. In the first section, the reactions of Ag-In binary system are presented. In the second section, the high melting temperature, thermal and electrical conductivity joint materials bonding by either Ag-In binary system bonding or solid-state bonding processes for different bonded pairs and flip-chip application are designed, developed, and reported. Our group have studied Ag-In system for several years and developed the bonding processes successfully. However, the detailed reactions of Ag and In were seldom studied. To design a proper bonding structure, it is necessary to understand the reaction between Ag and In. The systematic experiments were performed to investigate these reactions. A 40 um Ag layer was electroplated on copper (Cu) substrates, followed by indium layers of 1, 3, 5, 10, and 15 um, respectively. The samples were annealed at 180 °C in 0.1 torr vacuum. For samples with In thickness less than 5 mum, the joint compositions are Ag2In only (1 um) or AgIn2, Ag2In, and Ag solid solution (Ag) after annealing. No indium is identified. For 10 and 15 um thick In samples, In covers almost over the entire sample surface after annealing. Later, an Ag layer was annealed at 450 °C for 3 hours to grow Ag grains, followed by plating 10 um In and annealing at 180 °C. By annealing Ag before plating In, more In is kept in the structure during annealing at 180 °C. Based on above results, for those designs with In thinner than 5 um, the Ag layer needs to be annealed, prior to In plating in order to make a successful bonding. In this section, we further studied the Ag-In bonding and solid-state bonding for different bonded pairs and flip-chip application. For the silicon (Si) and aluminum (Al) pair, Al has been used as the material for interconnect pads on the ICs. However, its high CTE (23 x 10-6/°C) and non-solderable property limit its applications in electronic products. To overcome these problems, a fluxless Ag-In bonding was developed. Al was deposited Cr/Cu layer on the surface by E-beam evaporator to make it solderable. 15 um of Ag and 8 um of In were sequentially plated on the Al substrates and 15 um of Ag was on Si chips with Cr/Au coating layer. The bonding was performed at 180 °C in 0.1 torr vacuum. The joint consists of Ag/(Ag)/Ag2In/(Ag)/Ag. The joint can achieve a solidus temperature of beyond 600 °C. From shear test results, the shear strengths far exceed the requirement in MIL-STD-883H. Al is not considered as a favorable substrate material because it is not solderable and has a high CTE. The new method presented in this thesis seems to have surmounted these two challenges. Since Ag2In is weak inside the joint in Ag-In system, an annealed process was used to convert the joints into Ag solid solution (Ag) to increase the joint strength and ductility. Two copper (Cu) substrates were bonded at 180 °C without flux. Bonding samples were annealed at 200 °C for 1,000 hours (first design) and at 250 °C for 350 hours (second design), respectively. Scanning electron microscope with energy dispersive X-ray (EDX) analysis results indicate that the joint of the first design is an alloy of mostly (Ag) with micron-size Ag2In and Ag3In regions, and that of second design has converted to a single (Ag) phase. Shear test results show that the breaking forces far exceed the requirement in MIL-STD-883H. The joint solidus temperatures are 600 °C and 800 °C for the first and second designs, respectively. The research results have shown that high-strength and high temperature joints can be manufactured using fluxless low temperature processes with the Ag-In system and are valuable in developing high temperature package. (Abstract shortened by UMI.).

Triclosan antimicrobial polymers

PubMed Central

Petersen, Richard C.

2016-01-01

Triclosan antimicrobial molecular fluctuating energies of nonbonding electron pairs for the oxygen atom by ether bond rotations are reviewed with conformational computational chemistry analyses. Subsequent understanding of triclosan alternating ether bond rotations is able to help explain several material properties in Polymer Science. Unique bond rotation entanglements between triclosan and the polymer chains increase both the mechanical properties of polymer toughness and strength that are enhanced even better through secondary bonding relationships. Further, polymer blend compatibilization is considered due to similar molecular relationships and polarities. With compatibilization of triclosan in polymers a more uniform stability for nonpolar triclosan in the polymer solid state is retained by the antimicrobial for extremely low release with minimum solubility into aqueous solution. As a result, triclosan is projected for long extended lifetimes as an antimicrobial polymer additive. Further, triclosan rapid alternating ether bond rotations disrupt secondary bonding between chain monomers in the resin state to reduce viscosity and enhance polymer blending. Thus, triclosan is considered for a polymer additive with multiple properties to be an antimicrobial with additional benefits as a nonpolar toughening agent and a hydrophobic wetting agent. The triclosan material relationships with alternating ether bond rotations are described through a complete different form of medium by comparisons with known antimicrobial properties that upset bacterial cell membranes through rapid fluctuating mechanomolecular energies. Also, triclosan bond entanglements with secondary bonding can produce structural defects in weak bacterial lipid membranes requiring pliability that can then interfere with cell division. Regarding applications with polymers, triclosan can be incorporated by mixing into a resin system before cure, melt mixed with thermoplastic polymers that set on cooling into a solid or alternatively applied as a coating through several different methods with dissolving into an organic solvent and dried on by evaporation as a common means. PMID:27280150

Synthesis, electronic and ESR spectral studies on copper(II) nitrate complexes with some acylhydrazines and hydrazones.

PubMed

Singh, Vinod P

2008-11-01

This paper describes the preparation of [Cu(bh)2(H2O)2](NO3)2], [Cu(ibh)2(NO3)2], [Cu(ibh)2(H2O)2](NO3)2 and [Cu(iinh)2(NO3)2] (bh = benzoyl hydrazine (C6H5CONHNH2); ibh = isonicotinoyl hydrazine (NC5H4CONHNH2); ibh = isopropanone benzoyl hydrazone (C6H5CONHN=C(CH3)2; iinh = isopropanone isonicotinoyl hydrazone (NC5H4CONHN=C(CH3)2). These copper(II) complexes are characterized by elemental analyses, molar conductances, dehydration studies, ESR, IR and electronic spectral studies. The electronic and ESR spectra indicate that each complex exhibits a six-coordinate tetragonally distorted octahedral geometry in the solid state and in DMSO solution. The ESR spectra of most of the complexes are typically isotropic type at room temperature (300 K) in solid state as well as in DMSO solution. However, all the complexes exhibit invariably axial signals at 77 K in DMSO solution. The trend g(||) > g(perpendicular) > g(e,) observed in all the complexes suggests the presence of an unpaired electron in the d x2-y2 orbital of the Cu(II). The bh and inh ligands bond to Cu(II) through the >C=O and -NH2 groups whereas, ibh and iinh bond through >C=O and >C=N- groups. The IR spectra of bh and ibh complexes also show H-O-H stretching and bending modes of coordinated water.

Electron-beam-irradiation-induced crystallization of amorphous solid phase change materials

NASA Astrophysics Data System (ADS)

Zhou, Dong; Wu, Liangcai; Wen, Lin; Ma, Liya; Zhang, Xingyao; Li, Yudong; Guo, Qi; Song, Zhitang

2018-04-01

The electron-beam-irradiation-induced crystallization of phase change materials in a nano sized area was studied by in situ transmission electron microscopy and selected area electron diffraction. Amorphous phase change materials changed to a polycrystalline state after being irradiated with a 200 kV electron beam for a long time. The results indicate that the crystallization temperature strongly depends on the difference in the heteronuclear bond enthalpy of the phase change materials. The selected area electron diffraction patterns reveal that Ge2Sb2Te5 is a nucleation-dominated material, when Si2Sb2Te3 and Ti0.5Sb2Te3 are growth-dominated materials.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brammer, L.; Mareque Rivas, J.C.; Zhao, D.

Low-temperature crystal structures of QuinH{sup +}Co(CO){sub 4}{sup {minus}}, 1 (QuinH{sup +} = quinuclidinium), (DABCO)H{sup +}Co(CO){sub 3}P-(p-tolyl){sub 3}{sup {minus}}, 2, and (DABCO)H{sup +}Co(CO){sub 3}PPh{sub 2}(p-tolyl){sup {minus}}, 3 (DABCO = 1,4-diazabicyclooctane), 2 and 3 as their acetonitrile solvates, demonstrate that these salts exhibit intermolecular N--H{hor_ellipsis}Co hydrogen bonding between the cation and anion components. NMR and IR data demonstrate the persistence of these interactions in toluene solution. Such solution-state data, which examine solvated ion pairs, suggest little difference between these salts and the corresponding previously reported salts (DABCO)H{sup +}Co(CO){sub 3}L{sup {minus}} (4, L = CO; 5, L = PPh{sub 3}). However, in themore » solid state, the N--H{hor_ellipsis}Co hydrogen bonds in 1--3 are some 0.1--0.15 {angstrom} longer than would be predicted from consideration of the structures of 4 and 5 and the aforementioned similarity to 4 and 5 in solution. In previous reports the authors have shown that major steric or electronic changes to the anion or cation have resulted in substantial changes (0.15--0.3 {angstrom}) in the N{hor_ellipsis}Co [H{hor_ellipsis}] separation for N--H{hor_ellipsis}Co hydrogen bonds in related R{sub 3}NH{sup +}Co(CO){sub 3}L{sup {minus}} (L = CO, PR{sub 3}) salts. In this report, the authors present examples in which small changes are made to the anion or cation remote from the N--H{hor_ellipsis}Co hydrogen bond. In the solid state, the effect of these small changes on this hydrogen bond is subsumed by the effect of changes in the supramolecular structure. This clearly indicates the sensitivity of the geometry of these hydrogen bonds to the overall balance of intermolecular interactions in the solid state and as such is pertinent to current interest in weak (intermolecular) interactions for which characterization by X-ray crystallography is important.« less

Study of structural, spectroscopic and dielectric properties of multiferroic cadmium doped Samarium manganite synthesized by solid state reaction method

NASA Astrophysics Data System (ADS)

Gupta, Vandana; Raina, Bindu; Verma, Seema; Bamzai, K. K.

2018-05-01

Samarium manganite doped with cadmium having general formula Sm1-xCdxMnO3 for x = 0.05, 0.15 were synthesized by solid state reaction technique. These compositions were characterized by various techniques like X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and dielectric. XRD analysis confirms the single phase formation with pervoskites structure having orthorhombic phase. Densities were determined and compared with the results obtained by Archimedes principle. The scanning electron micrograph shows that the particle size distribution is almost homogeneous and spherical in shape. FTIR analysis confirms the presence of various atomic bonds within a molecule. A very large value of dielectric constant was observed at low frequencies due to the presence of grains and interfaces. The dielectric constant value decreases with increase in cadmium doping at samarium site.

Solid-state reaction of iron on β-SiC

NASA Astrophysics Data System (ADS)

Kaplan, R.; Klein, P. H.; Addamiano, A.

1985-07-01

The solid-state reaction between Fe and β-SiC has been studied using Auger-electron and electron-energy-loss spectroscopies and ion sputter profiling. Fe films from submonolayer coverage to 1000 Å thickness were grown in ultrahigh vacuum, and annealed at temperatures up to 550 °C. Auger line-shape changes occurred even for initial Fe coverage at 190 °C, indicating substantial bond alteration in the SiC substrate. A 1000-Å film was largely consumed by reaction with Si and C diffused from the substrate during a 500 °C anneal, and exhibited both Fe silicide and carbide throughout most of its original volume and free C present as graphite primarily at the surface. As an aid in identifying the reaction products studied in this work, Auger line shapes were first determined for the SiLVV peak in Fe silicide and for the CKLL transition in Fe carbide.

Solid state and dynamic solution structures of O-carbamidine amidoximes gives further insight into the mechanism of zinc(II)-mediated generation of 1,2,4-oxadiazoles

NASA Astrophysics Data System (ADS)

Kulish, Kirill I.; Novikov, Alexander S.; Tolstoy, Peter M.; Bolotin, Dmitrii S.; Bokach, Nadezhda A.; Zolotarev, Andrey A.; Kukushkin, Vadim Yu.

2016-05-01

Three new iminium salts [H2Ndbnd C(R)ONdbnd C(R‧)NH2](p-TolSO3)·½H2O ([1-3](p-TolSO3)·½H2O; R/R‧ = NMe2/PhCH21, NMe2/p-BrC6H42, N(CH2)5/p-BrC6H43) were synthesized via ZnII-mediated amidoxime-cyanamide coupling and their solid structures were studied by X-ray diffraction. Solution structure and conformational changes of [1-3](p-TolSO3)·½H2O were studied by dynamic NMR. The obtained quantitative data were supported by DFT calculations. All the obtained results help to understand the relative stability of the salts [H2Ndbnd C(R)ONdbnd C(R‧)NH2](X) (R = NAlk2, Alk, Ar) and give a further insight into the mechanism of ZnII-mediated generation of 1,2,4-oxadiazoles. The electron delocalization and sesquialteral bonds in the [H2Ndbnd C(NR2)ONdbnd C(R‧)NH2]+ system was recognized by estimation of values of activation energy barriers (14-18 kcal/mol by DNMR and 16-17 kcal/mol by DFT calculations) for the rotation around the CN bonds for the NR2 groups and inspection of the solid-state X-ray data along with the Wiberg bond indices (intermediate single/double bond order for the CN distances). This electron delocalization is responsible for the stabilization of the positively charged iminium cation. The moderate strength hydrogen bonding between the oxime N atom and the =NH2 group, which is verified from the X-ray, DNMR experiments, and by using quantum chemical calculations, stabilizes the iminium salt, but it is still weak to prevent the heterocyclization. Theoretical calculations of the heterocyclization of [H2Ndbnd C(R)ONdbnd C(R‧)NH2]+ to 1,2,4-oxadiazoles demonstrated that it is kinetically hindered to a greater extent for R = NAlk2 and this explains their lower reactivity as compared to the iminium salts with R = Alk, Ar.

Origin of the Counterintuitive Dynamic Charge in the Transition-Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Pike, Nicholas; van Troeye, Benoit; Dewandre, Antoine; Gonze, Xavier; Verstraete, Matthieu

Our recent first-principles calculations of the electronic and vibrational properties of the hexagonal transition-metal dichalcogenides reveal that their Born effective charges display a counterintuitive sign when compared to most other materials or transition-metal dichalcogenides with trigonal symmetry. We determine the origin of this counterintuitive sign by calculating the electronic, vibrational, and optical properties of these systems. We show that the sign of the Born effective charge is directly related to the electric field response of the electronic density, and, in turn, to the bonding characteristics of the material.There is a filled anti-bonding molecular orbital at the Fermi level, which is localized on the transition-metal atom and corresponds to a form of solid state π back-bonding in these material. We propose a method of determining if other materials display a similar counterintuitive sign, based on their bonding characteristics, and propose experiments which could measure the sign of the Born effective charge using different spectroscopies. The authors acknowledge the Belgian Fonds National de la Recherche Scientifique FNRS under PDR T.1077.15-1/7, a FRIA Grant, ULg, and from the Communauté Française de Belgique (ARC AIMED 15/19-09).

Solid-State Electrolyte Anchored with a Carboxylated Azo Compound for All-Solid-State Lithium Batteries.

PubMed

Luo, Chao; Ji, Xiao; Chen, Ji; Gaskell, Karen J; He, Xinzi; Liang, Yujia; Jiang, Jianjun; Wang, Chunsheng

2018-05-23

Organic electrode materials are promising for green and sustainable lithium-ion batteries. However, the high solubility of organic materials in the liquid electrolyte results in the shuttle reaction and fast capacity decay. Herein, azo compounds are firstly applied in all-solid-state lithium batteries (ASSLB) to suppress the dissolution challenge. Due to the high compatibility of azobenzene (AB) based compounds to Li 3 PS 4 (LPS) solid electrolyte, the LPS solid electrolyte is used to prevent the dissolution and shuttle reaction of AB. To maintain the low interface resistance during the large volume change upon cycling, a carboxylate group is added into AB to provide 4-(phenylazo) benzoic acid lithium salt (PBALS), which could bond with LPS solid electrolyte via the ionic bonding between oxygen in PBALS and lithium ion in LPS. The ionic bonding between the active material and solid electrolyte stabilizes the contact interface and enables the stable cycle life of PBALS in ASSLB. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superstrong encapsulated monolayer graphene by the modified anodic bonding

NASA Astrophysics Data System (ADS)

Jung, Wonsuk; Yoon, Taeshik; Choi, Jongho; Kim, Soohyun; Kim, Yong Hyup; Kim, Taek-Soo; Han, Chang-Soo

2013-12-01

We report a superstrong adhesive of monolayer graphene by modified anodic bonding. In this bonding, graphene plays the role of a superstrong and ultra-thin adhesive between SiO2 and glass substrates. As a result, monolayer graphene presented a strong adhesion energy of 1.4 J m-2 about 310% that of van der Waals bonding (0.45 J m-2) to SiO2 and glass substrates. This flexible solid state graphene adhesive can tremendously decrease the adhesive thickness from about several tens of μm to 0.34 nm for epoxy or glue at the desired bonding area. As plausible causes of this superstrong adhesion, we suggest conformal contact with the rough surface of substrates and generation of C-O chemical bonding between graphene and the substrate due to the bonding process, and characterized these properties using optical microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.We report a superstrong adhesive of monolayer graphene by modified anodic bonding. In this bonding, graphene plays the role of a superstrong and ultra-thin adhesive between SiO2 and glass substrates. As a result, monolayer graphene presented a strong adhesion energy of 1.4 J m-2 about 310% that of van der Waals bonding (0.45 J m-2) to SiO2 and glass substrates. This flexible solid state graphene adhesive can tremendously decrease the adhesive thickness from about several tens of μm to 0.34 nm for epoxy or glue at the desired bonding area. As plausible causes of this superstrong adhesion, we suggest conformal contact with the rough surface of substrates and generation of C-O chemical bonding between graphene and the substrate due to the bonding process, and characterized these properties using optical microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr03822j

Using Solution- and Solid-State S K-edge X-ray Absorption Spectroscopy with Density Functional Theory to Evaluate M–S Bonding for MS42- (M = Cr, Mo, W) Dianions

PubMed Central

Olson, Angela C.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Daly, Scott R.; Kozimor, Stosh A.; MacInnes, Molly M.; Martin, Richard L.; Scott, Brian L.

2014-01-01

Herein, we have evaluated relative changes in M–S electronic structure and orbital mixing in Group 6 MS42- dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t2* electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as 1A1 → 1T2 transitions. For MoS42-, both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS42-, solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t2* orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO42- dianions, which allowed M–S and M–O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M–E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M–S bonds, but increased appreciably for M–O interactions. For the t2* orbitals (σ* + π*), mixing decreased slightly for M–S bonding and increased only slightly for the M–O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME42- (E = O, S) dianions. PMID:25311904

Using solution- and solid-state S K-edge X-ray absorption spectroscopy with density functional theory to evaluate M-S bonding for MS4(2-) (M = Cr, Mo, W) dianions.

PubMed

Olson, Angela C; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Daly, Scott R; Kozimor, Stosh A; MacInnes, Molly M; Martin, Richard L; Scott, Brian L

2014-12-14

Herein, we have evaluated relative changes in M-S electronic structure and orbital mixing in Group 6 MS4(2-) dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as (1)A1 → (1)T2 transitions. For MoS4(2-), both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS4(2-), solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO4(2-) dianions, which allowed M-S and M-O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M-E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M-S bonds, but increased appreciably for M-O interactions. For the t orbitals (σ* + π*), mixing decreased slightly for M-S bonding and increased only slightly for the M-O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME4(2-) (E = O, S) dianions.

Probing the Oxygen Environment in UO22+ by Solid-State O-17 Nuclear Magnetic Resonance Spectroscopy and Relativistic Density Functional Calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cho, Herman M.; De Jong, Wibe A.; Soderquist, Chuck Z.

A combined theoretical and solid-state O-17 NMR study of the electronic structure of the uranyl ion UO22+ in (NH4)4UO2(CO3)3 and rutherfordine UO2CO3 is presented, the former representing a system with a hydrogen-bonding environment around the uranyl oxygens, and the latter exemplifying a uranyl environment without hydrogens. A fully relativistic ab initio treatment reveals unique features of the U-O covalent bond, including the finding of O-17 chemical shift anisotropies that are among the largest ever reported (>1200 ppm). Computational results for the oxygen electric field gradient tensor are found to be consistently larger in magnitude than experimental solid-state O-17 NMR measurementsmore » in a 7.05 T magnetic field indicate. A modified version of the Solomon theory of the two-spin echo amplitude for a spin-5/2 nucleus is developed and applied to the analysis of the O-17 echo signal of UO22+. The William R. Wiley environmental Molecular Sciences Laboratory is a US Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. PNNL is operated by Battelle for the US Department of Energy.« less

Synergy of elastic and inelastic energy loss on ion track formation in SrTiO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weber, William J.; Zarkadoula, Eva; Pakarinen, Olli H.

2015-01-12

While the interaction of energetic ions with solids is well known to result in inelastic energy loss to electrons and elastic energy loss to atomic nuclei in the solid, the coupled effects of these energy losses on defect production, nanostructure evolution and phase transformations in ionic and covalently bonded materials are complex and not well understood due to dependencies on electron-electron scattering processes, electron-phonon coupling, localized electronic excitations, diffusivity of charged defects, and solid-state radiolysis. Here we show that a colossal synergy occurs between inelastic energy loss and pre-existing atomic defects created by elastic energy loss in single crystal strontiummore » titanate (SrTiO 3), resulting in the formation of nanometer-sized amorphous tracks, but only in the narrow region with pre-existing defects. These defects locally decrease the electronic and atomic thermal conductivities and increase electron-phonon coupling, which locally increase the intensity of the thermal spike for each ion. This work identifies a major gap in understanding on the role of defects in electronic energy dissipation and electron-phonon coupling; it also provides insights for creating novel interfaces and nanostructures to functionalize thin film structures, including tunable electronic, ionic, magnetic and optical properties.« less

Bonding in phase change materials: concepts and misconceptions.

PubMed

Jones, R O

2018-04-18

Bonding concepts originating in chemistry are surveyed from a condensed matter perspective, beginning around 1850 with 'valence' and the word 'bond' itself. The analysis of chemical data in the 19th century resulted in astonishing progress in understanding the connectivity and stereochemistry of molecules, almost without input from physicists until the development of quantum mechanics in 1925 and afterwards. The valence bond method popularized by Pauling and the molecular orbital methods of Hund, Mulliken, Bloch, and Hückel play major roles in the subsequent development, as does the central part played by the kinetic energy in covalent bonding (Ruedenberg and others). 'Metallic' (free electron) and related approaches, including pseudopotential and density functional theories, have been remarkably successful in understanding structures and bonding in molecules and solids. We discuss these concepts in the context of phase change materials, which involve the rapid and reversible transition between amorphous and crystalline states, and note the confusion that some have caused, in particular 'resonance' and 'resonant bonding'.

79/81Br nuclear quadrupole resonance spectroscopic characterization of halogen bonds in supramolecular assemblies.

PubMed

Cerreia Vioglio, P; Szell, P M J; Chierotti, M R; Gobetto, R; Bryce, D L

2018-05-28

Despite the applicability of solid-state NMR to study the halogen bond, the direct NMR detection of 79/81 Br covalently bonded to carbon remains impractical due to extremely large spectral widths, even at ultra-high magnetic fields. In contrast, nuclear quadrupole resonance (NQR) offers comparatively sharp resonances. Here, we demonstrate the abilities of 79/81 Br NQR to characterize the electronic changes in the C-Br···N halogen bonding motifs found in supramolecular assemblies constructed from 1,4-dibromotetrafluorobenzene and nitrogen-containing heterocycles. An increase in the bromine quadrupolar coupling constant is observed, which correlates linearly with the halogen bond distance ( d Br···N ). Notably, 79/81 Br NQR is able to distinguish between two symmetry-independent halogen bonds in the same crystal structure. This approach offers a rapid and reliable indication for the occurrence of a halogen bond, with experimental times limited only by the observation of 79/81 Br NQR resonances.

Electronic Structure of CO2 at High Pressure

NASA Astrophysics Data System (ADS)

Shieh, S. R.; Jarrige, I.; Hiraoka, N.; Cai, Y.

2009-12-01

Carbon dioxide (CO2) is one of the important planetary materials that can be found in the Venus, Earth and Mars. Therefore, the behavior of CO2 under different pressure and temperature conditions is of great importance for understanding the evolution of these planets. Recent studies showed that there are six solid phases and one amorphous phase of CO2 found at various pressure and temperature conditions. This indicates that CO2 may exhibit different forms within planetary interiors. To better understand the behavior of CO2 polymorphs and their interactions with other materials it is necessary to study the electronic structures of CO2 polymorphs. Here we report the electronic structures of CO2-I and -III at high pressure and room temperature. The high-pressure inelastic scattering measurements of CO2 were conducted at beamline 12XU, SPring-8. A monochromatic beam with incident energy about 10 KeV was focused by a pair of KB mirrors to a size of 20 by 30 μm2. The inelastic x-ray scattering photons were collected at about 35 degrees and a solid state Si detector with resolution of about 1.4eV was used. Each spectrum was collected for 8-20 hours. Our results show that a strong pi bond, together with weak sigma bonds of oxygen K-edge were observed in CO2-I and -III phase. For the carbon K-edge of CO2-I, only a single pi bond was observed. This suggests that the molecular solid phase of CO2-I exhibits a gas-like phase instead of a crystal-like phase. Similar results were also observed form CO2-III.

Chemical bonding analysis on amphoteric hydrogen - alkaline earth ammine borohydrides

NASA Astrophysics Data System (ADS)

Kiruthika, S.; Ravindran, P.

2018-04-01

Usually the ions in solid are in the positive oxidation states or in the negative oxidation state depending upon the chemical environment. It is highly unusual for an ion having both positive as well as negative oxidation state in a particular compound. Structural analysis suggest that the alkaline earth ammine borohydrides (AABH) with the chemical formula M (BH4)2(NH3)2 (M = Mg, Ca, or Sr) where hydrogen is present in +1 and -1 oxidation states. In order to understand the oxidation states of hydrogen and also the character of chemical bond present in AABH we have made charge density, electron localization function, Born effective charge, Bader effective charge, and density of states analyses using result from the density functional calculations. Our detailed analyses show that hydrogen is in amphoteric behavior with hydrogen closer to boron is in negative oxidation state and that closer to nitrogen is in the positive oxidation state. Due to the presence of finite covalent bonding between the consitutents in AABH the oxidation state of hydrogen is non-interger value. The confirmation of the presence of amphtoric behavior of hydrogen in AABH has implication in hydrogen storage applications.

Method of making sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

DOEpatents

Isenberg, Arnold O.

1989-01-01

An electrochemical apparatus is made containing an exterior electorde bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

DOEpatents

Isenberg, Arnold O.

1987-01-01

An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Barochemistry: Predictive Solid State Chemistry

NASA Astrophysics Data System (ADS)

Yoo, Choong-Shik

The application of compression energy comparable to that of chemical bonds, but substantially greater than those of defects and grain boundaries in solids allows us to pursue novel concepts of high-pressure chemistry (or barochemistry) in materials development by design. At such extreme pressures, simple molecular solids covert into densely packed extended network structures that can be predicted from first principles. In recent years, a significant number of new materials and novel extended structures have been designed and discovered in highly compressed states of the first- and second- row elemental solids, including Li, C, H2,N2, O2, CO, CO2, and H2O. These extended solids are extremely hard, have high energy density, and exhibit novel electronic and nonlinear optical properties that are superior to other known materials at ambient conditions. However, these materials are often formed at formidable pressures and are highly metastable at ambient conditions; only a few systems have been recovered, limiting the materials within a realm of fundamental scientific discoveries. Therefore, an exciting new research area has emerged on the barochemistry to understand and, ultimately, control the stability, bonding, structure, and properties of low Z extended solids. In this paper, we will present our recent research to develop hybrid low Z extended solids amenable to scale up synthesis and ambient stabilization, utilizing kinetically controlled processes in dense solid mixtures and discuss the governing fundamental principles of barochemistry. This work was performed in support of the NSF (DMR-1203834), DTRA (HDTRA1-12-01-0020), and DARPA (W31P4Q-12-1-0009).

A detailed study of intermolecular interactions, electronic and vibrational properties of the metal complex bis(uracilato)diammine copper(ii) dihydrate

NASA Astrophysics Data System (ADS)

Gramajo Feijoo, M.; Fernández-Liencres, M. P.; Gil, D. M.; Gómez, M. I.; Ben Altabef, A.; Navarro, A.; Tuttolomondo, M. E.

2018-03-01

Density Functional Theory (DFT) calculations were performed with the aim of investigating the vibrational, electronic and structural properties of [Cu(uracilato-N1)2 (NH3)2]ṡ2H2O complex. The IR and Raman spectra were recorded leading to a complete analysis of the normal modes of vibration of the metal complex. A careful study of the intermolecular interactions observed in solid state was performed by using the Hirshfeld surface analysis and their associated 2D fingerprint plots. The results indicated that the crystal packing is stabilized by Nsbnd H⋯O hydrogen bonds and π-stacking interactions. In addition, Csbnd H···π interactions were also observed. Time-dependent density functional theory (TD-DFT) calculations revealed that all the low-lying electronic states correspond to a mixture of intraligand charge transfer (ILCT) and ligand-to-metal charge transfer (LMCT) transitions. Finally, Natural Bond Orbital (NBO) and Atoms in Molecules (AIM) analysis were performed to shed light on the intermolecular interactions in the coordination sphere.

Short and medium range structures of 80GeSe2–20Ga2Se3 chalcogenide glasses

NASA Astrophysics Data System (ADS)

Petracovschi, Elena; Calvez, Laurent; Cormier, Laurent; Le Coq, David; Du, Jincheng

2018-05-01

The short and medium range structures of 80GeSe2–20Ga2Se3 (or Ge23.5Ga11.8Se64.7) chalcogenide glasses have been studied by combining ab initio molecular dynamics (AIMD) simulations and experimental neutron diffraction studies. The structure factor and total correlation function were calculated from glass structures generated from AIMD simulations and compared with neutron diffraction experiments showing reasonable agreement. The atomic structures of ternary chalcogenide glasses were analyzed in detail, and it was found that gallium atoms are four-fold coordinated by selenium (Se) and form [GaSe4] tetrahedra. Germanium atoms on average also have four-fold coordination, among which Se is 3.5 with the remaining being Ge–Ge homo-nuclear bonds. Ga and Ge tetrahedra link together mainly through corner-sharing and some edge-sharing of Se. No homo-nuclear bonds were observed among Ga atoms or between Ge and Ga. In addition, Se–Se homo-nuclear bonds and Se chains with various lengths were observed. A small fraction of Se atom triclusters that bond to three cations of Ge and Ga were also observed, confirming earlier proposals from 77Se solid state nuclear magnetic resonance studies. Furthermore, the electronic structures of ternary chalcogenide glasses were studied in terms of atomic charge and electronic density of states in order to gain insights into the chemical bonding and electronic properties, as well as to provide an explanation of the observed atomic structures in these ternary chalcogenide glasses.

Electron spin resonance investigations of /sup 11/B/sup 12/C, /sup 11/B/sup 13/C, and /sup 10/B/sup 12/C in neon, argon, and krypton matrices at 4 K: Comparison with theoretical results

DOE Office of Scientific and Technical Information (OSTI.GOV)

Knight L.B. Jr.; Cobranchi, S.T.; Petty, J.T.

1989-01-15

The first spectroscopic study of the diatomic radical BC is reported which confirms previous theoretical predictions of a /sup 4/summation/sup -/ electronic ground state. The nuclear hyperfine interactions (A tensors) obtained for /sup 11/B, /sup 10/B, and /sup 13/C from the electron spin resonance (ESR) measurements are compared with extensive ab initio CI calculations. The BC molecule is one of the first examples of a small high spin radical for such an in-depth experimental--theoretical comparison. The electronic structure of BC obtained from an analysis of the nuclear hyperfine interaction (hfi) is compared to that obtained from a Mulliken-type population analysismore » conducted on a CI wave function which yields A/sub iso/ and A/sub dip/ results in good agreement with the observed values. The BC radical was generated by the laser vaporization of a boron--carbon mixture and trapped in neon, argon, and krypton matrices at 4 K for a complete ESR characterization. The magnetic parameters (MHz) obtained for /sup 11/B/sup 13/C in solid neon are: g/sub parallel/ = 2.0015(3); g/sub perpendicular/ = 2.0020(3); D(zfs) = 1701(2); /sup 11/B: chemically bondA/sub parallel/chemically bond = 100(1); chemically bondA/sub perpendicular/chemically bond = 79(1); /sup 13/C: chemically bondA/sub parallel/chemically bond = 5(2) and chemically bondA/sub perpendicular/chemically bond = 15(1). Based on comparison with the theoretical results, the most likely choice of signs is that all A values are positive.« less

An intrinsically self-healing NiCo//Zn rechargeable battery by self-healable ferric-ion-crosslinking sodium polyacrylate hydrogel electrolyte.

PubMed

Huang, Yan; Liu, Jie; Wang, Jiaqi; Hu, Mengmeng; Mo, Funian; Liang, Guojin; Zhi, Chunyi

2018-06-15

Self-healing solid-state aqueous rechargeable NiCo//Zn batteries are an essential element of flexible/wearable electronics due to their inherent safety, high energy density and mechanical robustness etc. However, the self-healability of solid-state batteries is only realized by few studies, in which electron/ion-inactive self-healable substrates are utilized. This fundamentally arises from the lack of self-healable electrolytes for solid-state batteries, and therefore, results in low healing efficiency and volume/mass diseconomy. Here we develop an intrinsically self-healing battery by designing a new electrolyte that is intrinsically self-healable. Sodium polyacrylate hydrogel chains are crosslinked by ferric ions to promote dynamic reconstruction of an integral network. These non-covalent crosslinkers can form ionic bonds to reconnect damaged surfaces when the hydrogel is cut off, providing an ultimate solution to the intrinsic self-healability problem of batteries. As a result, our NiCo//Zn battery with this hydrogel electrolyte can be autonomically self-healed with over 87% of capacity retained after 4 cycles of breaking/healing. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Relationship between crystal structure and solid-state properties of pharmaceuticals

NASA Astrophysics Data System (ADS)

Sheth, Agam R.

This thesis strives to understand the structure-property relationships of some pharmaceutical crystals at the molecular level with emphasis on the effect of secondary processing on the solid phase. Using single crystal X-ray diffractometry (SCXRD), the structure of warfarin sodium 2-propanol adduct (W) was established to be a true solvate, contrary to previous reports. Using dynamic water vapor sorption, optical and environmental scanning electron microscopy, SCXRD, powder X-ray diffractometry (PXRD), volume computations and molecular modeling, the effect of relative humidity and temperature on the crystal structure of W was investigated. Ab initio calculations on piroxicam showed that the difference in energy between the two polymorphs, I and II, arises predominantly from the difference between their lattice energies. The detailed hydrogen bonding networks of the two polymorphs are described and compared using graph sets. Despite stabilization of the polymorphs by hydrogen bonds, pair-wise distribution function transforms show a loss of polymorphic memory upon cryogrinding the two polymorphs, leading to a difference in recrystallization behavior between amorphous piroxicam prepared from polymorphs I and II. Structural and solid-state changes of piroxicam polymorphs under mechanical stress were investigated using cryogenic grinding, PXRD, diffuse-reflectance solid-state ultraviolet-visible spectroscopy, 13C solid-state nuclear magnetic resonance spectroscopy, and diffuse-reflectance solid-state Fourier-transform infrared spectroscopy. Intermolecular proton transfer was found to accompany changes in phase and color observed upon cryogrinding the two polymorphs. Model-free and model-fitting studies of the dehydration kinetics of piroxicam monohydrate (PM) showed the dependence of activation energy ( Ea) on both isothermal and non-isothermal heating conditions, and on the fraction of conversion. In the constant-E a region, isothermal dehydration follows the two-dimensional phase boundary model, while non-isothermal dehydration follows a mechanism intermediate between two- and three-dimensional diffusion that cannot be described by any of the common models. Structural studies suggest that the complex hydrogen bond pattern in PM is responsible for the observed dehydration behavior. Ab initio calculations provide an explanation for the changes in the molecular and crystal structures accompanying the reversible change in hydration state between anhydrous piroxicam Form I and PM. The thesis further demonstrates the utility of model-free analysis in describing complex dehydration kinetics.

Cu-Sn Intermetallic Compound Joints for High-Temperature Power Electronics Applications

NASA Astrophysics Data System (ADS)

Lee, Byung-Suk; Yoon, Jeong-Won

2018-01-01

Cu-Sn solid-liquid interdiffusion (SLID) bonded joints were fabricated using a Sn-Cu solder paste and Cu for high-temperature power electronics applications. The interfacial reaction behaviors and the mechanical properties of Cu6Sn5 and Cu3Sn SLID-bonded joints were compared. The intermetallic compounds formed at the interfaces in the Cu-Sn SLID-bonded joints significantly affected the die shear strength of the joint. In terms of thermal and mechanical properties, the Cu3Sn SLID-bonded joint was superior to the conventional solder and the Cu6Sn5 SLID-bonded joints.

Hydrogen bonding pattern in N-benzoyl(- DL-)- L-phenylalanines as revealed by solid-state NMR spectroscopy

NASA Astrophysics Data System (ADS)

Potrzebowski, M. J.; Schneider, C.; Tekely, P.

1999-11-01

The nature of the hydrogen bonding pattern has been investigated in N-benzoyl- DL-phenylalanine ( 1) and N-benzoyl- L-phenylalanine ( 2) polymorphes by solid-state NMR spectroscopy. It has been shown that the multiple resonances of carboxyl carbon in 2 are directly connected to different types of hydrogen bonding. The differences in intermolecular distances of carboxyl groups involved in different types of hydrogen bonding have been visualized by the 2D exchange and 1D ODESSA experiments. Potential applications of such a new approach include the exploration of intermolecular distances in hydrogen bonded compounds with singly labeled biomolecules.

Welding, Bonding and Fastening, 1984

NASA Technical Reports Server (NTRS)

Buckley, J. D. (Editor); Stein, B. A. (Editor)

1985-01-01

A compilation of papers presented in a joint NASA, American Society for Metals, The George Washington University, American Welding Soceity, and Society of Manufacturing Engineers conference on Welding, Bonding, and Fastening at Langley Research Center, Hampton, VA, on October 23 to 25, 1984 is given. Papers were presented on technology developed in current research programs relevant to welding, bonding, and fastening of structural materials required in fabricating structures and mechanical systems used in the aerospace, hydrospace, and automotive industries. Topics covered in the conference included equipment, hardware and materials used when welding, brazing, and soldering, mechanical fastening, explosive welding, use of unique selected joining techniques, adhesives bonding, and nondestructive evaluation. A concept of the factory of the future was presented, followed by advanced welding techniques, automated equipment for welding, welding in a cryogenic atmosphere, blind fastening, stress corrosion resistant fasteners, fastening equipment, explosive welding of different configurations and materials, solid-state bonding, electron beam welding, new adhesives, effects of cryogenics on adhesives, and new techniques and equipment for adhesive bonding.

Thermal conductivity switch: Optimal semiconductor/metal melting transition

NASA Astrophysics Data System (ADS)

Kim, Kwangnam; Kaviany, Massoud

2016-10-01

Scrutinizing distinct solid/liquid (s /l ) and solid/solid (s /s ) phase transitions (passive transitions) for large change in bulk (and homogenous) thermal conductivity, we find the s /l semiconductor/metal (S/M) transition produces the largest dimensionless thermal conductivity switch (TCS) figure of merit ZTCS (change in thermal conductivity divided by smaller conductivity). At melting temperature, the solid phonon and liquid molecular thermal conductivities are comparable and generally small, so the TCS requires localized electron solid and delocalized electron liquid states. For cyclic phase reversibility, the congruent phase transition (no change in composition) is as important as the thermal transport. We identify X Sb and X As (X =Al , Cd, Ga, In, Zn) and describe atomic-structural metrics for large ZTCS, then show the superiority of S/M phonon- to electron-dominated transport melting transition. We use existing experimental results and theoretical and ab initio calculations of the related properties for both phases (including the Kubo-Greenwood and Bridgman formulations of liquid conductivities). The 5 p orbital of Sb contributes to the semiconductor behavior in the solid-phase band gap and upon disorder and bond-length changes in the liquid phase this changes to metallic, creating the large contrast in thermal conductivity. The charge density distribution, electronic localization function, and electron density of states are used to mark this S/M transition. For optimal TCS, we examine the elemental selection from the transition, basic, and semimetals and semiconductor groups. For CdSb, addition of residual Ag suppresses the bipolar conductivity and its ZTCS is over 7, and for Zn3Sb2 it is expected to be over 14, based on the structure and transport properties of the better-known β -Zn4Sb3 . This is the highest ZTCS identified. In addition to the metallic melting, the high ZTCS is due to the electron-poor nature of II-V semiconductors, leading to the significantly low phonon conductivity.

DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(iii) complex with dithiocarbamate and phenanthroline.

PubMed

Gowda, Vasantha; Laitinen, Risto S; Telkki, Ville-Veikko; Larsson, Anna-Carin; Antzutkin, Oleg N; Lantto, Perttu

2016-12-06

The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13 C and 15 N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and 13 C and 15 N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P2 1 /n. Both 13 C and 15 N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules. This was supported by single-crystal X-ray crystallography showing that the title compound crystallised in the triclinic space group P1[combining macron]. In addition, the crystal structure also revealed that one of the dithiocarbamate ligands has a conformational disorder. NMR chemical shift calculations employing the periodic gauge including projector augmented wave (GIPAW) approach supported the assignment of the experimental 13 C and 15 N NMR spectra. However, the best correspondences were obtained with the structure where the atomic positions in the X-ray unit cell were optimised at the DFT level. The roles of the scalar and spin-orbit relativistic effects on NMR shielding were investigated using the zeroth-order regular approximation (ZORA) method with the outcome that already the scalar relativistic level qualitatively reproduces the experimental chemical shifts. The electronic properties of the complex were evaluated based on the results of the natural bond orbital (NBO) and topology of the electron density analyses. Overall, we apply a multidisciplinary approach acquiring comprehensive information about the solid-state structure and the metal-ligand bonding of the heteroleptic lanthanum complex.

Bonding prediction in friction stir consolidation of aluminum alloys: A preliminary study

NASA Astrophysics Data System (ADS)

Baffari, Dario; Reynolds, Anthony P.; Li, Xiao; Fratini, Livan

2018-05-01

Friction Stir Consolidation (FSC) is a solid-state process that results in consolidation of metal powders or chips producing solid billet through severe plastic deformation and the solid-state bonding phenomena. This process can be used both for primary production and for metal scrap recycling. During the FSC process, a rotating die is plunged into a hollow chamber containing the finely divided, unconsolidated material to be processed. In this paper, a FEM numerical model for the prediction of the quality of the consolidated billet is presented. In particular, a dedicated bonding criterion that takes into account the peculiar process mechanics of this innovative technology is proposed.

Compression selective solid-state chemistry

NASA Astrophysics Data System (ADS)

Hu, Anguang

Compression selective solid-state chemistry refers to mechanically induced selective reactions of solids under thermomechanical extreme conditions. Advanced quantum solid-state chemistry simulations, based on density functional theory with localized basis functions, were performed to provide a remarkable insight into bonding pathways of high-pressure chemical reactions in all agreement with experiments. These pathways clearly demonstrate reaction mechanisms in unprecedented structural details, showing not only the chemical identity of reactive intermediates but also how atoms move along the reaction coordinate associated with a specific vibrational mode, directed by induced chemical stress occurred during bond breaking and forming. It indicates that chemical bonds in solids can break and form precisely under compression as we wish. This can be realized through strongly coupling of mechanical work to an initiation vibrational mode when all other modes can be suppressed under compression, resulting in ultrafast reactions to take place isothermally in a few femtoseconds. Thermodynamically, such reactions correspond to an entropy minimum process on an isotherm where the compression can force thermal expansion coefficient equal to zero. Combining a significantly brief reaction process with specific mode selectivity, both statistical laws and quantum uncertainty principle can be bypassed to precisely break chemical bonds, establishing fundamental principles of compression selective solid-state chemistry. Naturally this leads to understand the ''alchemy'' to purify, grow, and perfect certain materials such as emerging novel disruptive energetics.

Electronic spectroscopy of UO(2)Cl(2) isolated in solid Ar.

PubMed

Jin, Jin; Gondalia, Raj; Heaven, Michael C

2009-11-12

Laser-induced fluorescence spectra have been recorded for uranyl chloride isolated in a solid Ar matrix. Pulsed excitation was examined using a XeCl excimer laser (308 nm) and a dye laser operating in the 19500-27500 cm-1 range. Several absorption and emission band systems were observed. The emission spectra were characterized by a nearly harmonic vibrational progression with a frequency of 840 cm-1 starting at 20323 cm-1. The electronic absorption spectra were dominated by five harmonic vibrational progressions with frequencies of approximately 710 cm-1. Comparisons with theoretical calculations indicate that all of the transitions observed were associated with the UO2+2 subunit. They involved the promotion of an electron from a bonding orbital to the metal-centered 5f(delta) and 5f(phi) orbitals. Band origins and vibrational constants for five excited states were obtained. Fluorescence was observed from the lowest-energy excited state alone, regardless of the excitation wavelength. The decay curve was found to be biexponential, with characteristic decay lifetimes of 50 and 260 micros.

Quantitative characterization of new supramolecular synthons involving fluorine atoms in the crystal structures of di- and tetrafluorinated benzamides.

PubMed

Mondal, Pradip Kumar; Yadav, Hare Ram; Choudhury, Angshuman Roy; Chopra, Deepak

2017-10-01

Strong hydrogen bonds play a significant role in crystal packing. In particular, the involvement of interactions involving fluorine in controlling the crystal packing requires appropriate attention, especially in the presence of other strong hydrogen bonds. In the present study, a detailed quantitative assessment has been performed of the nature, energetics and topological properties derived from the electron density in model compounds based on fluorinated benzamides (a total of 46 fluorine-substituted benzamides containing multiple fluorine atoms) in the solid state. The primary motivation in the design of such molecules is to enhance the acidity of the interacting H atoms in the presence of an increasing number of F atoms on the molecular scaffold, resulting in increased propensity towards the formation of intermolecular interactions involving organic fluorine. This exercise has resulted in the identification of new and frequently occurring supramolecular synthons involving F atoms in the packing of molecules in the solid state. The energetics associated with short and directional intermolecular Csp 2 -H...F-Csp 2 interactions with significantly high electrostatic contributions is noteworthy, and the topological analysis reveals the bonding character of these ubiquitous interactions in crystal packing in addition to the presence of Csp 2 -F...F-Csp 2 contacts.

Cleanliness inspection tool for RSRM bond surfaces

NASA Technical Reports Server (NTRS)

Mattes, Robert A.

1995-01-01

Using optically stimulated electron emission (OSEE), Thiokol has monitored bond surfaces in process for contamination on the Redesigned Solid Rocket Motor (RSRM). This technique provides process control information to help assure bond surface quality and repeatability prior to bonding. This paper will describe OSEE theory of operation and the instrumentation implemented at Thiokol Corporation since 1987. Data from process hardware will be presented.

Investigation for the amorphous state of ER-34122, a dual 5-lipoxygenase/cyclooxygenase inhibitor with poor aqueous solubility, in HPMC solid dispersion prepared by the solvent evaporation method.

PubMed

Kushida, Ikuo; Gotoda, Masaharu

2013-10-01

ER-34122, a poorly water-soluble dual 5-lipoxygenase/cyclooxygenase inhibitor, exists as a crystalline form. According to an Oak Ridge thermal ellipsoid plot drawing, carbonyl oxygen O (5) makes an intermolecular hydrogen bond with the hydrogen bonded to N (3) in the crystal structure. The FTIR and the solid-state ¹³C NMR spectra suggest that the network is spread out in the amorphous state and the hydrogen bonding gets weaker than that in the crystalline phase, because the carbonyl signals significantly shift in both spectra. When amorphous ER-34122 was heated, crystallization occurred at around 140°C. Similar crystallization happened in the solid dispersion; however, the degree of crystallization was much lower than that observed in the pure amorphous material. Also, the DSC thermogram of the solid dispersion did not show any exothermic peaks implying crystallization. The heat of fusion (ΔHf) determined in the pure amorphous material was nearly equal to that for the crystalline form, whereas the ΔHf value obtained in the solid dispersion was less than a third of them. These data prove that crystallization of the amorphous form is dramatically restrained in the solid dispersion system. The carbonyl wavenumber shifts in the FTIR spectra indicate that the average hydrogen bond in the solid dispersion is lower than that in the pure amorphous material. Therefore, HPMC will suppress formation of the intermolecular network observed in ER-34122 crystal and preserve the amorphous state, which is thermodynamically less stable, in the solid dispersed system.

Chemical Bonding, Interdiffusion and Electronic Structure at InP, GaAs, and Si-Metal Interfaces.

DTIC Science & Technology

1985-10-01

4. H.H. Wieder, J. Vac. Sci. Technol. 15, 1498 (1978). C. 5. W.E. Spicer, 1. Lindau, P. Skeath, C.Y. Su, and P. Chye , Phys. Rev. Lett. 44, 10 420...Spicer, Solid State Electron. 28 307 (1985). 25. N. Newman, K.K. Chin , W.G. Petro, T. Kendelewicz, M.D. Williams, C.E. McCants, and W.E. Spicer, J. Vac...Technol. 19, 661 (1981). 11. Y. Shapira, L.J. Brillson and A. Heller, J. Vac. Sci. U Technol., Al, 766 (1983). 12. P.W. Chye , I. Lindau, P. Pianetta, C.M

Comprehensive theoretical studies on the low-lying electronic states of NiF, NiCl, NiBr, and NiI.

PubMed

Zou, Wenli; Liu, Wenjian

2006-04-21

The low-lying electronic states of the nickel monohalides, i.e., NiF, NiCl, NiBr, and NiI, are investigated by using multireference second-order perturbation theory with relativistic effects taken into account. For the energetically lowest 11 lambda-S states and 26 omega states there into, the potential energy curves and corresponding spectroscopic constants (vertical and adiabatic excitation energies, equilibrium bond lengths, vibrational frequencies, and rotational constants) are reported. The calculated results are grossly in very good agreement with those solid experimental data. In particular, the ground state of NiI is shown to be different from those of NiF, NiCl, and NiBr, being in line with the recent experimental observation. Detailed analyses are provided on those states that either have not been assigned or have been incorrectly assigned by previous experiments.

Ceramic microstructure and adhesion

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1984-01-01

When a ceramic is brought into contact with a ceramic, a polymer, or a metal, strong bond forces can develop between the materials. The bonding forces will depend upon the state of the surfaces, cleanliness and the fundamental properties of the two solids, both surface and bulk. Adhesion between a ceramic and another solid are discussed from a theoretical consideration of the nature of the surfaces and experimentally by relating bond forces to interface resulting from solid state contact. Surface properties of ceramics correlated with adhesion include, orientation, reconstruction and diffusion as well as the chemistry of the surface specie. Where a ceramic is in contact with a metal their interactive chemistry and bond strength is considered. Bulk properties examined include elastic and plastic behavior in the surficial regions, cohesive binding energies, crystal structures and crystallographic orientation. Materials examined with respect to interfacial adhesive interactions include silicon carbide, nickel zinc ferrite, manganese zinc ferrite, and aluminum oxide. The surfaces of the contacting solids are studied both in the atomic or molecularly clean state and in the presence of selected surface contaminants.

Ceramic microstructure and adhesion

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1985-01-01

When a ceramic is brought into contact with a ceramic, a polymer, or a metal, strong bond forces can develop between the materials. The bonding forces will depend upon the state of the surfaces, cleanliness and the fundamental properties of the two solids, both surface and bulk. Adhesion between a ceramic and another solid are discussed from a theoretical consideration of the nature of the surfaces and experimentally by relating bond forces to interface resulting from solid state contact. Surface properties of ceramics correlated with adhesion include, orientation, reconstruction and diffusion as well as the chemistry of the surface specie. Where a ceramic is in contact with a metal their interactive chemistry and bond strength is considered. Bulk properties examined include elastic and plastic behavior in the surficial regions, cohesive binding energies, crystal structures and crystallographic orientation. Materials examined with respect to interfacial adhesive interactions include silicon carbide, nickel zinc ferrite, manganese zinc ferrite, and aluminum oxide. The surfaces of the contacting solids are studied both in the atomic or molecularly clean state and in the presence of selected surface contaminants.

Charge-transfer excited state in pyrene-1-carboxylic acids adsorbed on titanium dioxide nanoparticles

NASA Astrophysics Data System (ADS)

Krawczyk, S.; Nawrocka, A.; Zdyb, A.

2018-06-01

The electronic structure of excited photosensitizer adsorbed at the surface of a solid is the key factor in the electron transfer processes that underlie the efficiency of dye-sensitized solar cells and photocatalysts. In this work, Stark effect (electroabsorption) spectroscopy has been used to measure the polarizability and dipole moment changes in electronic transitions of pyrene-1-carboxylic (PCA), -acetic (PAA) and -butyric (PBA) acids in ethanol, both free and adsorbed on colloidal TiO2, in glassy ethanol at low temperature. The lack of appreciable increase of dipole moment in the excited state of free and adsorbed PAA and PBA points that two or more single bonds completely prevent the expansion of π-electrons from the aromatic ring towards the carboxylic group, thus excluding the possibility of direct electron injection into TiO2. In free PCA, the pyrene's forbidden S0 → S1 transition has increased intensity, exhibits a long progression in 1400 cm-1 Ag mode and is associated with |Δμ| of 2 D. Adsorption of PCA on TiO2 causes a broadening and red shift of the S0 → S1 absorption band and an increase in dipole moment change on electronic excitation to |Δμ| = 6.5 D. This value increased further to about 15 D when the content of acetic acid in the colloid was changed from 0.2% to 2%, and this effect is ascribed to the surface electric field. The large increase of |Δμ| points that the electric field effect can not only change the energetics of electron transfer from the excited sensitizer into the solid, but can also shift the molecular electronic density, thus directly influencing the electronic coupling factor relevant for electron transfer at the molecule-solid interface.

Multiple hydrogen bonding in excited states of aminopyrazine in methanol solution: time-dependent density functional theory study.

PubMed

Chai, Shuo; Yu, Jie; Han, Yong-Chang; Cong, Shu-Lin

2013-11-01

Aminopyrazine (AP) and AP-methanol complexes have been theoretically studied by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). The excited-state hydrogen bonds are discussed in detail. In the ground state the intermolecular multiple hydrogen bonds can be formed between AP molecule and protic solvents. The AP monomer and hydrogen-bonded complex of AP with one methanol are photoexcited initially to the S2 state, and then transferred to the S1 state via internal conversion. However the complex of AP with two methanol molecules is directly excited to the S1 state. From the calculated electronic excited energies and simulated absorption spectra, we find that the intermolecular hydrogen bonds are strengthened in the electronic excited states. The strengthening is confirmed by the optimized excited-state geometries. The photochemical processes in the electronic excited states are significantly influenced by the excited-state hydrogen bond strengthening. Copyright © 2013 Elsevier B.V. All rights reserved.

Preparation, electronic structure, and chemical bonding of lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3 solid solution

NASA Astrophysics Data System (ADS)

Sasikumar, S.; Saravanan, R.; Saravanakumar, S.; Robert, M. Charles

2018-01-01

Polycrystalline lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3, ((1 - x)KBT- xBT) ( x = 0.00, 0.08, 0.12) ceramics were synthesized via solid-state reaction method. The powder X-ray diffraction (PXRD) and structural refinement results confirm that a single-phase tetragonal structure with space group P4mm. Charge density distribution inside the unit cell of (1 - x)KBT- xBT was investigated by the maximum entropy method. Charge density analysis reveals the reduction in ionic nature along K/Bi-O bond and enhancement of covalent nature along Ti-O bond with the addition of BaTiO3. The charge density distribution studies done using maximum entropy method for (1 - x)KBT- xBT have not been done so far. The surface morphology study was done using scanning electron microscopy (SEM). Energy dispersive X-rays spectra (EDS) were used to investigate the elemental compositions present in the system. The dielectric constant and loss tangent were studied as a function of frequency. The dielectric constant and loss were decreased with increase of frequency. Room temperature dielectric constant ( ɛ) and loss (tan δ) were measured for x = 0.00 about 511 and 0.51, respectively, at a frequency of 10 kHz.

Bonding in phase change materials: concepts and misconceptions

NASA Astrophysics Data System (ADS)

Jones, R. O.

2018-04-01

Bonding concepts originating in chemistry are surveyed from a condensed matter perspective, beginning around 1850 with ‘valence’ and the word ‘bond’ itself. The analysis of chemical data in the 19th century resulted in astonishing progress in understanding the connectivity and stereochemistry of molecules, almost without input from physicists until the development of quantum mechanics in 1925 and afterwards. The valence bond method popularized by Pauling and the molecular orbital methods of Hund, Mulliken, Bloch, and Hückel play major roles in the subsequent development, as does the central part played by the kinetic energy in covalent bonding (Ruedenberg and others). ‘Metallic’ (free electron) and related approaches, including pseudopotential and density functional theories, have been remarkably successful in understanding structures and bonding in molecules and solids. We discuss these concepts in the context of phase change materials, which involve the rapid and reversible transition between amorphous and crystalline states, and note the confusion that some have caused, in particular ‘resonance’ and ‘resonant bonding’.

Method for joining metal by solid-state bonding

DOEpatents

Burkhart, L. Elkin; Fultz, Chester R.; Maulden, Kerry A.

1979-01-01

The present development is directed to a method for joining metal at relatively low temperatures by solid-state bonding. Planar surfaces of the metal workpieces are placed in a parallel abutting relationship with one another. A load is applied to at least one of the workpieces for forcing the workpieces together while one of the workpieces is relatively slowly oscillated in a rotary motion over a distance of about 1.degree.. After a preselected number of oscillations, the rotary motion is terminated and the bond between the abutting surfaces is effected. An additional load may be applied to facilitate the bond after terminating the rotary motion.

Translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I

NASA Astrophysics Data System (ADS)

Takahashi, Masae; Ishikawa, Yoichi

2013-06-01

We perform dispersion-corrected first-principles calculations, and far-infrared (terahertz) spectroscopic experiments at 4 K, to examine translational vibrations between chains of hydrogen-bonded molecules in solid-state aspirin form I. The calculated frequencies and relative intensities reproduce the observed spectrum to accuracy of 11 cm-1 or less. The stronger one of the two peaks assigned to the translational mode includes the stretching vibration of the weak hydrogen bond between the acetyl groups of a neighboring one-dimensional chain. The calculation of aspirin form II performed for comparison gives the stretching vibration of the weak hydrogen bond in one-dimensional chain.

Transient lattice contraction in the solid-to-plasma transition

PubMed Central

Ferguson, Ken R.; Bucher, Maximilian; Gorkhover, Tais; Boutet, Sébastien; Fukuzawa, Hironobu; Koglin, Jason E.; Kumagai, Yoshiaki; Lutman, Alberto; Marinelli, Agostino; Messerschmidt, Marc; Nagaya, Kiyonobu; Turner, Jim; Ueda, Kiyoshi; Williams, Garth J.; Bucksbaum, Philip H.; Bostedt, Christoph

2016-01-01

In condensed matter systems, strong optical excitations can induce phonon-driven processes that alter their mechanical properties. We report on a new phenomenon where a massive electronic excitation induces a collective change in the bond character that leads to transient lattice contraction. Single large van der Waals clusters were isochorically heated to a nanoplasma state with an intense 10-fs x-ray (pump) pulse. The structural evolution of the nanoplasma was probed with a second intense x-ray (probe) pulse, showing systematic contraction stemming from electron delocalization during the solid-to-plasma transition. These findings are relevant for any material in extreme conditions ranging from the time evolution of warm or hot dense matter to ultrafast imaging with intense x-ray pulses or, more generally, any situation that involves a condensed matter-to-plasma transition. PMID:27152323

A review of electron-phonon coupling seen in the high-Tc superconductors by angle-resolved photoemission studies (ARPES)

NASA Astrophysics Data System (ADS)

Cuk, T.; Lu, D. H.; Zhou, X. J.; Shen, Z.-X.; Devereaux, T. P.; Nagaosa, N.

2005-01-01

This issue of pss (b) - basic solid state physics contains a collection of Review Articles on the rather controversially discussed topic of Electron-Phonon Interaction in High-Temperature Superconductors, guest-edited by Miodrag Kuli, Johann Wolfgang Goethe-Universität Frankfurt/Main, Germany, with a Preface written by V. L. Ginzburg and E. G. Maksimov [1].The cover picture, taken from the review [2] by T. Cuk et al., shows plots of the electron-phonon coupling vertex, g2(k, k), where k, k are the initial and final electron momentum for electrons scattered by the bond-buckling phonon B1g (the out-of-phase vibration of the in-plane oxygen) in a tight-binding model of the copper-oxygen plane. The momentum dependence of this vertex, along with the d-wave superconducting gap and the van Hove singularity at the anti-node, accounts for the momentum dependence of the collective mode coupling seen in angle-resolved photoemission data on Bi2212.The present issue also sees the start of our rapid research letters, the fastest peer-reviewed publication medium in solid state physics. For more information see www.pss-rapid.com and the Editorial by the Editor-in-Chief Martin Stutzmann on page 7 [3].

Theoretical Studies of Relaxation and Optical Properties of Polymers

NASA Astrophysics Data System (ADS)

Jin, Bih-Yaw

1993-01-01

This thesis is composed of two parts. In the part one, the empirical correlation between the logarithm of tunneling splittings and the temperature at which the spin-lattice relaxation time is minimum for methyl groups in different molecular crystals is explained successfully by taking multiphonon processes into account. We show that one phonon transitions dominate in the low barrier limit. However, in the intermediate barrier range and high barrier limit, it is necessary to include multiphonon processes. We also show that the empirical correlation depends only logarithmically on the details of the phonon bath. In the part two, we have investigated the optical and relaxation properties of conjugated polymers. The connection between the vibronic picture of Raman scattering and the third order perturbation approach in solid state physics is clarified in chapter 2. Starting from the Kramers -Heissenberg-Dirac formula for Raman scattering, we derive expressions for the Condon and Herzberg-Teller terms from a simple two-level system to a two-band system, i.e. polyacetylene, by using traditional vibronic picture. Both the Condon and Herzberg-Teller terms contribute to two-band processes, while three-band processes consist only of Herzberg-Teller terms in the solid state limit. Close to resonance the Condon term dominates and converges to the usual solid state result. In the off-resonance region the Herzberg -Teller term is comparable to Condon term for both small molecule and solid state system. In chapter 3, we will concentrate on the lattice relaxation of the lowest optically allowed 1B_ {u} state, especially, the effect of electron correlation on the excited state geometric relaxation for finite polyenes. We have examined the competition between electron-electron interaction and electron-phonon coupling on the formation of localized lattice distortion in the 1B_{u} state for finite polyene with chain length up to 30 double bonds. The chain length dependence of the lattice relaxation in 1B _{u} state has been studied thoroughly within singly excited configuration interaction for short range Hubbard, extended Hubbard model and long-range Pariser -Parr-Pople model. We have found that local distortion is not favored until a critical chain length is reached. Beyond this critical length, which is a function of electron-electron interaction and electron-phonon coupling strength, a self -trapped exciton is formed rather than the separated soliton -antisoliton configuration as expected in the independent electron theory. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617 -253-5668; Fax 617-253-1690.).

Ab Initio Study of Electronic Excitation Effects on SrTiO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Shijun; Zhang, Yanwen; Weber, William J.

Interaction of energetic ions or lasers with solids often induces electronic excitations that may modify material properties significantly. In this study, effects of electronic excitations on strontium titanate SrTiO 3 (STO) are investigated based on first-principles calculations. The lattice structure, electronic properties, lattice vibrational frequencies, and dynamical stabilities are studied in detail. The results suggest that electronic excitation induces charge redistribution that is mainly observed in Ti–O bonds. The electronic band gap increases with increasing electronic excitation, as excitation mainly induces depopulation of Ti 3d states. Phonon analysis indicates that there is a large phonon band gap induced by electronicmore » excitation because of the changes in the vibrational properties of Ti and O atoms. In addition, a new peak appears in the phonon density of states with imaginary frequencies, an indication of lattice instability. Further dynamics simulations confirm that STO undergoes transition to an amorphous structure under strong electronic excitations. In conclusion, the optical properties of STO under electronic excitation are consistent with the evolution of atomic and electronic structures, which suggests a possibility to probe the properties of STO in nonequilibrium state using optical measurement.« less

Ab Initio Study of Electronic Excitation Effects on SrTiO 3

DOE PAGES

Zhao, Shijun; Zhang, Yanwen; Weber, William J.

2017-11-14

Interaction of energetic ions or lasers with solids often induces electronic excitations that may modify material properties significantly. In this study, effects of electronic excitations on strontium titanate SrTiO 3 (STO) are investigated based on first-principles calculations. The lattice structure, electronic properties, lattice vibrational frequencies, and dynamical stabilities are studied in detail. The results suggest that electronic excitation induces charge redistribution that is mainly observed in Ti–O bonds. The electronic band gap increases with increasing electronic excitation, as excitation mainly induces depopulation of Ti 3d states. Phonon analysis indicates that there is a large phonon band gap induced by electronicmore » excitation because of the changes in the vibrational properties of Ti and O atoms. In addition, a new peak appears in the phonon density of states with imaginary frequencies, an indication of lattice instability. Further dynamics simulations confirm that STO undergoes transition to an amorphous structure under strong electronic excitations. In conclusion, the optical properties of STO under electronic excitation are consistent with the evolution of atomic and electronic structures, which suggests a possibility to probe the properties of STO in nonequilibrium state using optical measurement.« less

Can Csbnd H⋯Fsbnd C hydrogen bonds alter crystal packing features in the presence of Nsbnd H⋯Odbnd C hydrogen bond?

NASA Astrophysics Data System (ADS)

Yadav, Hare Ram; Choudhury, Angshuman Roy

2017-12-01

Intermolecular interactions involving organic fluorine have been the contemporary field of research in the area of organic solid state chemistry. While a group of researchers had refuted the importance of "organic fluorine" in guiding crystal structures, others have provided evidences for in favor of fluorine mediated interactions in the solid state. Many systematic studies have indicated that the "organic fluorine" is capable of offering weak hydrogen bonds through various supramolecular synthons, mostly in the absence of other stronger hydrogen bonds. Analysis of fluorine mediated interaction in the presence of strong hydrogen bonds has not been highlighted in detail. Hence a thorough structural investigation is needed to understand the role of "organic fluorine" in crystal engineering of small organic fluorinated molecules having the possibility of strong hydrogen bond formation in the solution and in the solid state. To fulfil this aim, we have synthesized a series of fluorinated amides using 3-methoxyphenylacetic acid and fluorinated anilines and studied their structural properties through single crystal and powder X-ray diffraction methods. Our results indicated that the "organic fluorine" plays a significant role in altering the packing characteristics of the molecule in building specific crystal lattices even in the presence of strong hydrogen bond.

Synthesis of Pyridine– and Pyrazine–BF 3 Complexes and Their Characterization in Solution and Solid State

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chénard, Etienne; Sutrisno, Andre; Zhu, Lingyang

2016-03-31

Following the discovery of the redox-active 1,4- bis-BF 3-quinoxaline complex, we undertook a structure- activity study with the objective to understand the active nature of the quinoxaline complex. Through systematic synthesis and characterization, we have compared complexes prepared from pyridine and pyrazine derivatives, as heterocyclic core analogues. This paper reports the structural requirements that give rise to the electrochemical features of the 1,4-bis-BF 3-quinoxaline adduct. Using solution and solidstate NMR spectroscopy, the role of aromatic ring fusion and nitrogen incorporation in bonding and electronics was elucidated. We establish the boron atom location and its interaction with its environment from 1Dmore » and 2D solution NMR, X-ray diffraction analysis, and 11B solid-state NMR experiments. Crystallographic analysis of single crystals helped to correlate the boron geometry with 11B quadrupolar coupling constant (CQ) and asymmetry parameter (ηQ), extracted from 11B solid-state NMR spectra. Additionally, computations based on density functional theory were performed to predict electrochemical behavior of the BF 3-heteroaromatic complexes. We then experimentally measured electrochemical potential using cyclic voltammetry and found that the redox potentials and CQ values are similarly affected by electronic changes in the complexes.« less

Electronic structure studies of Ni( 1 0 0 ) surface reconstructions resulting from carbon, nitrogen, or oxygen atom adsorption

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2003-01-01

Solid-state Fenske-Hall band structure calculations have been used to study the different surface structures which result from adsorption of a half monolayer of C, N, or O atoms on the Ni(1 0 0) surface. C or N atoms sit nearly coplanar with the surface Ni atoms and induce the "clock" reconstruction of the surface. In contrast, adsorbed O atoms sit slightly above the Ni(1 0 0) surface plane and have little effect on the overall surface structure. The local environments of the C, N, and O atoms on these surfaces are similar to their environments in a series of late transition metal carbonyl clusters, suggesting that some of the same electronic factors may play a role in favoring the different structures. Results of the calculations indicate that when adsorbates occupy coplanar sites on Ni(1 0 0), much of the Ni-Ni bonding within the surface layer and between the surface- and second-layers is disrupted. On the C- and N-covered surfaces the disruption is more than compensated for by the formation of strong adsorbate-Ni bonds and by new Ni-Ni surface bonds resulting from the clock reconstruction. When O is forced into a coplanar site, however, both the higher electron count and increased electronegativity of the O atoms lead to severe disruption of the surface bonding and weak Ni-O bonds. When O atoms sit above the surface, they form more polar Ni-O bonds, contribute less electron density to the Ni surface bands, and cause less disruption to Ni-Ni surface bonds. These results suggest that, similar to the organometallic clusters, the site preferences of C, N, and O atoms are directly related to their electron count, and in turn to the relative occupation of both Ni-Ni and X-Ni (X=C, N, O) antibonding bands.

Amyloid Hydrogen Bonding Polymorphism Evaluated by (15)N{(17)O}REAPDOR Solid-State NMR and Ultra-High Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

PubMed

Wei, Juan; Antzutkin, Oleg N; Filippov, Andrei V; Iuga, Dinu; Lam, Pui Yiu; Barrow, Mark P; Dupree, Ray; Brown, Steven P; O'Connor, Peter B

2016-04-12

A combined approach, using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and solid-state NMR (Nuclear Magnetic Resonance), shows a high degree of polymorphism exhibited by Aβ species in forming hydrogen-bonded networks. Two Alzheimer's Aβ peptides, Ac-Aβ(16-22)-NH2 and Aβ(11-25), selectively labeled with (17)O and (15)N at specific amino acid residues were investigated. The total amount of peptides labeled with (17)O as measured by FTICR-MS enabled the interpretation of dephasing observed in (15)N{(17)O}REAPDOR solid-state NMR experiments. Specifically, about one-third of the Aβ peptides were found to be involved in the formation of a specific >C═(17)O···H-(15)N hydrogen bond with their neighbor peptide molecules, and we hypothesize that the rest of the molecules undergo ± n off-registry shifts in their hydrogen bonding networks.

Formation of doubly and triply bonded unsaturated compounds HCN, HNC, and CH2NH via N + CH4 low-temperature solid state reaction: from molecular clouds to solar system objects

NASA Astrophysics Data System (ADS)

Mencos, Alejandro; Krim, Lahouari

2018-06-01

We show in the current study carried out in solid phase at cryogenic temperatures that methane (CH4) ice exposed to nitrogen atoms is a source of two acids HCN, HNC, and their corresponding hydrogenated unsaturated species CH2NH, in addition to CH3, C2H6, CN-, and three nitrogen hydrides NH, NH2, and NH3. The solid state N + CH4 reaction taken in the ground state seems to be strongly temperature dependent. While at temperatures lower than 10 K only CH3, NH, NH2, and NH3 species formation is promoted due to CH bond dissociation and NH bond formation, stable compounds with CN bonds are formed at temperatures ranged between 10 and 40 K. Many of these reaction products, resulting from CH4 + N reaction, have already been observed in N2-rich regions such as the atmospheres of Titan, Kuiper belt objects, and molecular clouds of the interstellar medium. Our results show the power of the solid state N-atom chemistry in the transformation of simple astrochemical relevant species, such as CH4 molecules and N atoms into complex organic molecules which are also potentially prebiotic species.

Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sridharan, Niyanth; Isheim, D.; Seidman, David N.

Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

Colossal super saturation of oxygen at the iron-aluminum interfaces fabricated using solid state welding

DOE PAGES

Sridharan, Niyanth; Isheim, D.; Seidman, David N.; ...

2016-12-14

Solid state joining is achieved in three steps, (i) interface asperity deformation, (ii) oxide dispersion, followed by (iii) atomic contact and bonding. Atomically clean metallic surfaces without an oxide layer bond spontaneously. Despite its importance the oxide dispersion mechanism is not well studied. In this work the first ever atom probe study of iron-aluminum solid state welds show that the oxygen concentration at the interface is 20 at.%. This is significantly lower than any equilibrium oxide concentration. Here, we therefore propose that the high-strain rate deformation at the interfaces renders the oxide unstable resulting in the observed concentration of oxygen.

Halogen bonding, chalcogen bonding, pnictogen bonding, tetrel bonding: origins, current status and discussion.

PubMed

Brammer, Lee

2017-10-13

The role of the closing lecture in a Faraday Discussion is to summarise the contributions made to the Discussion over the course of the meeting and in so doing capture the main themes that have arisen. This article is based upon my Closing Remarks Lecture at the 203 rd Faraday Discussion meeting on Halogen Bonding in Supramolecular and Solid State Chemistry, held in Ottawa, Canada, on 10-12 th July, 2017. The Discussion included papers on fundamentals and applications of halogen bonding in the solid state and solution phase. Analogous interactions involving main group elements outside group 17 were also examined. In the closing lecture and in this article these contributions have been grouped into the four themes: (a) fundamentals, (b) beyond the halogen bond, (c) characterisation, and (d) applications. The lecture and paper also include a short reflection on past work that has a bearing on the Discussion.

Probing hydrogen bond networks in half-sandwich Ru(II) building blocks by a combined 1H DQ CRAMPS solid-state NMR, XRPD, and DFT approach.

PubMed

Chierotti, Michele R; Gobetto, Roberto; Nervi, Carlo; Bacchi, Alessia; Pelagatti, Paolo; Colombo, Valentina; Sironi, Angelo

2014-01-06

The hydrogen bond network of three polymorphs (1α, 1β, and 1γ) and one solvate form (1·H2O) arising from the hydration-dehydration process of the Ru(II) complex [(p-cymene)Ru(κN-INA)Cl2] (where INA is isonicotinic acid), has been ascertained by means of one-dimensional (1D) and two-dimensional (2D) double quantum (1)H CRAMPS (Combined Rotation and Multiple Pulses Sequences) and (13)C CPMAS solid-state NMR experiments. The resolution improvement provided by homonuclear decoupling pulse sequences, with respect to fast MAS experiments, has been highlighted. The solid-state structure of 1γ has been fully characterized by combining X-ray powder diffraction (XRPD), solid-state NMR, and periodic plane-wave first-principles calculations. None of the forms show the expected supramolecular cyclic dimerization of the carboxylic functions of INA, because of the presence of Cl atoms as strong hydrogen bond (HB) acceptors. The hydration-dehydration process of the complex has been discussed in terms of structure and HB rearrangements.

Combined crystal chemistry and DFT studies of ThNCl and Th2N2X (X: chalcogen) behaving as pseudo-binaries

NASA Astrophysics Data System (ADS)

Matar, Samir F.; Kfoury, Charbel N.

2018-02-01

Common features and peculiar differentiations characterize binary and ternary thorium nitride Th3N4, thorium nitride chloride ThNCl and the family of thorium nitride chalcogenides Th2N2X (X = O, S, Se, Te) investigated in the framework of the quantum density functional theory DFT. Particularly the dominant effect of the Th-N covalent bond stronger than ionic Th-Cl/Th-X ones as identified from analyses of bonding from overlap integral, electron localization function mapping, electronic density of states and charge transfer, is found at the origin of the layered-like structural arrangements in Th-N monolayers within ThNCl (Cl / [ThN]/ Cl) and Th-N double layers in Th2N2X (X / [Th2N2] / X) with the result of pseudo binary compounds: [ThN]+Cl- and [Th2N2] 2+X2-. All compounds are found semi-conducting with ∼2 eV band gap. It is claimed that such insights into Solid State Chemistry can help rationalizing complex compounds more comprehensively (two examples given).

Hydrogen bond strengthening between o-nitroaniline and formaldehyde in electronic excited states: A theoretical study

NASA Astrophysics Data System (ADS)

Yang, Juan; Li, An Yong

2018-06-01

To study the hydrogen bonds upon photoexcited, the time dependent density function method (TD DFT) was performed to investigate the excited state hydrogen bond properties of between o-nitroaniline (ONA) and formaldehyde (CH2O). The optimized structures of the complex and the monomers both in the ground state and the electronically excited states are calculated using DFT and TD DFT method respectively. Quantum chemical calculations of the electronic and vibrational absorption spectra are also carried out by TD DFT method at the different level. The complex ONA⋯CH2O forms the intramolecular hydrogen bond and intermolecular hydrogen bonds. Since the strength of hydrogen bonds can be measured by studying the vibrational absorption spectra of the characteristic groups on the hydrogen bonding acceptor and donor, it evidently confirms that the hydrogen bonds is strengthened in the S1/S2/T1 excited states upon photoexcitation. As a result, the hydrogen bonds cause that the CH stretch frequency of the proton donor CH2O has a blue shift, and the electron excitations leads to a frequency red shift of Ndbnd O and Nsbnd H stretch modes in the o-nitroaniline(ONA) and a small frequency blue shift of CH stretch mode in the formaldehyde(CH2O) in the S1 and S2 excited states. The excited states S1, S2 and T1 are locally excited states where only the ONA moiety is excited, but the CH2O moiety remains in its ground state.

Characterization of Pharmaceutical Cocrystals and Salts by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Li; Hanrahan, Michael P.; Chakravarty, Paroma

Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less

Characterization of Pharmaceutical Cocrystals and Salts by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy

DOE PAGES

Zhao, Li; Hanrahan, Michael P.; Chakravarty, Paroma; ...

2018-02-15

Multicomponent solids such as cocrystals have emerged as a way to control and engineer the stability, solubility and manufacturability of solid active pharmaceutical ingredients (APIs). Cocrystals are typically formed by solution- or solid-phase reactions of APIs with suitable cocrystal coformers, which are often weak acids. One key structural question about a given multicomponent solid is whether it should be classified as a salt, where the basic API is protonated by the acid, or as a cocrystal, where the API and coformer remain neutral and engage in hydrogen bonding interactions. It has previously been demonstrated that solid-state NMR spectroscopy is amore » powerful probe of structure in cocrystals and salts of APIs, however, the poor sensitivity of solid-state NMR spectroscopy usually restricts the types of experiments that can be performed. Here relayed dynamic nuclear polarization (DNP) was applied to reduce solid-state NMR experiments by one to two orders of magnitude for salts and cocrystals of a complex API. The large sensitivity gains from DNP facilitates rapid acquisition of natural isotopic abundance 13C and 15N solid-state NMR spectra. Critically, DNP enables double resonance 1H-15N solid-state NMR experiments such as 2D 1H-15N HETCOR, 1H-15N CP-build up, 15N{1H} J-resolved/attached proton tests, 1H-15N DIPSHIFT and 1H-15N PRESTO. The latter two experiments allow 1H-15N dipolar coupling constants and H-N bond lengths to be accurately measured, providing an unambiguous assignment of nitrogen protonation state and definitive classification of the multi-component solids as cocrystals or salts. In conclusion, these types of measurements should also be extremely useful in the context of polymorph discrimination, NMR crystallography structure determination and for probing hydrogen bonding in a variety of organic materials.« less

Lightning tests and analyses of tunnel bond straps and shielded cables on the Space Shuttle solid rocket booster

NASA Technical Reports Server (NTRS)

Druen, William M.

1993-01-01

The purposes of the tests and analyses described in this report are as follows: (1) determine the lightning current survivability of five alternative changed designs of the bond straps which electrically bond the solid rocket booster (SRB) systems tunnel to the solid rocket motor (SRM) case; (2) determine the amount of reduction in induced voltages on operational flight (OF) tunnel cables obtained by a modified design of tunnel bond straps (both tunnel cover-to-cover and cover-to-motor case); (3) determine the contribution of coupling to the OF tunnel cables by ground electrical and instrumentation (GEI) cables which enter the systems tunnel from unshielded areas on the surfaces of the motor case; and (4) develop a model (based on test data) and calculate the voltage levels at electronic 'black boxes' connected to the OF cables that run in the systems tunnel.

Putting Cocrystal Stoichiometry to Work: A Reactive Hydrogen-Bonded "Superassembly" Enables Nanoscale Enlargement of a Metal-Organic Rhomboid via a Solid-State Photocycloaddition.

PubMed

Chu, Qianli; Duncan, Andrew J E; Papaefstathiou, Giannis S; Hamilton, Tamara D; Atkinson, Manza B J; Mariappan, S V Santhana; MacGillivray, Leonard R

2018-04-11

Enlargement of a self-assembled metal-organic rhomboid is achieved via the organic solid state. The solid-state synthesis of an elongated organic ligand was achieved by a template directed [2 + 2] photodimerization in a cocrystal. Initial cocrystals obtained of resorcinol template and reactant alkene afforded a 1:2 cocrystal with the alkene in a stacked yet photostable geometry. Cocrystallization performed in the presence of excess template resulted in a 3:2 cocrystal composed of novel discrete 10-component hydrogen-bonded "superassemblies" wherein the alkenes undergo a head-to-head [2 + 2] photodimerization. Isolation and reaction of elongated photoproduct with Cu(II) ions afforded a metal-organic rhomboid of nanoscale dimensions that hosts small molecules in the solid state as guests.

Effect of electronic structure of the diamond surface on the strength of the diamond-metal interface

NASA Technical Reports Server (NTRS)

Pepper, S. V.

1981-01-01

A diamond surface undergoes a transformation in its electronic structure by a vacuum anneal at approximately 900 C. The polished surface has no electronic states in the band gap, whereas the annealed surface has both occupied and unoccupied states in the and gap and exhibits some electrical conductivity. The effect of this transformation on the strength of the diamond metal interface was investigated by measuring the static friction force of an atomically clean meta sphere on a diamond flat in ultrahigh vacuum. It was found that low friction (weak bonding) is associated with the diamond surface devoid of gap states whereas high friction (strong bonding) is associated with the diamond surface with gap states. Exposure of the annealed surface to excited hydrogen also leads to weak bonding. The interfacial bond is discussed in terms of interaction of the metal conduction band electrons with the band gap states on the diamond surface. Effects of surface electrical conductivity on the interfacial bond are also be considered.

Structure, Chemistry and Property Correlations in FeSe and 122 Pnictides

NASA Astrophysics Data System (ADS)

Cava, Robert

2010-03-01

Determining how crystal structure and chemical bonding influence the properties of solids is at the heart of collaborative research programs between materials physicists and solid state chemists. In some materials, the high Tc copper oxides and colossal magnetoresistance manganates, for example, the subtleties of how structure, bonding and properties are coupled yields an almost baffling complexity, while in others, such as many classical intermetallic superconductors, the properties are more easily understood, with bonding and structure playing a less profound role. The new superconducting pnictides appear to fall somewhere between these two limits, and have so far been the subject of relatively little study by solid state chemists. Here I will describe some of our recent work on superconducting FeSe and superconductor-related ``122'' (ThCr2Si2-type) solid solution phases as examples of the kinds of insights that structural and chemical studies can contribute to understanding these important materials.

Role of bond adaptability in the passivation of colloidal quantum dot solids.

PubMed

Thon, Susanna M; Ip, Alexander H; Voznyy, Oleksandr; Levina, Larissa; Kemp, Kyle W; Carey, Graham H; Masala, Silvia; Sargent, Edward H

2013-09-24

Colloidal quantum dot (CQD) solids are attractive materials for photovoltaic devices due to their low-cost solution-phase processing, high absorption cross sections, and their band gap tunability via the quantum size effect. Recent advances in CQD solar cell performance have relied on new surface passivation strategies. Specifically, cadmium cation passivation of surface chalcogen sites in PbS CQDs has been shown to contribute to lowered trap state densities and improved photovoltaic performance. Here we deploy a generalized solution-phase passivation strategy as a means to improving CQD surface management. We connect the effects of the choice of metal cation on solution-phase surface passivation, film-phase trap density of states, minority carrier mobility, and photovoltaic power conversion efficiency. We show that trap passivation and midgap density of states determine photovoltaic device performance and are strongly influenced by the choice of metal cation. Supported by density functional theory simulations, we propose a model for the role of cations, a picture wherein metals offering the shallowest electron affinities and the greatest adaptability in surface bonding configurations eliminate both deep and shallow traps effectively even in submonolayer amounts. This work illustrates the importance of materials choice in designing a flexible passivation strategy for optimum CQD device performance.

Quantitative secondary electron detection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Agrawal, Jyoti; Joy, David C.; Nayak, Subuhadarshi

Quantitative Secondary Electron Detection (QSED) using the array of solid state devices (SSD) based electron-counters enable critical dimension metrology measurements in materials such as semiconductors, nanomaterials, and biological samples (FIG. 3). Methods and devices effect a quantitative detection of secondary electrons with the array of solid state detectors comprising a number of solid state detectors. An array senses the number of secondary electrons with a plurality of solid state detectors, counting the number of secondary electrons with a time to digital converter circuit in counter mode.

Solid state electro-optic color filter and iris

NASA Technical Reports Server (NTRS)

1975-01-01

A pair of solid state electro-optic filters (SSEF) in a binocular holder were designed and fabricated for evaluation of field sequential stereo TV applications. The electronic circuitry for use with the stereo goggles was designed and fabricated, requiring only an external video input. A polarizing screen suitable for attachment to various size TV monitors for use in conjunction with the stereo goggles was designed and fabricated. An improved engineering model 2 filter was fabricated using the bonded holder technique developed previously and integrated to a GCTA color TV camera. An engineering model color filter was fabricated and assembled using PLZT control elements. In addition, a ruggedized holder assembly was designed, fabricated and tested. This assembly provides electrical contacts, high voltage protection, and support for the fragile PLZT disk, and also permits mounting and optical alignment of the associated polarizers.

Effect of raw material ratios on the compressive strength of magnesium potassium phosphate chemically bonded ceramics.

PubMed

Wang, Ai-juan; Yuan, Zhi-long; Zhang, Jiao; Liu, Lin-tao; Li, Jun-ming; Liu, Zheng

2013-12-01

The compressive strength of magnesium potassium phosphate chemically bonded ceramics is important in biomedical field. In this work, the compressive strength of magnesium potassium phosphate chemically bonded ceramics was investigated with different liquid-to-solid and MgO-to-KH2PO4 ratios. X-ray diffractometer was applied to characterize its phase composition. The microstructure was imaged using a scanning electron microscope. The results showed that the compressive strength of the chemically bonded ceramics increased with the decrease of liquid-to-solid ratio due to the change of the packing density and the crystallinity of hydrated product. However, with the increase of MgO-to-KH2PO4 weight ratio, its compressive strength increased firstly and then decreased. The low compressive strength in lower MgO-to-KH2PO4 ratio might be explained by the existence of the weak phase KH2PO4. However, the low value of compressive strength with the higher MgO-to-KH2PO4 ratio might be caused by lack of the joined phase in the hydrated product. Besides, it has been found that the microstructures were different in these two cases by the scanning electron microscope. Colloidal structure appeared for the samples with lower liquid-to-solid and higher MgO-to-KH2PO4 ratios possibly because of the existence of amorphous hydrated products. The optimization of both liquid-to-solid and MgO-to-KH2PO4 ratios was important to improve the compressive strength of magnesium potassium phosphate chemically bonded ceramics. © 2013.

Theoretical study of actinide monocarbides (ThC, UC, PuC, and AmC)

NASA Astrophysics Data System (ADS)

Pogány, Peter; Kovács, Attila; Visscher, Lucas; Konings, Rudy J. M.

2016-12-01

A study of four representative actinide monocarbides, ThC, UC, PuC, and AmC, has been performed with relativistic quantum chemical calculations. The two applied methods were multireference complete active space second-order perturbation theory (CASPT2) including the Douglas-Kroll-Hess Hamiltonian with all-electron basis sets and density functional theory with the B3LYP exchange-correlation functional in conjunction with relativistic pseudopotentials. Beside the ground electronic states, the excited states up to 17 000 cm-1 have been determined. The molecular properties explored included the ground-state geometries, bonding properties, and the electronic absorption spectra. According to the occupation of the bonding orbitals, the calculated electronic states were classified into three groups, each leading to a characteristic bond distance range for the equilibrium geometry. The ground states of ThC, UC, and PuC have two doubly occupied π orbitals resulting in short bond distances between 1.8 and 2.0 Å, whereas the ground state of AmC has significant occupation of the antibonding orbitals, causing a bond distance of 2.15 Å.

Performance of the strongly constrained and appropriately normed density functional for solid-state materials

DOE PAGES

Isaacs, Eric B.; Wolverton, Chris

2018-06-22

Constructed to satisfy 17 known exact constraints for a semilocal density functional, the strongly constrained and appropriately normed (SCAN) meta-generalized-gradient-approximation functional has shown early promise for accurately describing the electronic structure of molecules and solids. One open question is how well SCAN predicts the formation energy, a key quantity for describing the thermodynamic stability of solid-state compounds. To answer this question, we perform an extensive benchmark of SCAN by computing the formation energies for a diverse group of nearly 1000 crystalline compounds for which experimental values are known. Due to an enhanced exchange interaction in the covalent bonding regime, SCANmore » substantially decreases the formation energy errors for strongly bound compounds, by approximately 50% to 110 meV/atom, as compared to the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE). However, for intermetallic compounds, SCAN performs moderately worse than PBE with an increase in formation energy error of approximately 20%, stemming from SCAN's distinct behavior in the weak bonding regime. The formation energy errors can be further reduced via elemental chemical potential fitting. We find that SCAN leads to significantly more accurate predicted crystal volumes, moderately enhanced magnetism, and mildly improved band gaps as compared to PBE. Altogether, SCAN represents a significant improvement in accurately describing the thermodynamics of strongly bound compounds.« less

Performance of the strongly constrained and appropriately normed density functional for solid-state materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Isaacs, Eric B.; Wolverton, Chris

Constructed to satisfy 17 known exact constraints for a semilocal density functional, the strongly constrained and appropriately normed (SCAN) meta-generalized-gradient-approximation functional has shown early promise for accurately describing the electronic structure of molecules and solids. One open question is how well SCAN predicts the formation energy, a key quantity for describing the thermodynamic stability of solid-state compounds. To answer this question, we perform an extensive benchmark of SCAN by computing the formation energies for a diverse group of nearly 1000 crystalline compounds for which experimental values are known. Due to an enhanced exchange interaction in the covalent bonding regime, SCANmore » substantially decreases the formation energy errors for strongly bound compounds, by approximately 50% to 110 meV/atom, as compared to the generalized gradient approximation of Perdew, Burke, and Ernzerhof (PBE). However, for intermetallic compounds, SCAN performs moderately worse than PBE with an increase in formation energy error of approximately 20%, stemming from SCAN's distinct behavior in the weak bonding regime. The formation energy errors can be further reduced via elemental chemical potential fitting. We find that SCAN leads to significantly more accurate predicted crystal volumes, moderately enhanced magnetism, and mildly improved band gaps as compared to PBE. Altogether, SCAN represents a significant improvement in accurately describing the thermodynamics of strongly bound compounds.« less

Vapour-induced solid-state C-H bond activation for the clean synthesis of an organopalladium biothiol sensor.

PubMed

Monas, Andrea; Užarević, Krunoslav; Halasz, Ivan; Kulcsár, Marina Juribašić; Ćurić, Manda

2016-10-27

Room-temperature accelerated aging in the solid state has been applied for atom- and energy-efficient activation of either one or two C-H bonds of azobenzene and methyl orange by palladium(ii) acetate. Organopalladium complexes are prepared in quantitative reactions without potentially harmful side products. Dicyclopalladated methyl orange is water-soluble and is a selective chromogenic biothiol sensor at physiologically-relevant micromolar concentrations in buffered aqueous media.

Intermediate couplings: NMR at the solids-liquids interface

NASA Astrophysics Data System (ADS)

Spence, Megan

2006-03-01

Anisotropic interactions like dipolar couplings and chemical shift anisotropy have long offered solid-state NMR spectroscopists valuable structural information. Recently, solution-state NMR structural studies have begun to exploit residual dipolar couplings of biological molecules in weakly anisotropic solutions. These residual couplings are about 0.1% of the coupling magnitudes observed in the solid state, allowing simple, high-resolution NMR spectra to be retained. In this work, we examine the membrane-associated opioid, leucine enkephalin (lenk), in which the ordering is ten times larger than that for residual dipolar coupling experiments, requiring a combination of solution-state and solid-state NMR techniques. We adapted conventional solid-state NMR techniques like adiabatic cross- polarization and REDOR for use with such a system, and measured small amide bond dipolar couplings in order to determine the orientation of the amide bonds (and therefore the peptide) with respect to the membrane surface. However, the couplings measured indicate large structural rearrangements on the surface and contradict the published structures obtained by NOESY constraints, a reminder that such methods are of limited use in the presence of large-scale dynamics.

Secondary Structures in a Freeze-Dried Lignite Humic Acid Fraction Caused by Hydrogen-Bonding of Acidic Protons with Aromatic Rings.

PubMed

Cao, Xiaoyan; Drosos, Marios; Leenheer, Jerry A; Mao, Jingdong

2016-02-16

A lignite humic acid (HA) was separated from inorganic and non-HA impurities (i.e., aluminosilicates, metals) and fractionated by a combination of dialysis and XAD-8 resin. Fractionation revealed a more homogeneous structure of lignite HA. New and more specific structural information on the main lignite HA fraction is obtained by solid-state nuclear magnetic resonance (NMR) spectroscopy. Quantitative (13)C multiple cross-polarization (multiCP) NMR indicated oxidized phenyl propane structures derived from lignin. MultiCP experiments, conducted on potassium HA salts titrated to pH 10 and pH 12, revealed shifts consistent with carboxylate and phenolate formation, but structural changes associated with enolate formation from aromatic beta keto acids were not detected. Two-dimensional (1)H-(13)C heteronuclear correlation (2D HETCOR) NMR indicated aryl-aliphatic ketones, aliphatic and aromatic carboxyl groups, phenol, and methoxy phenyl ethers. Acidic protons from carboxyl groups in both the lignite HA fraction and a synthetic HA-like polycondensate were found to be hydrogen-bonded with electron-rich aromatic rings. Our results coupled with published infrared spectra provide evidence for the preferential hydrogen bonding of acidic hydrogens with electron-rich aromatic rings rather than adjacent carbonyl groups. These hydrogen-bonding interactions likely result from stereochemical arrangements in primary structures and folding.

X-ray photoelectron spectroscopy and paramagnetic resonance evidence for shock-induced intramolecular bond breaking in some energetic solids

NASA Astrophysics Data System (ADS)

Owens, F. J.; Sharma, J.

1980-03-01

Solid samples of 1,3,5, trinitro 1,3,5, triazacyclohexane (RDX), trinitrotoluene (TNT), and ammonium nitrate were subjected to shock pulses of strength and duration less than the threshold to cause detonation. The recovered shocked samples were studied by x-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). The results of these measurements indicate that the shock pulse either broke or altered the internal bonds of the molecules of the solid. The results of the shock decomposition are compared with measurements of the uv and slow thermal decomposition of these materials using the same experimental techniques.

Electronic structure studies of adsorbate-induced surface reconstructions: oxygen on Rh(1 0 0)

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2004-03-01

Solid-state Fenske-Hall band structure calculations have been used to study the electronic structure and bonding that occur on an "asymmetric" clock reconstructed Rh(1 0 0) surface with a half-monolayer of O atom adsorbates. The displacement of the top-layer Rh atoms on reconstructed O/Rh(1 0 0) is similar to that observed when a half-monolayer of C or N atoms adsorb onto clean Ni(1 0 0). Unlike the five-coordinate C or N adsorbates that adsorb into effectively coplanar sites on the Ni(1 0 0) surface, however, O atoms sit well above the Rh surface plane and occupy three-coordinate adsorption sites. The results of these calculations show that the asymmetric clock reconstruction of O/Rh(1 0 0) increases the negative charge localized on the highly electronegative O atoms and strengthens the O-Rh bonding relative to an unreconstructed surface. This suggests that, in contrast to the C(N)/Ni(1 0 0) clock, which appears to be driven primarily by the restoration of metal-metal bonding, the asymmetric O/Rh(1 0 0) clock reconstruction is driven by the optimization of the O atom bonding environment. Comparisons of the O/Rh(1 0 0) and C(N, O)/Ni(1 0 0) surfaces further indicate that the electronegativity and electron count of the adsorbed species, as well as the electron count and physical size of the metal, all play a role in determining the preferred atomic geometries of these adsorbate-covered transition metal surfaces.

Exploration and exploitation of homologous series of bis(acrylamido)alkanes containing pyridyl and phenyl groups: β-sheet versus two-dimensional layers in solid-state photochemical [2 + 2] reactions.

PubMed

Garai, Mousumi; Biradha, Kumar

2015-09-01

The homologous series of phenyl and pyridyl substituted bis(acrylamido)alkanes have been synthesized with the aim of systematic analysis of their crystal structures and their solid-state [2 + 2] reactivities. The changes in the crystal structures with respect to a small change in the molecular structure, that is by varying alkyl spacers between acrylamides and/or by varying the end groups (phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl) on the C-terminal of the amide, were analyzed in terms of hydrogen-bonding interference (N-H⋯Npy versus N-H⋯O=C) and network geometries. In this series, a greater tendency towards the formation of N-H⋯O hydrogen bonds (β-sheets and two-dimensional networks) over N-H⋯N hydrogen bonds was observed. Among all the structures seven structures were found to have the required alignments of double bonds for the [2 + 2] reaction such that the formations of single dimer, double dimer and polymer are facilitated. However, only four structures were found to exhibit such a solid-state [2 + 2] reaction to form a single dimer and polymers. The two-dimensional hydrogen-bonding layer via N-H⋯O hydrogen bonds was found to promote solid-state [2 + 2] photo-polymerization in a single-crystal-to-single-crystal manner. Such two-dimensional layers were encountered only when the spacer between acryl amide moieties is butyl. Only four out of the 16 derivatives were found to form hydrates, two each from 2-pyridyl and 4-pyridyl derivatives. The water molecules in these structures govern the hydrogen-bonding networks by the formation of an octameric water cluster and one-dimensional zigzag water chains. The trends in the melting points and densities were also analyzed.

Relating hydrogen-bonding interactions with the phase behavior of naproxen/PVP K 25 solid dispersions: evaluation of solution-cast and quench-cooled films.

PubMed

Paudel, Amrit; Nies, Erik; Van den Mooter, Guy

2012-11-05

In this work, we investigated the relationship between various intermolecular hydrogen-bonding (H-bonding) interactions and the miscibility of the model hydrophobic drug naproxen with the hydrophilic polymer polyvinylpyrrolidone (PVP) across an entire composition range of solid dispersions prepared by quasi-equilibrium film casting and nonequilibrium melt quench cooling. The binary phase behavior in solid dispersions exhibited substantial processing method dependence. The solid state solubility of crystalline naproxen in PVP to form amorphous solid dispersions was 35% and 70% w/w naproxen in solution-cast films and quench-cooled films, respectively. However, the presence of a single mixed phase glass transition indicated the amorphous miscibility to be 20% w/w naproxen for the films, beyond which amorphous-amorphous and/or crystalline phase separations were apparent. This was further supported by the solution state interactions data such as PVP globular size distribution and solution infrared spectral profiles. The borderline melt composition showed cooling rate dependence of amorphization. The glass transition and melting point depression profiles of the system were treated with the analytical expressions based on Flory-Huggins mixing theory to interpolate the equilibrium solid solubility. FTIR analysis and subsequent spectral deconvolution revealed composition and miscibility dependent variations in the strength of drug-polymer intermolecular H-bonding. Two types of H-bonded populations were evidenced from 25% w/w and 35% w/w naproxen in solution-cast films and quench-cooled films, respectively, with the higher fraction of strongly H-bonded population in the drug rich domains of phase separated amorphous film compositions and highly drug loaded amorphous quench-cooled dispersions.

Compositional, Atomic and Molecular Analysis in Support of Materials Needs of the U.S. Air Force.

DTIC Science & Technology

1982-09-01

internally hydrogen-bonded monomer in .which the keto group is involved in the hydrogen bond but the acid carbonyl is not. 3 ) 3 - Bromopyruvic Acid...The spectra and structure of 3 - bromopyruvic acid were investigated and compared to those of pyruvic acid. It has been found that the spectra of 3 ...phase, cyclic monomer in dilute solution). The solid state spectra are quite different, however. The solid states spectra of 3 - bromopyruvic acid show a

A corpuscular picture of electrons in chemical bond

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ando, Koji

We introduce a theory of chemical bond with a corpuscular picture of electrons. It employs a minimal set of localized electron wave packets with “floating and breathing” degrees of freedom and the spin-coupling of non-orthogonal valence-bond theory. Its accuracy for describing potential energy curves of chemical bonds in ground and excited states of spin singlet and triplet is examined.

Stopping power beyond the adiabatic approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Caro, M.; Correa, A. A.; Artacho, E.

2017-06-01

Energetic ions traveling in solids deposit energy in a variety of ways, being nuclear and electronic stopping the two avenues in which dissipation is usually treated. This separation between electrons and ions relies on the adiabatic approximation in which ions interact via forces derived from the instantaneous electronic ground state. In a more detailed view, in which non-adiabatic effects are explicitly considered, electronic excitations alter the atomic bonding, which translates into changes in the interatomic forces. In this work, we use time dependent density functional theory and forces derived from the equations of Ehrenfest dynamics that depend instantaneously on themore » time-dependent electronic density. With them we analyze how the inter-ionic forces are affected by electronic excitations in a model of a Ni projectile interacting with a Ni target, a metallic system with strong electronic stopping and shallow core level states. We find that the electronic excitations induce substantial modifications to the inter-ionic forces, which translate into nuclear stopping power well above the adiabatic prediction. Particularly, we observe that most of the alteration of the adiabatic potential in early times comes from the ionization of the core levels of the target ions, not readily screened by the valence electrons.« less

From dense monomer salt crystals to CO2 selective microporous polyimides via solid-state polymerization.

PubMed

Unterlass, Miriam M; Emmerling, Franziska; Antonietti, Markus; Weber, Jens

2014-01-14

Fully aromatic polyimides are synthesized via solid-state polymerization of the corresponding monomer salts. The crystal structure of salts shows strong hydrogen bonding of the reactive groups and thereby paves the way for solid-state transformations. The polycondensation yields copies of the initial salt crystallite habits, accompanied by the development of a porosity especially suited for CO2.

Core-level photoabsorption study of defects and metastable bonding configurations in boron nitride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jimenez, I.; Jankowski, A.F.; Terminello, L.J.

1997-04-01

Boron nitride is an interesting material for technological applications and for fundamental solid state physics investigations. It is a compound isoelectronic with carbon and, like carbon can possess sp{sup 2} and sp{sup 3} bonded phases resembling graphite and diamond. BN crystallizes in the sp{sup 2}-bonded hexagonal (h-BN), rhombohedral (r-BN) and turbostratic phases, and in the sp{sup 3}-bonded cubic (c-BN) and wurtzite (w-BN) phases. A new family of materials is obtained when replacing C-C pairs in graphite with isoelectronic B-N pairs, resulting in C{sub 2}BN compounds. Regarding other boron compounds, BN is exceptional in the sense that it has standard two-centermore » bonds with conventional coordination numbers, while other boron compounds (e.g. B{sub 4}C) are based on the boron icosahedron unit with three-center bonds and high coordination numbers. The existence of several allotropic forms and fullerene-like structures for BN suggests a rich variety of local bonding and poses the questions of how this affects the local electronic structure and how the material accommodates the stress induced in the transition regions between different phases. One would expect point defects to play a crucial role in stress accommodation, but these must also have a strong influence in the electronic structure, since the B-N bond is polar and a point defect will thus be a charged structure. The study of point defects in relationship to the electronic structure is of fundamental interest in these materials. Recently, the authors have shown that Near-Edge X-ray Absorption Fine Structure (NEXAFS) is sensitive to point defects in h-BN, and to the formation of metastable phases even in amorphous materials. This is significant since other phase identification techniques like vibrational spectroscopies or x-ray diffraction yield ambiguous results for nanocrystalline and amorphous samples. Serendipitously, NEXAFS also combines chemical selectivity with point defect sensitivity.« less

The shear modulus of metastable amorphous solids with strong central and bond-bending interactions

NASA Astrophysics Data System (ADS)

Zaccone, Alessio

2009-07-01

We derive expressions for the shear modulus of deeply quenched, glassy solids, in terms of a Cauchy-Born free energy expansion around a rigid (quenched) reference state, following the approach due to Alexander (1998 Phys. Rep. 296 65). Continuum-limit explicit expressions of the shear modulus are derived starting from the microscopic Hamiltonians of central and bond-bending interactions. The applicability of the expressions to dense covalent glasses as well as colloidal glasses involving strongly attractive or adhesive bonds is discussed.

NO3- anions can act as Lewis acid in the solid state

NASA Astrophysics Data System (ADS)

Bauzá, Antonio; Frontera, Antonio; Mooibroek, Tiddo J.

2017-02-01

Identifying electron donating and accepting moieties is crucial to understanding molecular aggregation, which is of pivotal significance to biology. Anions such as NO3- are typical electron donors. However, computations predict that the charge distribution of NO3- is anisotropic and minimal on nitrogen. Here we show that when the nitrate's charge is sufficiently dampened by resonating over a larger area, a Lewis acidic site emerges on nitrogen that can interact favourably with electron rich partners. Surveys of the Cambridge Structural Database and Protein Data Bank reveal geometric preferences of some oxygen and sulfur containing entities around a nitrate anion that are consistent with this `π-hole bonding' geometry. Computations reveal donor-acceptor orbital interactions that confirm the counterintuitive Lewis π-acidity of nitrate.

Role of Secondary Low-Energy Electrons in the Concomitant Chemoradiation Therapy of Cancer

NASA Astrophysics Data System (ADS)

Zheng, Yi; Hunting, Darel J.; Ayotte, Patrick; Sanche, Léon

2008-05-01

Solid films of DNA with and without the chemotherapeutic agent cisplatin bonded to guanine were bombarded with electrons of 1, 10, 100, and 60 000 eV causing single and double strand breaks. In the presence of cisplatin this damage was increased by factors varying from 1.3 to 4.4 owing to an increase in bond dissociation triggered by the formation of transient anions. This mechanism may lie at the basis of the efficiency of concomitant cisplatin-radiation therapy.

MN15-L: A New Local Exchange-Correlation Functional for Kohn-Sham Density Functional Theory with Broad Accuracy for Atoms, Molecules, and Solids.

PubMed

Yu, Haoyu S; He, Xiao; Truhlar, Donald G

2016-03-08

Kohn-Sham density functional theory is widely used for applications of electronic structure theory in chemistry, materials science, and condensed-matter physics, but the accuracy depends on the quality of the exchange-correlation functional. Here, we present a new local exchange-correlation functional called MN15-L that predicts accurate results for a broad range of molecular and solid-state properties including main-group bond energies, transition metal bond energies, reaction barrier heights, noncovalent interactions, atomic excitation energies, ionization potentials, electron affinities, total atomic energies, hydrocarbon thermochemistry, and lattice constants of solids. The MN15-L functional has the same mathematical form as a previous meta-nonseparable gradient approximation exchange-correlation functional, MN12-L, but it is improved because we optimized it against a larger database, designated 2015A, and included smoothness restraints; the optimization has a much better representation of transition metals. The mean unsigned error on 422 chemical energies is 2.32 kcal/mol, which is the best among all tested functionals, with or without nonlocal exchange. The MN15-L functional also provides good results for test sets that are outside the training set. A key issue is that the functional is local (no nonlocal exchange or nonlocal correlation), which makes it relatively economical for treating large and complex systems and solids. Another key advantage is that medium-range correlation energy is built in so that one does not need to add damped dispersion by molecular mechanics in order to predict accurate noncovalent binding energies. We believe that the MN15-L functional should be useful for a wide variety of applications in chemistry, physics, materials science, and molecular biology.

Solid state diffusion bonded damascus steel and its role within custom knifemaking

NASA Astrophysics Data System (ADS)

Horne, Grace

This thesis describes practice-based research that applied new technology to an ancient process of laminating metals for blades and explored the application of the new possibilities to a craft context. This research built on work by Ferguson on solid-state diffusion bonded Mokume Gane by moving from metal combinations suitable for vessel-making to metal combinations suitable for knife-making. Solid-state diffusion bonding1 is well established within industry. This research applied the industrial process to a craft based setting, and explored the bonding of metals with very dissimilar properties; ferrous and non-ferrous metals, hard and soft, high and low melting points. The materials included in this study were stainless and carbon steel, iron, nickel, vanadium and silver. The characteristics of the carbon steel and silver laminates were explored further by knifemakers, including heat-treating, forging, machining, flex and pattern creation. Analysis of the knifemakers feedback showed that the steel/silver metal was of interest to makers who machined or ground their blades rather than relying on forging.The study used a multi-method approach. The two broad researchquestions were; Is it possible to make a damascus steel using solid-state diffusion bonding that would be impossible using traditional techniques? And would the results be worth the work? Although carried out mainly within a craft setting the investigation is highly metallurgical in subject matter. The methodology was developed to reflect this crossing of subject areas and answer the research questions outlined above. The results are communicated through this thesis and a documentation of an exhibition of the work produced by the researcher and other selected knifemakers.The research produced a coherent composite of steel and pure silver and successfully produced a number of knives using the material.

Optical properties of Si and Ge nanocrystals: Parameter-free calculations

NASA Astrophysics Data System (ADS)

Ramos, L. E.; Weissker, H.-Ch.; Furthmüller, J.; Bechstedt, F.

2005-12-01

The cover picture of the current issue refers to the Edi-tor's Choice article of Ramos et al. [1]. The paper gives an overview of the electronic and optical properties of silicon and germanium nanocrystals determined by state-of-the-art ab initio methods. Nanocrystals have promising applications in opto-electronic devices, since they can be used to confine electrons and holes and facilitate radiative recombination. Since meas-urements for single nanoparticles are difficult to make, ab initio theoretical investigations become important to understand the mechanisms of luminescence.The cover picture shows nanocrystals of four sizes with tetrahedral coordination whose dangling bonds at the surface are passivated with hydrogen. As often observed in experiments, the nanocrystals are not perfectly spherical, but contain facets. Apart from the size of the nanocrystals, which determines the quantum confinement, the way their dangling bonds are passivated is relevant for their electronic and optical properties. For instance, the passivation with hydroxyls reduces the quantum confine-ment. On the other hand, the oxidation of the silicon nanocrys-tals increases the quantum confinement and reduces the effect of single surface terminations on the gap. Due to the oscillator strengths of the lowest-energy optical transitions, Ge nanocrys-tals are in principle more suitable for opto-electronic applica-tions than Si nanocrystals.The first author, Luis E. Ramos, is a postdoc at the Institute of Solid-State Physics and Optics (IFTO), Friedrich-Schiller University Jena, Germany. He investigates electronic and optical properties of semiconductor nanocrystallites and is a member of the European Network of Excellence NANO-QUANTA and of the European Theoretical Spectroscopy Facility (ETSF).

The first experimental investigation of the KLL Auger spectrum of Ni generated in the electron capture decay of radioactive 64Cu in a solid state matrix

NASA Astrophysics Data System (ADS)

Inoyatov, A. Kh.; Perevoshchikov, L. L.; Kovalík, A.; Filosofov, D. V.; Gorozhankin, V. M.; Ryšavý, M.

2012-09-01

The KLL Auger spectrum of Ni generated in the electron capture decay of radioactive 64Cu in a solid state matrix was measured for the first time using a combined electrostatic electron spectrometer adjusted to a 7 eV instrumental resolution. Energies and relative intensities of the all nine basic spectrum components were determined and compared with data obtained from X-ray induced spectra of metallic Ni and with theoretical results as well. Absolute energy of 6562.5 ± 1.3 eV (related to the Fermi level) measured for the dominant KL2L3(1D2) than a value obtained from the X-ray induced spectra which is probably caused by the effects of chemical bonding and physico-chemical environment. Moreover, it is higher by 20.4 eV (16 σ) than a prediction of the semi-empirical calculations by Larkins which indicates an influence of the "atomic structure effect" on absolute energies of the Auger transitions following the electron capture decay and, possibly, some imperfections in the calculations. Good agreement of the measured and predicted KL1L2(3P0/1P1) transition intensity ratios indicates perceptible influence of the relativistic effects on the KLL Auger spectrum even at Z = 28.

Fundamental tribological properties of ceramics

NASA Technical Reports Server (NTRS)

Buckley, D. H.; Miyoshi, K.

1985-01-01

When a ceramic is brought into contact with itself, another ceramic, or a metal, strong bond forces can develop between the materials. Adhesion between a ceramic and itself or another solid are discussed from a theoretical consideration of the nature of the surfaces and experimentally by relating bond forces to the interface resulting from solid state contact. Elastic, plastic, and fracture behavior of ceramics in solid-state contact are discussed as they relate to friction and wear. The contact load necessary to initiate fracture in ceramics is shown to be appreciably reduced with tangential motion. Both friction and wear of ceramics are anisotropic and relate to crystal structure as with metals. Both free energy of oxide formation and the d valence bond character of metals are related to the friction and wear characteristics for metals in contact with ceramics. Lubrication is found to increase the critical load necessary to initiate fracture of ceramics with sliding or rubbing contact.

Chemical Bonding and Thermodynamics in Superconductivity and Superfluidity

NASA Astrophysics Data System (ADS)

Love, Peter

2012-05-01

Superconductivity and superfluidity are physical states that occur in a variety of chemical and physical systems. These physical states share a common type of real, or virtual, chemical bonding. Each of the systems discussed herein contain at least one real, or effective, coordinate covalent bond. This is formed from an electron pair donor species and an electron pair acceptor species. When the electronegativity difference between the electron pair donor and acceptor species is sufficiently small, the resultant coordinate covalent bond density can be substantial. If delocalized, this bond density can result in a significant increase in the electron pair orbital volume relative to that of the parent species, and an increase in the valence shell orbital entropy. In terms of the normalized Gibbs-Helmholtz equation, this results in a concomitant decrease in free energy of the delocalized electronic system. A decrease in free energy to negative values can support a boson state, and superconductivity. A clear example of these principles is the occurrence of superconductivity in the ceramic material, MgB2. These generalizations apply to superconducting elements, high temperature superconductors, superconducting alloys, and equivalently to superfluid 4He.

Study of Diffusion Bonding of 45 Steel through the Compacted Nickel Powder Layer

NASA Astrophysics Data System (ADS)

Zeer, G. M.; Zelenkova, E. G.; Temnykh, V. I.; Tokmin, A. M.; Shubin, A. A.; Koroleva, Yu. P.; Mikheev, A. A.

2018-02-01

The microstructure of the transition zone and powder spacer, the concentration distribution of chemical elements over the width of the diffusion-bonded joint, and microhardness of 45 steel-compacted Ni powder spacer-45 steel layered composites formed by diffusion bonding have been investigated. It has been shown that the relative spacer thickness χ < 0.06 is optimal for obtaining a high-quality joint has been formed under a compacting pressure of 500 MPa. The solid-state diffusion bonding is accompanied by sintering the nickel powder spacer and the formation of the transition zone between the spacer and steel. The transition zone consists of solid solution of nickel in the α-Fe phase and ordered solid solution of iron in nickel (FeNi3).

Acid/base-regulated reversible electron transfer disproportionation of N–N linked bicarbazole and biacridine derivatives† †Electronic supplementary information (ESI) available: Experimental information, synthesis and characterization data, NMR spectra, solid state NMR data, X-ray data, ESR spectra, UV-Vis-NIR spectra, fluorescence spectra, kinetic experiments, theoretical calculations, Tables S1–S8, Scheme S1, Fig. S1–12, References. CCDC 1025063, 1038914, 1049677 and 1040722. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00946d

PubMed Central

Pandit, Palash; Yamamoto, Koji; Nakamura, Toshikazu; Nishimura, Katsuyuki; Kurashige, Yuki; Yanai, Takeshi; Nakamura, Go; Masaoka, Shigeyuki; Furukawa, Ko; Yakiyama, Yumi; Kawano, Masaki

2015-01-01

Regulation of electron transfer on organic substances by external stimuli is a fundamental issue in science and technology, which affects organic materials, chemical synthesis, and biological metabolism. Nevertheless, acid/base-responsive organic materials that exhibit reversible electron transfer have not been well studied and developed, owing to the difficulty in inventing a mechanism to associate acid/base stimuli and electron transfer. We discovered a new phenomenon in which N–N linked bicarbazole (BC) and tetramethylbiacridine (TBA) derivatives undergo electron transfer disproportionation by acid stimulus, forming their stable radical cations and reduced species. The reaction occurs through a biradical intermediate generated by the acid-triggered N–N bond cleavage reaction of BC or TBA, which acts as a two electron acceptor to undergo electron transfer reactions with two equivalents of BC or TBA. In addition, in the case of TBA the disproportionation reaction is highly reversible through neutralization with NEt3, which recovers TBA through back electron transfer and N–N bond formation reactions. This highly reversible electron transfer reaction is possible due to the association between the acid stimulus and electron transfer via the acid-regulated N–N bond cleavage/formation reactions which provide an efficient switching mechanism, the ability of the organic molecules to act as multi-electron donors and acceptors, the extraordinary stability of the radical species, the highly selective reactivity, and the balance of the redox potentials. This discovery provides new design concepts for acid/base-regulated organic electron transfer systems, chemical reagents, or organic materials. PMID:29218181

Near-infrared analysis of hydrogen-bonding in glass- and rubber-state amorphous saccharide solids.

PubMed

Izutsu, Ken-ichi; Hiyama, Yukio; Yomota, Chikako; Kawanishi, Toru

2009-01-01

Near-infrared (NIR) spectroscopic analysis of noncrystalline polyols and saccharides (e.g., glycerol, sorbitol, maltitol, glucose, sucrose, maltose) was performed at different temperatures (30-80 degrees C) to elucidate the effect of glass transition on molecular interaction. Transmission NIR spectra (4,000-12,000 cm(-1)) of the liquids and cooled-melt amorphous solids showed broad absorption bands that indicate random configuration of molecules. Heating of the samples decreased an intermolecular hydrogen-bonding OH vibration band intensity (6,200-6,500 cm(-1)) with a concomitant increase in a free and intramolecular hydrogen-bonding OH group band (6,600-7,100 cm(-1)). Large reduction of the intermolecular hydrogen-bonding band intensity at temperatures above the glass transition (T(g)) of the individual solids should explain the higher molecular mobility and lower viscosity in the rubber state. Mixing of the polyols with a high T(g) saccharide (maltose) or an inorganic salt (sodium tetraborate) shifted both the glass transition and the inflection point of the hydrogen-bonding band intensity to higher temperatures. The implications of these results for pharmaceutical formulation design and process monitoring (PAT) are discussed.

Positronium formation studies in crystalline molecular complexes: Triphenylphosphine oxide - Acetanilide

NASA Astrophysics Data System (ADS)

Oliveira, F. C.; Denadai, A. M. L.; Guerra, L. D. L.; Fulgêncio, F. H.; Windmöller, D.; Santos, G. C.; Fernandes, N. G.; Yoshida, M. I.; Donnici, C. L.; Magalhães, W. F.; Machado, J. C.

2013-04-01

Hydrogen bond formation in the triphenylphosphine oxide (TPPO), acetanilide (ACN) supramolecular heterosynton system, named [TPPO0.5·ACN0.5], has been studied by Positron Annihilation Lifetime Spectroscopy (PALS) and supported by several analytical techniques. In toluene solution, Isothermal Titration Calorimetry (ITC) presented a 1:1 stoichiometry and indicated that the complexation process is driven by entropy, with low enthalpy contribution. X-ray structure determination showed the existence of a three-dimensional network of hydrogen bonds, allowing also the confirmation of the existence of a 1:1 crystalline molecular complex in solid state. The results of thermal analysis (TGA, DTA and DSC) and FTIR spectroscopy showed that the interactions in the complex are relatively weaker than those found in pure precursors, leading to a higher positronium formation probability at [TPPO0.5·ACN0.5]. These weak interactions in the complex enhance the possibility of the n- and π-electrons to interact with positrons and consequently, the probability of positronium formation is higher. Through the present work is shown that PALS is a sensible powerful tool to investigate intermolecular interactions in solid heterosynton supramolecular systems.

The base pairs and hydrogen-bond network of the 5-Amino-8-(β-L-furanosyl)pyrimido[4,5-d]pyrimidine-2,4(3H,8H)-dione

NASA Astrophysics Data System (ADS)

Meng, Liying; Zhou, Xinglong; Chai, Yingying; Li, Changfu; Liu, Jiang; Chen, Qianming; Li, Weimin; Zhao, Hang; He, Yang

2017-11-01

Supramolecular morphogenesis is a fundamentally important process in fields ranging from structural biology to materials chemistry. Our previous works demonstrated that the sugar structural parameters can decree the supramolecular morphogenesis of Janus-type nucleosides. However, the chiral effect in this regards has not yet been tackled. Here, the self-associated superstructures of J-AT L-ribonucleoside (J-AT-L, 1) was investigated in both solid state and solution by single-crystal X-ray analysis and scanning electron microscope (SEM). The results indicate a high mirror symmetry in both monomeric level and hydrogen bond patterns in solid state between compound 1 and its enantiomeric counterpart J-AT D-ribonucleoside (J-AT-D, 2), except the distinct interactions between A-B and B-B conformers. The SEM experiments display that J-AT-L forms a porous microsphere-flower-like superstructure, instead of a radial-petal-flower-like superstructure of the D-enantiomer (2), which could be attributed to the different interactions of A-B and B-B conformers among these two series. This study provides for the first time the evidences of how the chiral information of the monomeric J-AT nucleosides is translated into the diverse supramolecular morphologies.

Directly and indirectly detected through-bond heteronuclear correlation solid-state NMR spectroscopy under fast MAS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mao, Kanmi; Pruski, Marek

Two-dimensional through-bond {sup 1}H({sup 13}C) solid-state NMR experiments utilizing fast magic angle spinning (MAS) and homonuclear multipulse {sup 1}H decoupling are presented. Remarkable efficiency of polarization transfer can be achieved at MAS rates exceeding 40 kHz, which is instrumental in these measurements. Schemes utilizing direct and indirect detection of heteronuclei are compared in terms of resolution and sensitivity. A simple procedure for optimization of {sup 1}H homonuclear decoupling sequences under these conditions is proposed. The capabilities of these techniques were confirmed on two naturally abundant solids, tripeptide N-formyl-l-methionyl-l-leucyl-l-phenylalanine (f-MLF-OH) and brown coal.

Directly and indirectly detected through-bond heteronuclear correlation solid-state NMR spectroscopy under fast MAS

NASA Astrophysics Data System (ADS)

Mao, Kanmi; Pruski, Marek

2009-12-01

Two-dimensional through-bond 1H{ 13C} solid-state NMR experiments utilizing fast magic angle spinning (MAS) and homonuclear multipulse 1H decoupling are presented. Remarkable efficiency of polarization transfer can be achieved at MAS rates exceeding 40 kHz, which is instrumental in these measurements. Schemes utilizing direct and indirect detection of heteronuclei are compared in terms of resolution and sensitivity. A simple procedure for optimization of 1H homonuclear decoupling sequences under these conditions is proposed. The capabilities of these techniques were confirmed on two naturally abundant solids, tripeptide N- formyl- L-methionyl- L-leucyl- L-phenylalanine (f-MLF-OH) and brown coal.

Solid-state voltammetry-based electrochemical immunosensor for Escherichia coli using graphene oxide-Ag nanoparticle composites as labels.

PubMed

Jiang, Xiaochun; Chen, Kun; Wang, Jing; Shao, Kang; Fu, Tao; Shao, Feng; Lu, Donglian; Liang, Jiangong; Foda, M Frahat; Han, Heyou

2013-06-21

A new electrochemical immunosensor based on solid-state voltammetry was fabricated for the detection of Escherichia coli (E. coli) by using graphene oxide-Ag nanoparticle composites (P-GO-Ag) as labels. To construct the platform, Au nanoparticles (AuNPs) were first self-assembled on an Au electrode surface through cysteamine and served as an effective matrix for antibody (Ab) attachment. Under a sandwich-type immunoassay format, the analyte and the probe (P-GO-Ag-Ab) were successively captured onto the immunosensor. Finally, the bonded AgNPs were detected through a solid-state redox process in 0.2 M of KCl solution. Combining the advantages of the high-loading capability of graphene oxide with promoted electron-transfer rate of AuNPs, this immunosensor produced a 26.92-fold signal enhancement compared with the unamplified protocol. Under the optimal conditions, the immunosensor exhibited a wide linear dependence on the logarithm of the concentration of E. coli ranging from 50 to 1.0 × 10(6) cfu mL(-1) with a detection limit of 10 cfu mL(-1). Moreover, as a practical application, the proposed immunosensor was used to monitor E. coli in lake water with satisfactory results.

Mathematical analysis of compressive/tensile molecular and nuclear structures

NASA Astrophysics Data System (ADS)

Wang, Dayu

Mathematical analysis in chemistry is a fascinating and critical tool to explain experimental observations. In this dissertation, mathematical methods to present chemical bonding and other structures for many-particle systems are discussed at different levels (molecular, atomic, and nuclear). First, the tetrahedral geometry of single, double, or triple carbon-carbon bonds gives an unsatisfying demonstration of bond lengths, compared to experimental trends. To correct this, Platonic solids and Archimedean solids were evaluated as atoms in covalent carbon or nitrogen bond systems in order to find the best solids for geometric fitting. Pentagonal solids, e.g. the dodecahedron and icosidodecahedron, give the best fit with experimental bond lengths; an ideal pyramidal solid which models covalent bonds was also generated. Second, the macroscopic compression/tension architectural approach was applied to forces at the molecular level, considering atomic interactions as compressive (repulsive) and tensile (attractive) forces. Two particle interactions were considered, followed by a model of the dihydrogen molecule (H2; two protons and two electrons). Dihydrogen was evaluated as two different types of compression/tension structures: a coaxial spring model and a ring model. Using similar methods, covalent diatomic molecules (made up of C, N, O, or F) were evaluated. Finally, the compression/tension model was extended to the nuclear level, based on the observation that nuclei with certain numbers of protons/neutrons (magic numbers) have extra stability compared to other nucleon ratios. A hollow spherical model was developed that combines elements of the classic nuclear shell model and liquid drop model. Nuclear structure and the trend of the "island of stability" for the current and extended periodic table were studied.

Preparation and characterization of host-guest system between inosine and β-cyclodextrin through inclusion mode

NASA Astrophysics Data System (ADS)

Prabu, Samikannu; Sivakumar, Krishnamurty; Swaminathan, Meenakshisundaram; Rajamohan, Rajaram

2015-08-01

Inosine is a nucleoside that is formed when hypoxanthine is attached to a ribose ring (also known as a ribofuranose) via a β-N9-glycosidic bond. Inosine is commonly found in tRNAs. Inosine (INS) has been used widely as an antiviral drug. The inclusion complex of INS with β-CDx in solution phase is studied by ground and excited state with UV-visible and fluorescence spectroscopy, respectively. A binding constant and stoichiometric ratio between INS and β-CDx are calculated by BH equation. The lifetime and relative amplitude of INS is increases with increasing the concentrations of β-CDx, confirms the formation of inclusion complex in liquid state. The solid complexes are prepared by kneading method (KM) and co-precipitation method (CP). The solid complex is characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and differential scanning colorimetry (DSC). CP method gives the solid product with good yield than that of physical mixture and KM method. The structure of complex is proposed based on the study of Patch - Dock server.

Dispersion Corrected Structural Properties and Quasiparticle Band Gaps of Several Organic Energetic Solids.

PubMed

Appalakondaiah, S; Vaitheeswaran, G; Lebègue, S

2015-06-18

We have performed ab initio calculations for a series of energetic solids to explore their structural and electronic properties. To evaluate the ground state volume of these molecular solids, different dispersion correction methods were accounted in DFT, namely the Tkatchenko-Scheffler method (with and without self-consistent screening), Grimme's methods (D2, D3(BJ)), and the vdW-DF method. Our results reveal that dispersion correction methods are essential in understanding these complex structures with van der Waals interactions and hydrogen bonding. The calculated ground state volumes and bulk moduli show that the performance of each method is not unique, and therefore a careful examination is mandatory for interpreting theoretical predictions. This work also emphasizes the importance of quasiparticle calculations in predicting the band gap, which is obtained here with the GW approximation. We find that the obtained band gaps are ranging from 4 to 7 eV for the different compounds, indicating their insulating nature. In addition, we show the essential role of quasiparticle band structure calculations to correlate the gap with the energetic properties.

Effect of Bonding Time on Interfacial Reaction and Mechanical Properties of Diffusion-Bonded Joint Between Ti-6Al-4V and 304 Stainless Steel Using Nickel as an Intermediate Material

NASA Astrophysics Data System (ADS)

Thirunavukarasu, Gopinath; Kundu, Sukumar; Mishra, Brajendra; Chatterjee, Subrata

2014-04-01

In the current study, solid-state diffusion bonding between Ti-6Al-4V (TiA) and 304 stainless steel (SS) using pure nickel (Ni) of 200- μm thickness as an intermediate material was carried out in vacuum. Uniaxial compressive pressure and temperature were kept at 4 MPa and 1023 K (750 °C), respectively, and the bonding time was varied from 30 to 120 minutes in steps of 15 minutes. Scanning electron microscopy images, in backscattered electron mode, revealed the layerwise Ti-Ni-based intermetallics like either Ni3Ti or both Ni3Ti and NiTi at titanium alloy-nickel (TiA/Ni) interface, whereas nickel-stainless steel (Ni/SS) interface was free from intermetallic phases for all the joints. Chemical composition of the reaction layers was determined by energy dispersive spectroscopy (SEM-EDS) and confirmed by X-ray diffraction study. Maximum tensile strength of ~382 MPa along with ~3.7 pct ductility was observed for the joints processed for 60 minutes. It was found that the extent of diffusion zone at Ni/SS interface was greater than that of TiA/Ni interface. From the microhardness profile, fractured surfaces, and fracture path, it was demonstrated that the failure of the joints was initiated and propagated apparently at TiA/Ni interface near Ni3Ti intermetallic for bonding time less than 90 minutes, and through Ni for bonding time 90 minutes and greater.

Palladium complexes with simple iminopyridines as catalysts for polyketone synthesis.

PubMed

Rosar, V; Dedeic, D; Nobile, T; Fini, F; Balducci, G; Alessio, E; Carfagna, C; Milani, B

2016-10-07

Four iminopyridines (N-N') differing in the nature of the substituents on the iminic carbon and on the ortho positions of the aryl ring (H or CH3) on the iminic nitrogen were used for the synthesis of neutral and monocationic palladium(ii) complexes of general formulae [Pd(CH3)Cl(N-N')] and [Pd(CH3)(NCCH3)(N-N')][PF6]. The detailed NMR characterization in solution highlighted that: (i) for both series of complexes, the Pd-CH3 signal is progressively shifted to a lower frequency on increasing the number of methyl groups on the ligand skeleton; (ii) for the neutral derivatives, the chemical shift of the (15)N NMR signals, determined through {(1)H,(15)N}-HMBC spectra, is significantly affected by the coordination to palladium; (iii) the coordination induced shift (CIS) of the nitrogen atom trans to the CH3 ligand is smaller than the other. The structure in the solid state for the neutral derivatives with all the four ligands was solved, pointing out that: (iv) the Pd-C bond distance increases with the basicity of the nitrogen-donor ligand; (v) the Pd-N bond distance correlates well with the CIS value. The combining of the solution and solid state structural features allows stating that: (vi) the Pd-CH3 singlet is a good probe for the electron donor capability of the ligand; (vii) the CIS value might be used as a probe for the strength of the Pd-N bond. All monocationic complexes generated active catalysts for the CO/vinyl arene copolymerization, leading to prevailingly syndiotactic polyketones. The catalyst performances, both in terms of catalyst productivity and polymer molecular weight, correlate well with the precatalyst structural features.

Bonding structure in amorphous carbon nitride: A spectroscopic and nuclear magnetic resonance study

NASA Astrophysics Data System (ADS)

Sánchez-López, J. C.; Donnet, C.; Lefèbvre, F.; Fernández-Ramos, C.; Fernández, A.

2001-07-01

Since the prediction of Liu and Cohen [Science 245, 841 (1989)] of the potential extraordinary mechanical properties of crystalline β-C3N4, many authors have attempted its synthesis. However, in most cases, the obtained materials are amorphous phases with a complex bonding structure. Their characterization is complicated due to the absence of a reference compound, the lack of long-range order, and the poor knowledge about their bonding structure. In this article, we present 1H, 13C, and 15N solid-state nuclear magnetic resonance (NMR) measurements for the determination of the bonding types in amorphous CNx films. NMR measurements do not require long-range order and are able to clearly identify the signals from the sp2- and sp3-bonded phases. The analysis of the data obtained by other characterization techniques, such as infrared spectroscopy, x-ray photoelectron spectroscopy, electron energy-loss spectroscopy, and x-ray absorption near-edge spectroscopy on the same sample, based on the information acquired by NMR, enables the description of a structure model for the studied amorphous-CNx phase prepared by dc-magnetron sputtering and to revise the interpretation found in the literature.

Alloying effects on superionic conductivity in lithium indium halides for all-solid-state batteries

NASA Astrophysics Data System (ADS)

Zevgolis, Alysia; Wood, Brandon C.; Mehmedović, Zerina; Hall, Alex T.; Alves, Thomaz C.; Adelstein, Nicole

2018-04-01

Alloying of anions is a promising engineering strategy for tuning ionic conductivity in halide-based inorganic solid electrolytes. We explain the alloying effects in Li3InBr6-xClx, in terms of strain, chemistry, and microstructure, using first-principles molecular dynamics simulations and electronic structure analysis. We find that strain and bond chemistry can be tuned through alloying and affect the activation energy and maximum diffusivity coefficient. The similar conductivities of the x = 3 and x = 6 compositions can be understood by assuming that the alloy separates into Br-rich and Cl-rich regions. Phase-separation increases diffusivity at the interface and in the expanded Cl-region, suggesting microstructure effects are critical. Similarities with other halide superionic conductors are highlighted.

Combination of large and small basis sets in electronic structure calculations on large systems

NASA Astrophysics Data System (ADS)

Røeggen, Inge; Gao, Bin

2018-04-01

Two basis sets—a large and a small one—are associated with each nucleus of the system. Each atom has its own separate one-electron basis comprising the large basis set of the atom in question and the small basis sets for the partner atoms in the complex. The perturbed atoms in molecules and solids model is at core of the approach since it allows for the definition of perturbed atoms in a system. It is argued that this basis set approach should be particularly useful for periodic systems. Test calculations are performed on one-dimensional arrays of H and Li atoms. The ground-state energy per atom in the linear H array is determined versus bond length.

Strength design of Zr(x)Ti(x)Hf(x)Nb(x)Mo(x) alloys based on empirical electron theory of solids and molecules

NASA Astrophysics Data System (ADS)

Li, Y. K.; Chen, Y. W.; Cheng, X. W.; Wu, C.; Cheng, B.

2018-05-01

In this paper, the valence electron structure parameters of Zr(x)Ti(x)Hf(x)Nb(x)Mo(x) alloys were calculated based on the empirical electron theory of solids and molecules (EET), and their performance through these parameters were predicted. Subsequently, the alloys with special valence electron structure parameters were prepared byarc melting. The hardness and high-temperature mechanical properties were analyzed to verify the prediction. Research shows that the influence of shared electron number nA on the strongest bond determines the strength of these alloys and the experiments are consistent with the theoretical prediction.

Diffusion bonding aeroengine components

NASA Astrophysics Data System (ADS)

Fitzpatrick, G. A.; Broughton, T.

1988-10-01

The use of diffusion bonding processes at Rolls-Royce for the manufacture of titanium-alloy aircraft engine components and structures is described. A liquid-phase diffusion bonding process called activated diffusion bonding has been developed for the manufacture of the hollow titanium wide chord fan blade. In addition, solid-state diffusion bonding is being used in the manufacture of hollow vane/blade airfoil constructions mainly in conjunction with superplastic forming and hot forming techniques.

Solid-state radioluminescent compositions

DOEpatents

Clough, Roger L.; Gill, John T.; Hawkins, Daniel B.; Renschler, Clifford L.; Shepodd, Timothy J.; Smith, Henry M.

1991-01-01

A solid state radioluminescent composition for light source comprises an optically clear polymer organic matrix containing tritiated organic materials and dyes capable of "red" shifting primary scintillation emissions from the polymer matrix. The tritiated organic materials are made by reducing, with tritium, an unsaturated organic compound that prior to reduction contains olefinic or alkynylic bonds.

Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erickson, Karla A.; Lichtscheidl, Alejandro G.; Monreal, Marisa Jennifer

The terminal actinide fluoride bonds in (C 5Me 5) 2ThF 2(py) (py = pyridine) and (C 5Me 5) 2UF 2(O=PR 3) (R = Me, Ph) react with two equivalents of Me 3SiN 3 in toluene to form the polymeric thorium bis(azide), [(C 5Me 5) 2Th(N 3)2] ∞, and a new class of monometallic uranium bis(azide) complexes, (C 5Me 5) 2U(N 3)2(O=PR 3), respectively. Full characterization of the novel complexes (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2UF 2(O=PR 3) are reported, including the solid-state structures of (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2U(N 3) 2(O=PPhmore » 3). Lastly, electronic absorption spectral data are also reported for (C 5Me 5) 2AnF 2(py) (An = Th, U) and (C 5Me 5) 2U(N 3) 2(O=PR 3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.« less

Exploiting the Reactivity of Actinide Fluoride Bonds for the Synthesis of a New Class of Bis(azide) Uranium Complexes

DOE PAGES

Erickson, Karla A.; Lichtscheidl, Alejandro G.; Monreal, Marisa Jennifer; ...

2017-11-04

The terminal actinide fluoride bonds in (C 5Me 5) 2ThF 2(py) (py = pyridine) and (C 5Me 5) 2UF 2(O=PR 3) (R = Me, Ph) react with two equivalents of Me 3SiN 3 in toluene to form the polymeric thorium bis(azide), [(C 5Me 5) 2Th(N 3)2] ∞, and a new class of monometallic uranium bis(azide) complexes, (C 5Me 5) 2U(N 3)2(O=PR 3), respectively. Full characterization of the novel complexes (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2UF 2(O=PR 3) are reported, including the solid-state structures of (C 5Me 5) 2ThF 2(py) and (C 5Me 5) 2U(N 3) 2(O=PPhmore » 3). Lastly, electronic absorption spectral data are also reported for (C 5Me 5) 2AnF 2(py) (An = Th, U) and (C 5Me 5) 2U(N 3) 2(O=PR 3) to confirm metal oxidation state and enable elucidation of the fluoride and azide ligand bonding in these complexes.« less

Tribological properties of surfaces

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1978-01-01

The real area of contact between two solid surfaces is only a small portion of the apparent area. Deformation of these areas can result in solid state contact through surface films. For clean solid to solid contact strong adhesive bonding occurs across the interface. Under these conditions many properties of the solid such as the metallurgical and chemical nature of metals can influence adhesion, friction, and wear behavior. The presence of gases, liquids, and solid films on the surface of solids alter markedly tribological characteristics. These surface films can also considerably change the mechanical effects of solid state contact on bulk material behavior.

C sbnd H…F hydrogen bonds as the organising force in F-substituted α-phenyl cinnamic acid aggregates studied by the combination of FTIR spectroscopy and computations

NASA Astrophysics Data System (ADS)

Tolnai, B.; Kiss, J. T.; Felföldi, K.; Pálinkó, I.

2009-04-01

Various F-substituted E-2,3-diphenyl propenoic acid molecules were synthesised and their aggregation behaviour was studied by experimental (FT-IR spectroscopy) and computational (semiempirical and DFT) methods. Experimental approach embraced the identification of potential hydrogen bonding sites through finding the relevant IR bands and monitoring their shifts upon increasing the acid concentration and on going to the solid state. It was found that fluorine engaged in C sbnd H…F hydrogen bonding easily, where the carbon atom could be of any kind available in the molecule (aromatic, aliphatic or olefinic). Shifts were found even in moderately concentrated solutions and in the solid state too. Hydrogen bonding sites could be assigned and relevant aggregate models could be built. Molecular modelling allowed obtaining good estimates for hydrogen bond lengths and angles and visualisation of the geometric arrangements even of extended networks also became feasible.

Laser properties of Fe2+:ZnSe fabricated by solid-state diffusion bonding

NASA Astrophysics Data System (ADS)

Balabanov, S. S.; Firsov, K. N.; Gavrishchuk, E. M.; Ikonnikov, V. B.; Kazantsev, S. Yu; Kononov, I. G.; Kotereva, T. V.; Savin, D. V.; Timofeeva, N. A.

2018-04-01

The characteristics of an Fe2+:ZnSe laser at room temperature and its active elements with undoped faces were studied. Polycrystalline elements with one or two diffusion-doped internal layers were obtained by the solid-state diffusion bonding technique applied to chemical vapor deposition grown ZnSe plates preliminary doped with Fe2+ ions in the process of hot isostatic pressing. A non-chain electric-discharge HF laser was used to pump the crystals. It was demonstrated that increasing the number of doped layers allows increasing the maximum diameter of the pump radiation spot and the pump energy without the appearance of transversal parasitic oscillation. For the two-layer-doped active element with a diameter of 20 mm an output energy of 480 mJ was achieved with 37% total efficiency with respect to the absorbed energy. The obtained results demonstrate the potential of the developed technology for fabrication of active elements by the solid-state diffusion bonding technique combined with the hot isostatic pressing treatment for efficient IR lasers based on chalcogenides doped with transition metal ions.

Friction Stir Welding of SiC/Aluminum Metal Matrix Composites

NASA Technical Reports Server (NTRS)

Lee, Jonathan A.

1999-01-01

Friction Stir Welding (FSW) is a new solid state process for joining metals by plasticizing and consolidating materials around the bond line using thermal energy producing from frictional forces. A feasibility study for FSW of Metal Matrix Composites (MMC) was investigated using aluminum 6092 alloy reinforced with 17% SiC particulates. FSW process consists of a special rotating pin tool that is positioned to plunge into the MMC surface at the bond line. As the tool rotates and move forward along the bond line, the material at the bond line is heated up and forced to flow around the rotating tip to consolidate on the tip's backside to form a solid state joint. FSW has the potential for producing sound welds with MMC because the processing temperature occurs well below the melting point of the metal matrix; thereby eliminating the reinforcement-to-matrix solidification defects, reducing the undesirable chemical reactions and porosity problems.

The structure investigations of dehydroacetic acid and 1,8-diaminonaphthalene condensation product by NMR, MS, and X-ray measurements

NASA Astrophysics Data System (ADS)

Kołodziej, B.; Morawiak, M.; Kamieński, B.; Schilf, W.

2016-05-01

A new unexpected product of condensation reaction of 1,8-diaminonaphthalene (DAN) and carbonyl compound (here: dehydroacetic acid (dha)) was synthesized. Discussion about the molecular structure of possible products of this reaction was done on the base of NMR studies. The structure of the titled product in both DMSO solution and in the solid state was resolved by analysis of its spectral data (X-ray structure analysis, multinuclear NMR in solution and solid state spectra) and MS measurements. The presented studies provided clear evidence that the titled product exists in diluted DMSO solution as the mixture of two kinetic free ionic species whereas in concentrated DMSO solution as well as in the solid state this system forms associated ionic pairs bonded together by hydrogen bonds.

Solid-solution thermodynamics in Al-Li alloys

NASA Astrophysics Data System (ADS)

Alekseev, A. A.; Lukina, E. A.

2016-05-01

The relative equilibrium concentrations of lithium atoms distributed over different electron-structural states has been estimated. The possibility of the existence of various nonequilibrium electron-structural states of Li atoms in the solid solution in Al has been substantiated thermodynamically. Upon the decomposition of the supersaturated solid solution, the supersaturation on three electron-structural states of Li atoms that arises upon the quenching of the alloy can lead to the formation of lithium-containing phases in which the lithium atoms enter in one electron-structural state.

Solid-state acid-base interactions in complexes of heterocyclic bases with dicarboxylic acids: crystallography, hydrogen bond analysis, and 15N NMR spectroscopy.

PubMed

Li, Z Jane; Abramov, Yuriy; Bordner, Jon; Leonard, Jason; Medek, Ales; Trask, Andrew V

2006-06-28

A cancer candidate, compound 1, is a weak base with two heterocyclic basic nitrogens and five hydrogen-bonding functional groups, and is sparingly soluble in water rendering it unsuitable for pharmaceutical development. The crystalline acid-base pairs of 1, collectively termed solid acid-base complexes, provide significant increases in the solubility and bioavailability compared to the free base, 1. Three dicarboxylic acid-base complexes, sesquisuccinate 2, dimalonate 3, and dimaleate 4, show the most favorable physicochemical profiles and are studied in greater detail. The structural analyses of the three complexes using crystal structure and solid-state NMR reveal that the proton-transfer behavior in these organic acid-base complexes vary successively correlating with Delta pKa. As a result, 2 is a neutral complex, 3 is a mixed ionic and zwitterionic complex and 4 is an ionic salt. The addition of the acidic components leads to maximized hydrogen bond interactions forming extended three-dimensional networks. Although structurally similar, the packing arrangements of the three complexes are considerably different due to the presence of multiple functional groups and the flexible backbone of 1. The findings in this study provide insight into the structural characteristics of complexes involving heterocyclic bases and carboxylic acids, and demonstrate that X-ray crystallography and 15N solid-state NMR are truly complementary in elucidating hydrogen bonding interactions and the degree of proton transfer of these complexes.

Anisotropic high-harmonic generation in bulk crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

You, Yong Sing; Reis, David A.; Ghimire, Shambhu

2016-11-21

The microscopic valence electron density determines the optical, electronic, structural and thermal properties of materials. However, current techniques for measuring this electron charge density are limited: for example, scanning tunnelling microscopy is confined to investigations at the surface, and electron diffraction requires very thin samples to avoid multiple scattering. Therefore, an optical method is desirable for measuring the valence charge density of bulk materials. Since the discovery of high-harmonic generation (HHG) in solids, there has been growing interest in using HHG to probe the electronic structure of solids. Here, using single-crystal MgO, we demonstrate that high-harmonic generation in solids ismore » sensitive to interatomic bonding. We find that harmonic efficiency is enhanced (diminished) for semi-classical electron trajectories that connect (avoid) neighbouring atomic sites in the crystal. Finally, these results indicate the possibility of using materials’ own electrons for retrieving the interatomic potential and thus the valence electron density, and perhaps even wavefunctions, in an all-optical setting.« less

Uranium(III)-carbon multiple bonding supported by arene δ-bonding in mixed-valence hexauranium nanometre-scale rings.

PubMed

Wooles, Ashley J; Mills, David P; Tuna, Floriana; McInnes, Eric J L; Law, Gareth T W; Fuller, Adam J; Kremer, Felipe; Ridgway, Mark; Lewis, William; Gagliardi, Laura; Vlaisavljevich, Bess; Liddle, Stephen T

2018-05-29

Despite the fact that non-aqueous uranium chemistry is over 60 years old, most polarised-covalent uranium-element multiple bonds involve formal uranium oxidation states IV, V, and VI. The paucity of uranium(III) congeners is because, in common with metal-ligand multiple bonding generally, such linkages involve strongly donating, charge-loaded ligands that bind best to electron-poor metals and inherently promote disproportionation of uranium(III). Here, we report the synthesis of hexauranium-methanediide nanometre-scale rings. Combined experimental and computational studies suggest overall the presence of formal uranium(III) and (IV) ions, though electron delocalisation in this Kramers system cannot be definitively ruled out, and the resulting polarised-covalent U = C bonds are supported by iodide and δ-bonded arene bridges. The arenes provide reservoirs that accommodate charge, thus avoiding inter-electronic repulsion that would destabilise these low oxidation state metal-ligand multiple bonds. Using arenes as electronic buffers could constitute a general synthetic strategy by which to stabilise otherwise inherently unstable metal-ligand linkages.

SOLID STATE BONDING OF THORIUM WITH ALUMINUM

DOEpatents

Storchhelm, S.

1959-12-01

A method is described for bonding thorium and aluminum by placing clean surfaces of thorium and aluminum in contact with each other and hot pressing the metals together in a protective atmosphere at a temperature of about 375 to 575 deg C and at a pressure of at least 10 tsi to effect a bond.

Characterization of hot bonding of bi-metal C45/25CrMo4 by plane strain compression test

NASA Astrophysics Data System (ADS)

Enaim, Mohammed; Langlois, Laurent; Zimmer-Chevret, Sandra; Bigot, Régis; Krumpipe, Pierre

2018-05-01

The need to produce multifunctional parts in order to conform to complex specifications becomes crucial in today's industrial context. This is why new processes are under study to develop multi-material parts which can satisfy this kind of requirements. This paper investigates the possibility of producing hot bonding of bi-metal C45/25CrMo4 parts by forging. This manufacturing process is a solid state joining process that involves, simultaneously, the welding and shaping of multi-material part. In this study, the C45/25CrMo4 bimetal was investigated. The forging is conducted at 1100°C and the influence of reduction rate on microstructure and bonding was investigated. The bonding model is inspired from Bay's model. Following this model, two parameters govern the solid-state bonding at the interface between materials: normal contact pressure and surface expansion. The objective is to check the bonding quality under different pressure and surface expansion. To achieve this goal, the plane strain compression test is chosen as the characterization test. Finally, simulations and experiments of this test are compared.

Structure and magnetic properties of SiO{sub 2}/PCL novel sol–gel organic–inorganic hybrid materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Catauro, Michelina, E-mail: michelina.catauro@unina2.it; Bollino, Flavia; Cristina Mozzati, Maria

2013-07-15

Organic–inorganic nanocomposite materials have been synthesized via sol–gel. They consist of an inorganic SiO{sub 2} matrix, in which different percentages of poly(ε-caprolactone) (PCL) have been incorporated. The formation of H-bonds among the carbonyl groups of the polymer chains and Si–OH group of the inorganic matrix has been proved by means of Fourier transform infrared spectroscopy (FT-IR) analysis and has been confirmed by solid-state nuclear magnetic resonance (NMR). X-Ray diffraction (XRD) analysis highlighted the amorphous nature of the synthesized materials. Scanning electron microscope (SEM) micrograph and atomic force microscope (AFM) topography showed their homogeneous morphology and nanostructure nature. Considering the opportunitymore » to synthesize these hybrid materials under microgravity conditions by means of magnetic levitation, superconducting quantum interference device (SQUID) magnetometry has been used to quantify their magnetic susceptibility. This measure has shown that the SiO{sub 2}/PCL hybrid materials are diamagnetic and that their diamagnetic susceptibility is independent of temperature and increases with the PCL amount. - Graphical abstract: Characterization and magnetic properties of SiO{sub 2}/PCL organic–inorganic hybrid materials synthesized via sol–gel. FT-IR, Fourier transform infrared spectroscopy; solid-state NMR: solid-state nuclear magnetic resonance; SQUID: superconducting quantum interference device. - Highlights: • Sol–gel synthesis of SiO{sub 2}/PCL amorphous class I organic–inorganic hybrid materials. • FT-IR and NMR analyses show the hydrogen bonds formation between SiO{sub 2} and PCL. • AFM and SEM analyses confirm that the SiO{sub 2}/PCL are homogenous hybrid materials. • The SQUID measures show that the simples are diamagnetic. • Diamagnetic susceptibility of SiO{sub 2}/PCL materials increases with the PCL amount.« less

Solid-state supercapacitors with ionic liquid gel polymer electrolyte based on poly (3, 4-ethylenedioxythiophene), carbon nanotubes, and metal oxides nanocomposites for electrical energy storage

NASA Astrophysics Data System (ADS)

Obeidat, Amr M.

Clean and renewable energy systems have emerged as an important area of research having diverse and significant new applications. These systems utilize different energy storage methods such as the batteries and supercapacitors. Supercapacitors are electrochemical energy storage devices that are designed to bridge the gap between batteries and conventional capacitors. Supercapacitors which store electrical energy by electrical double layer capacitance are based on large surface area structured carbons. The materials systems in which the Faradaic reversible redox reactions store electrical energy are the transition metal oxides and electronically conducting polymers. Among the different types of conducting polymers, poly (3, 4- ethylenedioxythiophene) (PEDOT) is extensively investigated owing to its chemical and mechanical stability. Due to instability of aqueous electrolytes at high voltages and toxicity of organic electrolytes, potential of supercapacitors has not been fully exploited. A novel aspect of this work is in utilizing the ionic liquid gel polymer electrolyte to design solid-state supercapacitors for energy storage. Various electrochemical systems were investigated including graphene, PEDOT, PEDOT-carbon nanotubes, PEDOT-manganese oxide, and PEDOT-iron oxide nanocomposites. The electrochemical performance of solid-state supercapacitor devices was evaluated based on cyclic voltammetry (CV), charge-discharge (CD), prolonged cyclic tests, and electrochemical impedance spectroscopy (EIS) techniques. Raman spectroscopy technique was also utilized to analyze the bonding structure of the electrode materials. The graphene solid-state supercapacitor system displayed areal capacitance density of 141.83 mF cm-2 based on high potential window up to 4V. The PEDOT solid-state supercapacitor system was synthesized in acetonitrile and aqueous mediums achieving areal capacitance density of 219.17 mF cm-2. The hybrid structure of solid-state supercapacitors was also studied in solid-state design based on PEDOT and graphene electrodes that produced areal capacitance density of 198.26 mF cm-2. Symmetrical PEDOT-manganese oxide nanocomposites were synthesized by co-deposition and dip-coating techniques to fabricate solid-state supercapacitor systems achieving areal capacitance density of 122.08 mF cm-2 credited to the PEDOT-MnO2 supercapacitor that was synthesized by dipping the PEDOT electrode in pure KMnO4 solution. The electrochemical performance of PEDOT-carbon nanotube solid-state supercapacitors was also investigated in both acetonitrile and aqueous medium showing good dispersion characteristics with optimum CNT content of 1 mg. The PEDOT-CNT solid-state supercapacitor system synthesized in acetonitrile displayed areal capacitance density of 297.43 mF cm-2. PEDOT-Fe2O3 nanocomposites were synthesized by single-step co-deposition techniques, and these were used to fabricate solid-state supercapacitors achieving areal capacitance density of 96.89 mF cm-2. Furthermore, some of these thin flexible solid-state supercapacitors were integrated with solar cells for direct storage of solar electricity, which proved to be promising as autonomous power source for flexible and wearable electronics. This dissertation describes the electrode synthesis, design and properties of solid-state supercapacitors, and their electrochemical performance in the storage of electrical energy.

500(deg)C electronics for harsh environments

NASA Technical Reports Server (NTRS)

Sadwick, Laurence P.; Hwu, R. Jennifer; Chern, J. H. Howard; Lin, Ching-Hsu; Castillo, Linda Del; Johnson, Travis

2005-01-01

Solid state vacuum devices (SSVDs) are a relatively new class of electronic devices. Innosys is a leading producer of high frequency SSVDs for a number of applications, including RF communications. SSVDs combine features inherent to both solid state and vacuum transistors. Electron transport can be by solid state or vacuum or both. The focus of this talk is on thermionic SSVDs, in which the primary vacuum transport is by thermionically liberated electron emission.

Nonadiabatic quantum dynamics and laser control of Br2 in solid argon.

PubMed

Accardi, A; Borowski, A; Kühn, O

2009-07-02

A five-dimensional reaction surface-vibronic coupling model is introduced to describe the B- to C-state predissociation dynamics of Br(2) occupying a double substitutional lattice site in a face-centered cubic argon crystal at low temperatures. The quantum dynamics driven by a Franck-Condon vertical excitation is investigated, revealing the role of matrix cage compression for efficient nonadiabatic transitions. Vibrational preexcitation of the Br(2) bond in the electronic ground state can be used to access a different regime of predissociation which does not require substantial matrix compression because the Franck-Condon window shifts into the energetic range of the B-C level crossing. Using optimal control theory, it is shown how vibrational preexcitation can be achieved via a pump-dump-type mechanism involving the repulsive C state.

Generalized valence bond description of the ground states (X(1)Σg(+)) of homonuclear pnictogen diatomic molecules: N2, P2, and As2.

PubMed

Xu, Lu T; Dunning, Thom H

2015-06-09

The ground state, X1Σg+, of N2 is a textbook example of a molecule with a triple bond consisting of one σ and two π bonds. This assignment, which is usually rationalized using molecular orbital (MO) theory, implicitly assumes that the spins of the three pairs of electrons involved in the bonds are singlet-coupled (perfect pairing). However, for a six-electron singlet state, there are five distinct ways to couple the electron spins. The generalized valence bond (GVB) wave function lifts this restriction, including all of the five spin functions for the six electrons involved in the bond. For N2, we find that the perfect pairing spin function is indeed dominant at Re but that it becomes progressively less so from N2 to P2 and As2. Although the perfect pairing spin function is still the most important spin function in P2, the importance of a quasi-atomic spin function, which singlet couples the spins of the electrons in the σ orbitals while high spin coupling those of the electrons in the π orbitals on each center, has significantly increased relative to N2 and, in As2, the perfect pairing and quasi-atomic spin couplings are on essentially the same footing. This change in the spin coupling of the electrons in the bonding orbitals down the periodic table may contribute to the rather dramatic decrease in the strengths of the Pn2 bonds from N2 to As2 as well as in the increase in their chemical reactivity and should be taken into account in more detailed analyses of the bond energies in these species. We also compare the spin coupling in N2 with that in C2, where the quasi-atomic spin coupling dominants around Re.

Solid State Research, 1980:1.

DTIC Science & Technology

1980-02-15

ESD-TR-79-325 H 1 Solid State Research 1980 Prepared under Electronic Systems Division Contract FI%28-80-C-0002 by Lincoln Laboratory MASSkCHIISETTS...it is no longer needed. MASSACHUSETTS IN*STITUTE OF TECHNOLOGY LINCOLN LABORATORY V SOLID STATE RESEARCH QUARTERLY TECHNICAL SUMMARY REPORT I NOVEMBER...January 1990. The topics covered a-e Solid State Device Research , Quantum Electronics, Materials Rese.rch, Microelec- tronics, and Analog Device

Aromatic hydrazones derived from nicotinic acid hydrazide as fluorimetric pH sensing molecules: Structural analysis by computational and spectroscopic methods in solid phase and in solution

NASA Astrophysics Data System (ADS)

Benković, T.; Kenđel, A.; Parlov-Vuković, J.; Kontrec, D.; Chiş, V.; Miljanić, S.; Galić, N.

2018-02-01

Structural analyses of aroylhydrazones were performed by computational and spectroscopic methods (solid state NMR, 1 and 2D NMR spectroscopy, FT-IR (ATR) spectroscopy, Raman spectroscopy, UV-Vis spectrometry and spectrofluorimetry) in solid state and in solution. The studied compounds were N‧-(2,3-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (1), N‧-(2,5-dihydroxyphenylmethylidene)-3-pyridinecarbohydrazide (2), N‧-(3-chloro-2-hydroxy-phenylmethylidene)-3-pyridinecarbohydrazide (3), and N‧-(2-hydroxy-4-methoxyphenyl-methylidene)-3-pyridinecarbohydrazide (4). Both in solid state and in solution, all compounds were in ketoamine form (form I, sbnd COsbnd NHsbnd Ndbnd Csbnd), stabilized by intramolecular H-bond between hydroxyl proton and nitrogen atom of the Cdbnd N group. In solid state, the Cdbnd O group of 1-4 were involved in additional intermolecular H-bond between closely packed molecules. Among hydrazones studied, the chloro- and methoxy-derivatives have shown pH dependent and reversible fluorescence emission connected to deprotonation/protonation of salicylidene part of the molecules. All findings acquired by experimental methods (NMR, IR, Raman, and UV-Vis spectra) were in excellent agreement with those obtained by computational methods.

Expanded Definition of the Oxidation State

ERIC Educational Resources Information Center

Loock, Hans-Peter

2011-01-01

A proposal to define the oxidation state of an atom in a compound as the hypothetical charge of the corresponding atomic ion that is obtained by heterolytically cleaving its bonds such that the atom with the higher electronegativity in a bond is allocated all electrons in the bond. Bonds between like atoms are cleaved homolytically. This…

Real-space mapping of electronic orbitals.

PubMed

Löffler, Stefan; Bugnet, Matthieu; Gauquelin, Nicolas; Lazar, Sorin; Assmann, Elias; Held, Karsten; Botton, Gianluigi A; Schattschneider, Peter

2017-06-01

Electronic states are responsible for most material properties, including chemical bonds, electrical and thermal conductivity, as well as optical and magnetic properties. Experimentally, however, they remain mostly elusive. Here, we report the real-space mapping of selected transitions between p and d states on the Ångström scale in bulk rutile (TiO 2 ) using electron energy-loss spectrometry (EELS), revealing information on individual bonds between atoms. On the one hand, this enables the experimental verification of theoretical predictions about electronic states. On the other hand, it paves the way for directly investigating electronic states under conditions that are at the limit of the current capabilities of numerical simulations such as, e.g., the electronic states at defects, interfaces, and quantum dots. Copyright © 2017 Elsevier B.V. All rights reserved.

Numerical Simulation of Transient Liquid Phase Bonding under Temperature Gradient

NASA Astrophysics Data System (ADS)

Ghobadi Bigvand, Arian

Transient Liquid Phase bonding under Temperature Gradient (TG-TLP bonding) is a relatively new process of TLP diffusion bonding family for joining difficult-to-weld aerospace materials. Earlier studies have suggested that in contrast to the conventional TLP bonding process, liquid state diffusion drives joint solidification in TG-TLP bonding process. In the present work, a mass conservative numerical model that considers asymmetry in joint solidification is developed using finite element method to properly study the TG-TLP bonding process. The numerical results, which are experimentally verified, show that unlike what has been previously reported, solid state diffusion plays a major role in controlling the solidification behavior during TG-TLP bonding process. The newly developed model provides a vital tool for further elucidation of the TG-TLP bonding process.

Alchemical and structural distribution based representation for universal quantum machine learning

NASA Astrophysics Data System (ADS)

Faber, Felix A.; Christensen, Anders S.; Huang, Bing; von Lilienfeld, O. Anatole

2018-06-01

We introduce a representation of any atom in any chemical environment for the automatized generation of universal kernel ridge regression-based quantum machine learning (QML) models of electronic properties, trained throughout chemical compound space. The representation is based on Gaussian distribution functions, scaled by power laws and explicitly accounting for structural as well as elemental degrees of freedom. The elemental components help us to lower the QML model's learning curve, and, through interpolation across the periodic table, even enable "alchemical extrapolation" to covalent bonding between elements not part of training. This point is demonstrated for the prediction of covalent binding in single, double, and triple bonds among main-group elements as well as for atomization energies in organic molecules. We present numerical evidence that resulting QML energy models, after training on a few thousand random training instances, reach chemical accuracy for out-of-sample compounds. Compound datasets studied include thousands of structurally and compositionally diverse organic molecules, non-covalently bonded protein side-chains, (H2O)40-clusters, and crystalline solids. Learning curves for QML models also indicate competitive predictive power for various other electronic ground state properties of organic molecules, calculated with hybrid density functional theory, including polarizability, heat-capacity, HOMO-LUMO eigenvalues and gap, zero point vibrational energy, dipole moment, and highest vibrational fundamental frequency.

Syntheses, spectroscopic properties and molecular structure of silver phytate complexes - IR, UV-VIS studies and DFT calculations

NASA Astrophysics Data System (ADS)

Zając, A.; Dymińska, L.; Lorenc, J.; Ptak, M.; Hanuza, J.

2018-03-01

Silver phytate IP6, IP6Ag, IP6Ag2 and IP6Ag3 complexes in the solid state have been synthesized changing the phosphate to metal mole ratio. The obtained products have been characterized by means of chemical and spectroscopic studies. Attenuated total reflection Fourier transform infrared technique and Raman microscope were used in the measurements. These results were discussed in terms of DFT (Density Functional Theory) quantum chemical calculations using the B3LYP/6-31G(d,p) approach. The molecular structures of these compounds have been proposed on the basis of group theory and geometry optimization taking into account the shape and the number of the observed bands corresponding to the stretching and bending vibrations of the phosphate group and metal-oxygen polyhedron. The role of inter- and intra-hydrogen bonds in stabilization of the structure has been discussed. It was found that three types of hydrogen bonds appear in the studied compounds: terminal, and those engaged in the inter- and intra-molecular interactions. The Fermi resonance as a result of the strong intra-molecular Osbnd H⋯O hydrogen bonds was discovered. Electron absorption spectra have been measured to characterize the electron properties of the studied complexes and their local symmetry.

The structure of poly(carbonsuboxide) on the atomic scale: a solid-state NMR study.

PubMed

Schmedt auf der Günne, Jörn; Beck, Johannes; Hoffbauer, Wilfried; Krieger-Beck, Petra

2005-07-18

In this contribution we present a study of the structure of amorphous poly(carbonsuboxide) (C3O2)x by 13C solid-state NMR spectroscopy supported by infrared spectroscopy and chemical analysis. Poly(carbonsuboxide) was obtained by polymerization of carbonsuboxide C3O2, which in turn was synthesized from malonic acid bis(trimethylsilylester). Two different 13C labeling schemes were applied to probe inter- and intramonomeric bonds in the polymer by dipolar solid-state NMR methods and also to allow quantitative 13C MAS NMR spectra. Four types of carbon environments can be distinguished in the NMR spectra. Double-quantum and triple-quantum 2D correlation experiments were used to assign the observed peaks using the through-space and through-bond dipolar coupling. In order to obtain distance constraints for the intermonomeric bonds, double-quantum constant-time experiments were performed. In these experiments an additional filter step was applied to suppress contributions from not directly bonded 13C,13C spin pairs. The 13C NMR intensities, chemical shifts, connectivities and distances gave constraints for both the polymerization mechanism and the short-range order of the polymer. The experimental results were complemented by bond lengths predicted by density functional theory methods for several previously suggested models. Based on the presented evidence we can unambiguously exclude models based on gamma-pyronic units and support models based on alpha-pyronic units. The possibility of planar ladder- and bracelet-like alpha-pyronic structures is discussed.

Impact of helical organization on the photovoltaic properties of oligothiophene supramolecular polymers† †Electronic supplementary information (ESI) available: Synthesis and characterization of 3 and 4, UV-vis spectra, solar cell device properties and AFM images. See DOI: 10.1039/c7sc05093c

PubMed Central

Ouchi, Hayato; Kizaki, Takahiro; Yamato, Masaki; Lin, Xu; Hoshi, Nagahiro; Silly, Fabien; Kajitani, Takashi; Fukushima, Takanori

2018-01-01

Helical self-assembly of functional π-conjugated molecules offers unique photochemical and electronic properties in the spectroscopic level, but there are only a few examples that demonstrate their positive impact on the optoelectronic device level. Here, we demonstrate that hydrogen-bonded tapelike supramolecular polymers of a barbiturated oligo(alkylthiophene) show notable improvement in their photovoltaic properties upon organizing into helical nanofibers. A tapelike hydrogen-bonded supramolecular array of barbiturated oligo(butylthiophene) molecules was directly visualized by STM at a liquid–solid interface. TEM, AFM and XRD revealed that the tapelike supramolecular polymers further organize into helical nanofibers in solution and bulk states. Bulk heterojunction solar cells of the helical nanofibers and soluble fullerene showed a power conversion efficiency of 4.5%, which is markedly high compared to that of the regioisomer of butyl chains organizing into 3D lamellar agglomerates. PMID:29780493

Geometric, electronic, and bonding properties of AuNM (N = 1-7, M = Ni, Pd, Pt) clusters.

PubMed

Yuan, D W; Wang, Yang; Zeng, Zhi

2005-03-15

Employing first-principles methods, based on density functional theory, we report the ground state geometric and electronic structures of gold clusters doped with platinum group atoms, Au(N)M (N = 1-7, M = Ni, Pd, Pt). The stability and electronic properties of Ni-doped gold clusters are similar to that of pure gold clusters with an enhancement of bond strength. Due to the strong d-d or s-d interplay between impurities and gold atoms originating in the relativistic effects and unique properties of dopant delocalized s-electrons in Pd- and Pt-doped gold clusters, the dopant atoms markedly change the geometric and electronic properties of gold clusters, and stronger bond energies are found in Pt-doped clusters. The Mulliken populations analysis of impurities and detailed decompositions of bond energies as well as a variety of density of states of the most stable dopant gold clusters are given to understand the different effects of individual dopant atom on bonding and electronic properties of dopant gold clusters. From the electronic properties of dopant gold clusters, the different chemical reactivity toward O(2), CO, or NO molecule is predicted in transition metal-doped gold clusters compared to pure gold clusters.

Strong and Robust Polyaniline-Based Supramolecular Hydrogels for Flexible Supercapacitors.

PubMed

Li, Wanwan; Gao, Fengxian; Wang, Xiaoqian; Zhang, Ning; Ma, Mingming

2016-08-01

We report a supramolecular strategy to prepare conductive hydrogels with outstanding mechanical and electrochemical properties, which are utilized for flexible solid-state supercapacitors (SCs) with high performance. The supramolecular assembly of polyaniline and polyvinyl alcohol through dynamic boronate bond yields the polyaniline-polyvinyl alcohol hydrogel (PPH), which shows remarkable tensile strength (5.3 MPa) and electrochemical capacitance (928 F g(-1) ). The flexible solid-state supercapacitor based on PPH provides a large capacitance (306 mF cm(-2) and 153 F g(-1) ) and a high energy density of 13.6 Wh kg(-1) , superior to other flexible supercapacitors. The robustness of the PPH-based supercapacitor is demonstrated by the 100 % capacitance retention after 1000 mechanical folding cycles, and the 90 % capacitance retention after 1000 galvanostatic charge-discharge cycles. The high activity and robustness enable the PPH-based supercapacitor as a promising power device for flexible electronics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Constitutional self-organization of adenine-uracil-derived hybrid materials.

PubMed

Arnal-Hérault, Carole; Barboiu, Mihai; Pasc, Andreea; Michau, Mathieu; Perriat, Pascal; van der Lee, Arie

2007-01-01

The alkoxysilane nucleobase adenine (A) and uracil (U) precursors described in this paper generate in solution a complex library of hydrogen-bonded aggregates, which can be expressed in the solid state as discrete higher oligomers. The different interconverting outputs that nucleobases may form by oligomerization define a dynamic polyfunctional diversity that may be "extracted selectively" in solid state by sol-gel transcription, under the intrinsic stability of the system. After the sol-gel process, unique constitutional preference for specific geometries in hybrid materials is consistent with a preferential arrangement of nucleobase systems, favoring the self-assembly by the Hoogsteen geometry. FTIR and NMR spectroscopy and X-ray powder diffraction experiments demonstrate the formation of self-organized hybrid supramolecular materials. Electron microscopy reveals the micrometric platelike morphology of the hybrid materials. The M(A-U) hybrid material is nanostructured in ordered circular domains of 5 nm in diameter of alternative light and dark rows with an one-dimensional periodicity of 3.5 A.

Method of bonding a conductive layer on an electrode of an electrochemical cell

DOEpatents

Bowker, J.C.; Singh, P.

1989-08-29

A dense, electronically conductive interconnection layer is bonded onto a porous, tubular, electronically conductive air electrode structure, optionally supported by a ceramic support, by (A) providing an air electrode surface, (B) forming on a selected portion of the electrode surface, without the use of pressure, particles of LaCrO[sub 3] doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide; (C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300 C to 1,550 C, without the application of pressure, to provide a dense, sintered, interconnection material bonded to the air electrode, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO[sub 3]. A solid electrolyte layer can be applied to the uncovered portion of the air electrode, and a fuel electrode can be applied to the solid electrolyte, to provide an electrochemical cell. 4 figs.

Method of bonding a conductive layer on an electrode of an electrochemical cell

DOEpatents

Bowker, Jeffrey C.; Singh, Prabhakar

1989-01-01

A dense, electronically conductive interconnection layer 26 is bonded onto a porous, tubular, electronically conductive air electrode structure 16, optionally supported by a ceramic support 22, by (A) providing an air electrode surface, (B) forming on a selected portion of the electrode surface 24, without the use of pressure, particles of LaCrO.sub.3 doped with an element selected from the group consisting of Sr, Mg, Ca, Ba, Co, and mixtures thereof, where the particles have a deposit on their surface comprising calcium oxide and chromium oxide; (C) heating the particles with the oxide surface deposit in an oxidizing atmosphere at from 1,300.degree. C. to 1,550.degree. C., without the application of pressure, to provide a dense, sintered, interconnection material 26 bonded to the air electrode 16, where calcium and chromium from the surface deposit are incorporated into the structure of the LaCrO.sub.3. A solid electrolyte layer 18 can be applied to the uncovered portion of the air electrode, and a fuel electrode 20 can be applied to the solid electrolyte, to provide an electrochemical cell 10.

Observation of Spontaneous C=C Bond Breaking in the Reaction between Atomic Boron and Ethylene in Solid Neon.

PubMed

Jian, Jiwen; Lin, Hailu; Luo, Mingbiao; Chen, Mohua; Zhou, Mingfei

2016-07-11

A ground-state boron atom inserts into the C=C bond of ethylene to spontaneously form the allene-like compound H2 CBCH2 on annealing in solid neon. This compound can further isomerize to the propyne-like HCBCH3 isomer under UV light excitation. The observation of this unique spontaneous C=C bond insertion reaction is consistent with theoretical predictions that the reaction is thermodynamically exothermic and kinetically facile. This work demonstrates that the stronger C=C bond, rather than the less inert C-H bond, can be broken to form organoboron species from the reaction of a boron atom with ethylene even at cryogenic temperatures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanometre-scale 3D defects in Cr2AlC thin films.

PubMed

Chen, Y T; Music, D; Shang, L; Mayer, J; Schneider, J M

2017-04-20

MAX-phase Cr 2 AlC containing thin films were synthesized by magnetron sputtering in an industrial system. Nanometre-scale 3D defects are observed near the boundary between regions of Cr 2 AlC and of the disordered solid solution (CrAl) x C y . Shrinkage of the Cr-Cr interplanar distance and elongation of the Cr-Al distance in the vicinity of the defects are detected using transmission electron microscopy. The here observed deformation surrounding the defects was described using density functional theory by comparing the DOS of bulk Cr 2 AlC with the DOS of a strained and unstrained Cr 2 AlC(0001) surface. From the partial density of states analysis, it can be learned that Cr-C bonds are stronger than Cr-Al bonds in bulk Cr 2 AlC. Upon Cr 2 AlC(0001) surface formation, both bonds are weakened. While the Cr-C bonds recover their bulk strength as Cr 2 AlC(0001) is strained, the Cr-Al bonds experience only a partial recovery, still being weaker than their bulk counterparts. Hence, the strain induced bond strengthening in Cr 2 AlC(0001) is larger for Cr d - C p bonds than for Cr d - Al p bonds. The here observed changes in bonding due to the formation of a strained surface are consistent with the experimentally observed elongation of the Cr-Al distance in the vicinity of nm-scale 3D defects in Cr 2 AlC thin films.

Aryl C—H···Cl– Hydrogen Bonding in a Fluorescent Anion Sensor

PubMed Central

Tresca, Blakely W.; Zakharov, Lev N.; Carroll, Calden N.; Johnson, Darren W.; Haley, Michael M.

2014-01-01

A new phenyl-acetylene receptor containing a carbonaceous hydrogen bond donor activates anion binding in conjunction with two stabilizing ureas. The unusual CH···Cl– hydrogen bond is apparent in solution by large 1H NMR chemical shifts and by a short, linear contact in the solid state. PMID:23843050

Final Technical Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dr. Asok K. Ray

2012-05-22

During the past decades, considerable theoretical efforts have been devoted to studying the electronic and geometric structures and related properties of surfaces. Such efforts are particularly important for systems like the actinides for which experimental work is relatively difficult to perform due to material problems and toxicity. The actinides are characterized by a gradual filling of the 5f-electron shell with the degree of localization increasing with the atomic number Z along the last series of the periodic table. The open shell of the 5f electrons determines the atomic, molecular, and solid state properties of the actinide elements and their compoundsmore » and understanding the quantum mechanics of the 5f electrons is the defining issue in the chemistry and physics of actinide elements. These elements are also characterized by the increasing prominence of relativistic effects and their studies can, in fact, help us understand the role of relativity throughout the periodic table. However, the electronic and geometric structures of the actinides, specifically the trans-uranium actinides and the roles of the 5f electrons in chemical bonding are still not well understood. This is crucial not only for our understanding of the actinides but also for the fact that the actinides constitute 'the missing link' between the d transition elements and the lanthanides. The 5f orbitals have properties intermediate between those of localized 4f and delocalized 3d orbitals. Thus, a proper understanding of the actinides will help us understand the behavior of the lanthanides and transition metals as well. In fact, there is an urgent need for continued extensive and detailed theoretical research in this area to provide significant and deep understandings of the electronic and geometric structures of the actinides. In this work, we have performed electronic structure studies for plutonium (Pu), americium (Am), and curium (Cm) surfaces, and molecular adsorptions on Pu and Am surfaces. In particular, the region at the boundary of Pu and Am, is widely believed to be the crossover region between d-like itinerant and f-like localized behavior The eventual goal is a complete understanding of the surface chemistry and physics processes of all actinide surfaces, defining the chemistry and physics of such heavy elements. Among the actinides, plutonium, with five 5f electrons in the solid state, is arguably the most complex, fascinating, and enigmatic element known to mankind and has attracted extraordinary scientific and technological interests because of its unique properties, generating a significant body of research in diverse areas, including superconductivity. Pu has, at least, six stable allotropes between room temperature and melting at atmospheric pressure, indicating that the valence electrons can hybridize into a number of complex bonding arrangements. Central and critical questions relate to the electronic structure, localization of the 5f electrons and the magnetism of Pu. For the light-actinides, from Th to Pu, the 5f electrons are believed to be delocalized, hybridizing with the 6d and 7s electrons. For the heavier actinides, Am and beyond, the 5f electrons are localized with the 5f orbitals progressively lower in energy relative to the 6d configuration. Hence, Pu is in a position where the 5f electronic behavior changes from itinerant to localized. As far as magnetism is concerned, a majority of the theoretical calculations continues to claim the existence of magnetism while almost all the experimental results do not find any support for such claims. The second element of interest to us, namely americium, occupies a central position in the actinide series with respect to the involvement of 5f electrons in metallic bonding. It is widely believed that the 5f electrons in Am are localized and that Am undergoes a series of crystallographic phase changes with pressure. Fully-relativistic all electron surface studies of the different phases of Am, initially for the dhcp and the fcc surfaces, can and have provided us with valuable information about chemical bonding in Am and the transitions from f-electron delocalization to f-electron localization in trans-uranium compounds. In particular, a comparative study of the electronic structures of the Pu and Am surfaces using the techniques of all-electron modern density functional theory and beyond can provide significant information about the role of 5f electrons in bond formation as also the localization of the 5f electrons, matters of considerable controversies. The change from metallic 5f bonding into local-moment nonbonding configurations that takes place between Pu and Am is rather unique in the periodic table and is at the very heart of our understanding of electronic structure. We believe that, considering the narrow bandwidth of surface states, any transition from itinerant to localized behavior first takes place at the actinide surfaces with possible reconstructions.« less

Experimental and computational thermochemical study and solid-phase structure of 5,5-dimethylbarbituric acid.

PubMed

Roux, María Victoria; Notario, Rafael; Foces-Foces, Concepción; Temprado, Manuel; Ros, Francisco; Emel'yanenko, Vladimir N; Verevkin, Sergey P

2010-03-18

This paper reports an experimental and computational thermochemical study on 5,5-dimethylbarbituric acid and the solid-phase structure of the compound. The value of the standard (p(o) = 0.1 MPa) molar enthalpy of formation in the gas phase at T = 298.15 K has been determined. The energy of combustion was measured by static bomb combustion calorimetry, and from the result obtained, the standard molar enthalpy of formation in the crystalline state at T = 298.15 K was calculated as -(706.4 +/- 2.2) kJ x mol(-1). The enthalpy of sublimation was determined using a transference (transpiration) method in a saturated NB(2) stream, and a value of the enthalpy of sublimation at T = 298.15 K was derived as (115.8 +/- 0.5) kJ x mol(-1). From these results a value of -(590.6 +/- 2.3) kJ x mol(-1) for the gas-phase enthalpy of formation at T = 298.15 K was determined. Theoretical calculations at the G3 level were performed, and a study on molecular and electronic structure of the compound has been carried out. Calculated enthalpies of formation are in reasonable agreement with the experimental value. 5,5-Dimethylbarbituric acid was characterized by single crystal X-ray diffraction analysis. In the crystal structure, N-H...O=C hydrogen bonds lead to the formation of ribbons connected further by weak C-H...O=C hydrogen bonds into a three-dimensional network. The molecular and supramolecular structures observed in the solid state were also investigated in the gas phase by DFT calculations.

Applying Molecular Bonding Concepts to the Solid State

NASA Astrophysics Data System (ADS)

Dunnington, Benjamin D.

In this thesis, we describe the extension and application of Natural Bond Orbital (NBO) analysis to periodic systems. This enables the translation of rigorous, quantum mechanical calculation results of solid systems into the localized lone pairs and two-center bonds of Lewis structures. Such localized bonding descriptions form the basic language of chemistry, and application of these ideas to solids allows for the understanding of complex phenomena in bulk systems using readily accessible concepts from molecular science. In addition to the algorithmic adjustments needed for to account for periodic boundary conditions in the NBO process, we also discuss methodology to interface the ubiquitous plane wave basis sets of the solid state with the atom-centered basis functions needed as input for NBO analysis. We will describe one method using projection of the plane wave eigenstates, and a second projection-free method that involves the direct calculation of matrix elements of the plane wave Hamiltonian in an atom-centered basis. The reliance of many localized, post-computational analysis techniques on an atom-centered description of the orbitals, means these interfaces will have applicability beyond our NBO development. An ideal area for application of such molecular descriptions of periodic systems is heterogeneous catalysis, where reactants from a gas/liquid phase react on a solid catalyst surface. Previous studies of these systems have originated from the delocalized perspective of the bulk catalyst. NBO provides an explicit description of the perturbative effect of the catalyst on the covalent bonds of the reactant, which is correlated with the catalytic activity of the material. Such a shift to an adsorbate focused description of surface reactivity will enable understanding of catalysis across a variety of materials.

Competing orders in the Hofstadter t -J model

NASA Astrophysics Data System (ADS)

Tu, Wei-Lin; Schindler, Frank; Neupert, Titus; Poilblanc, Didier

2018-01-01

The Hofstadter model describes noninteracting fermions on a lattice in the presence of an external magnetic field. Motivated by the plethora of solid-state phases emerging from electron interactions, we consider an interacting version of the Hofstadter model, including a Hubbard repulsion U . We investigate this model in the large-U limit corresponding to a t -J Hamiltonian with an external (orbital) magnetic field. By using renormalized mean-field theory supplemented by exact diagonalization calculations of small clusters, we find evidence for competing symmetry-breaking phases, exhibiting (possibly coexisting) charge, bond, and superconducting orders. Topological properties of the states are also investigated, and some of our results are compared to related experiments involving ultracold atoms loaded on optical lattices in the presence of a synthetic gauge field.

Bonded exciplex formation: electronic and stereoelectronic effects.

PubMed

Wang, Yingsheng; Haze, Olesya; Dinnocenzo, Joseph P; Farid, Samir; Farid, Ramy S; Gould, Ian R

2008-12-18

As recently proposed, the singlet-excited states of several cyanoaromatics react with pyridine via bonded-exciplex formation, a novel concept in photochemical charge transfer reactions. Presented here are electronic and steric effects on the quenching rate constants, which provide valuable support for the model. Additionally, excited-state quenching in poly(vinylpyridine) is strongly inhibited both relative to that in neat pyridine and also to conventional exciplex formation in polymers, consistent with a restrictive orientational requirement for the formation of bonded exciplexes. Examples of competing reactions to form both conventional and bonded exciplexes are presented, which illustrate the delicate balance between these two processes when their reaction energetics are similar. Experimental and computational evidence is provided for the formation of a bonded exciplex in the reaction of the singlet excited state of 2,6,9,10-tetracyanoanthracene (TCA) with an oxygen-substituted donor, dioxane, thus expanding the scope of bonded exciplexes.

Internal Electric Field Modulation in Molecular Electronic Devices by Atmosphere and Mobile Ions.

PubMed

Chandra Mondal, Prakash; Tefashe, Ushula M; McCreery, Richard L

2018-06-13

The internal potential profile and electric field are major factors controlling the electronic behavior of molecular electronic junctions consisting of ∼1-10 nm thick layers of molecules oriented in parallel between conducting contacts. The potential profile is assumed linear in the simplest cases, but can be affected by internal dipoles, charge polarization, and electronic coupling between the contacts and the molecular layer. Electrochemical processes in solutions or the solid state are entirely dependent on modification of the electric field by electrolyte ions, which screen the electrodes and form the ionic double layers that are fundamental to electrode kinetics and widespread applications. The current report investigates the effects of mobile ions on nominally solid-state molecular junctions containing aromatic molecules covalently bonded between flat, conducting carbon surfaces, focusing on changes in device conductance when ions are introduced into an otherwise conventional junction design. Small changes in conductance were observed when a polar molecule, acetonitrile, was present in the junction, and a large decrease of conductance was observed when both acetonitrile (ACN) and lithium ions (Li + ) were present. Transient experiments revealed that conductance changes occur on a microsecond-millisecond time scale, and are accompanied by significant alteration of device impedance and temperature dependence. A single molecular junction containing lithium benzoate could be reversibly transformed from symmetric current-voltage behavior to a rectifier by repetitive bias scans. The results are consistent with field-induced reorientation of acetonitrile molecules and Li + ion motion, which screen the electrodes and modify the internal potential profile and provide a potentially useful means to dynamically alter junction electronic behavior.

Solid-state modeling of the terahertz spectrum of the high explosive HMX.

PubMed

Allis, Damian G; Prokhorova, Darya A; Korter, Timothy M

2006-02-09

The experimental solid-state terahertz (THz) spectrum (3-120 cm(-1)) of the beta-crystal form of the high explosive octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) has been analyzed using solid-state density functional theory calculations. Various density functionals (both generalized gradient approximation and local density approximation) are compared in terms of their abilities to reproduce the experimentally observed solid-state structure and low-frequency vibrational motions. Good-to-excellent agreement between solid-state theory and experiment can be achieved in the THz region where isolated-molecule calculations fail to reproduce the observed spectral features, demonstrating a clear limitation of using isolated-molecule calculations for the assignment of THz frequency motions in molecular solids. The deficiency of isolated-molecule calculations is traced to modification of the molecular structure in the solid state through crystal packing effects and the formation of weak C-H...O hydrogen bonds.

Effect of characteristics of compounds on maintenance of an amorphous state in solid dispersion with crospovidone.

PubMed

Shibata, Yusuke; Fujii, Makiko; Kokudai, Makiko; Noda, Shinobu; Okada, Hideko; Kondoh, Masuo; Watanabe, Yoshiteru

2007-06-01

Solid dispersion (SD) of indomethacin with crospovidone (CrosPVP) shows useful characteristics for preparation of dosage forms. This study aimed to determine the types of drugs that could adopt a stable amorphous form in SD. Twenty compounds with various melting points (70-218 degrees C), molecular weights (135-504) and functional groups (amide, amino, carbonyl, hydroxyl, ketone etc.) were prepared in SD with CrosPVP. The CrosPVP SDs were prepared using a mechanical mixing and heating method. Melting point and molecular weight were found to have no influence on the ability of a compound to maintain an amorphous state in SD. All compounds containing hydrogen-bond-donor functional groups existed in an amorphous state in SD for at least 6 months. Infrared spectra suggested an interaction between the functional groups of these compounds and amide carbonyl group of CrosPVP. Compounds without hydrogen-bond-donor groups could not maintain an amorphous state and underwent recrystallization within 1 month. It was suggested that the presence of a hydrogen-bond-donor functional group in a compound is an important factor affecting the stable formation of SD with CrosPVP, which contains a hydrogen-bond acceptor.

Structural and electronic properties of M-MOF-74 (M = Mg, Co or Mn)

NASA Astrophysics Data System (ADS)

de Oliveira, Aline; de Lima, Guilherme Ferreira; De Abreu, Heitor Avelino

2018-01-01

The Metal-Organic Frameworks M-MOF-74 (M = Mg, Co or Mn) were investigated through Density Functional Theory calculations. Structural parameters and band gap energies were determined in agreement with experimental data, with errors under 2%. The methods Electron Localization Function and Quantum Theory of Atoms in Molecules were applied to the analyses of the electronic density topology of the three solids. These methodologies indicated that the bonds between the metallic cations and the oxygen atoms are predominantly ionic while the other ones are predominantly covalent. Furthermore, non-conventional hydrogen bonds were identified to Mg-MOF-74 and Co-MOF-74, which were not observed to Mn-MOF-74.

Seeing through walls at the nanoscale: Microwave microscopy of enclosed objects and processes in liquids

DOE PAGES

Velmurugan, Jeyavel; Kalinin, Sergei V.; Kolmakov, Andrei; ...

2016-02-11

Here, noninvasive in situ nanoscale imaging in liquid environments is a current imperative in the analysis of delicate biomedical objects and electrochemical processes at reactive liquid–solid interfaces. Microwaves of a few gigahertz frequencies offer photons with energies of ≈10 μeV, which can affect neither electronic states nor chemical bonds in condensed matter. Here, we describe an implementation of scanning near-field microwave microscopy for imaging in liquids using ultrathin molecular impermeable membranes separating scanning probes from samples enclosed in environmental cells. We imaged a model electroplating reaction as well as individual live cells. Through a side-by-side comparison of the microwave imagingmore » with scanning electron microscopy, we demonstrate the advantage of microwaves for artifact-free imaging.« less

Controlled surface oxidation of multi-layered graphene anode to increase hole injection efficiency in organic electronic devices

NASA Astrophysics Data System (ADS)

Han, Tae-Hee; Kwon, Sung-Joo; Seo, Hong-Kyu; Lee, Tae-Woo

2016-03-01

Ultraviolet ozone (UVO) surface treatment of graphene changes its sp2-hybridized carbons to sp3-bonded carbons, and introduces oxygen-containing components. Oxidized graphene has a finite energy band gap, so UVO modification of the surface of a four-layered graphene anode increases its surface ionization potential up to ∼5.2 eV and improves the hole injection efficiency (η) in organic electronic devices by reducing the energy barrier between the graphene anode and overlying organic layers. By controlling the conditions of the UVO treatment, the electrical properties of the graphene can be tuned to improve η. This controlled surface modification of the graphene will provide a way to achieve efficient and stable flexible displays and solid-state lighting.

Powder X-ray diffraction, infrared and 13C NMR spectroscopic studies of the homologous series of some solid-state zinc(II) and sodium(I) n-alkanoates

NASA Astrophysics Data System (ADS)

Nelson, Peter N.; Taylor, Richard A.

2015-03-01

A comparative study of the room temperature molecular packing and lattice structures for the homologous series of zinc(II) and sodium(I) n-alkanoates adduced from Fourier transform infrared and solid-state 13C NMR spectroscopic data in conjunction with X-ray powder diffraction measurements is carried out. For zinc carboxylates, metal-carboxyl bonding is via asymmetric bridging bidentate coordination whilst for the sodium adducts, coordination is via asymmetric chelating bidentate bonding. All compounds are packed in a monoclinic crystal system. Furthermore, the fully extended all-trans hydrocarbon chains are arranged as lamellar bilayers. For zinc compounds, there is bilayer overlap, for long chain adducts (nc > 8) but not for sodium compounds where methyl groups from opposing layers in the lamellar are only closely packed. Additionally, the hydrocarbon chains are extended along the a-axis of the unit cell for zinc compounds whilst for sodium carboxylates they are extended along the c-axis. These packing differences are responsible for different levels of Van der Waals effects in the lattices of these two series of compounds, hence, observed odd-even alternation is different. The significant difference in lattice packing observed for these two series of compounds is proposed to be due to the difference in metal-carboxyl coordination mode, arising from the different electronic structure of the central metal ions.

Interface morphology and mechanical properties of Al-Cu-Al laminated composites fabricated by explosive welding and subsequent rolling process

NASA Astrophysics Data System (ADS)

Hoseini-Athar, M. M.; Tolaminejad, B.

2016-07-01

Explosive welding is a well-known solid state method for joining similar and dissimilar materials. In the present study, tri-layered Al-Cu-Al laminated composites with different interface morphologies were fabricated by explosive welding and subsequent rolling. Effects of explosive ratio and rolling thickness reduction on the morphology of interface and mechanical properties were evaluated through optical/scanning electron microscopy, micro-hardness, tensile and tensile-shear tests. Results showed that by increasing the thickness reduction, bonding strength of specimens including straight and wavy interfaces increases. However, bonding strength of the specimens with melted layer interface decreases up to a threshold thickness reduction, then rapidly increases by raising the reduction. Hardness Values of welded specimens were higher than those of original material especially near the interface and a more uniform hardness profile was obtained after rolling process.

Single-Molecule Sensing with Nanopore Confinement: From Chemical Reactions to Biological Interactions.

PubMed

Lin, Yao; Ying, Yi-Lun; Gao, Rui; Long, Yi-Tao

2018-03-25

The nanopore can generate an electrochemical confinement for single-molecule sensing that help understand the fundamental chemical principle in nanoscale dimensions. By observing the generated ionic current, individual bond-making and bond-breaking steps, single biomolecule dynamic conformational changes and electron transfer processes that occur within pore can be monitored with high temporal and current resolution. These single-molecule studies in nanopore confinement are revealing information about the fundamental chemical and biological processes that cannot be extracted from ensemble measurements. In this Concept article, we introduce and discuss the electrochemical confinement effects on single-molecule covalent reactions, conformational dynamics of individual molecules and host-guest interactions in protein nanopores. Then, we extend the concept of nanopore confinement effects to confine electrochemical redox reactions in solid-state nanopores for developing new sensing mechanisms. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid State Chemistry of Clathrate Phases: Crystal Structure, Chemical Bonding and Preparation Routes

NASA Astrophysics Data System (ADS)

Baitinger, Michael; Böhme, Bodo; Ormeci, Alim; Grin, Yuri

Clathrates represent a family of inorganic materials called cage compounds. The key feature of their crystal structures is a three-dimensional (host) framework bearing large cavities (cages) with 20-28 vertices. These polyhedral cages bear—as a rule—guest species. Depending on the formal charge of the framework, clathrates are grouped in anionic, cationic and neutral. While the bonding in the framework is of (polar) covalent nature, the guest-host interaction can be ionic, covalent or even van-der Waals, depending on the chemical composition of the clathrates. The chemical composition and structural features of the cationic clathrates can be described by the enhanced Zintl concept, whereas the composition of the anionic clathrates deviates often from the Zintl counts, indicating additional atomic interactions in comparison with the ionic-covalent Zintl model. These interactions can be visualized and studied by applying modern quantum chemical approaches such as electron localizability.

Defects in electro-optically active polymer solids

NASA Technical Reports Server (NTRS)

Martin, David C.

1993-01-01

There is considerable current interest in the application of organic and polymeric materials for electronic and photonic devices. The rapid, non-linear optical (NLO) response of these materials makes them attractive candidates for waveguides, interferometers, and frequency doublers. In order to realize the full potential of these systems, it is necessary to develop processing schemes which can fabricate these molecules into ordered arrangements. There is enormous potential for introducing well-defined, local variations in microstructure to control the photonic properties of organic materials by rational 'defect engineering.' This effort may eventually become as technologically important as the manipulation of the electronic structure of solid-state silicon based devices is at present. The success of this endeavor will require complimentary efforts in the synthesis, processing, and characterization of new materials. Detailed information about local microstructure will be necessary to understand the influence of symmetry breaking of the solid phases near point, line, and planar defects. In metallic and inorganic polycrystalline materials, defects play an important role in modifying macroscopic properties. To understand the influence of particular defects on the properties of materials, it has proven useful to isolate the defect by creating bicrystals between two-component single crystals. In this way the geometry of a grain boundary defect and its effect on macroscopic properties can be determined unambiguously. In crystalline polymers it would be valuable to establish a similar depth of understanding about the relationship between defect structure and macroscopic properties. Conventionally processed crystalline polymers have small crystallites (10-20 nm), which implies a large defect density in the solid state. Although this means that defects may play an important or even dominant role in crystalline or liquid crystalline polymer systems, it also makes it difficult to isolate the effect of a particular boundary on a macroscopically observed property. However, the development of solid-state and thin-film polymerization mechanisms have facilitated the synthesis of highly organized and ordered polymers. These systems provide a unique opportunity to isolate and investigate in detail the structure of covalently bonded solids near defects and the effect of these defects on the properties of the material. The study of defects in solid polymers has been the subject of a recent review (Martin, 1993).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bury, Charles S.; Carmichael, Ian; Garman, Elspeth F.

During macromolecular X-ray crystallography experiments, protein crystals held at 100 K have been widely reported to exhibit reproducible bond scission events at doses on the order of several MGy. With the objective to mitigate the impact of radiation damage events on valid structure determination, it is essential to correctly understand the radiation chemistry mechanisms at play. OH-cleavage from tyrosine residues is regularly cited as amongst the most available damage pathways in protein crystals at 100 K, despite a lack of widespread reports of this phenomenon in protein crystal radiation damage studies. Furthermore, no clear mechanism for phenolic C—O bond cleavagemore » in tyrosine has been reported, with the tyrosyl radical known to be relatively robust and long-lived in both aqueous solutions and the solid state. Here, the initial findings of Tyr –OH group damage in a myrosinase protein crystal have been reviewed. Consistent with that study, at increasing doses, clear electron density loss was detectable local to Tyr –OH groups. A systematic investigation performed on a range of protein crystal damage series deposited in the Protein Data Bank has established that Tyr –OH electron density loss is not generally a dominant damage pathway in protein crystals at 100 K. Full Tyr aromatic ring displacement is here proposed to account for instances of observable Tyr –OH electron density loss, with the original myrosinase data shown to be consistent with such a damage model. Also presented are systematic analysis of the effects of other environmental factors, including solvent accessibility and proximity to disulfide bonds or hydrogen bond interactions. Residues in known active sites showed enhanced sensitivity to radiation-induced disordering, as has previously been reported.« less

OH cleavage from tyrosine: debunking a myth

DOE PAGES

Bury, Charles S.; Carmichael, Ian; Garman, Elspeth F.

2017-01-01

During macromolecular X-ray crystallography experiments, protein crystals held at 100 K have been widely reported to exhibit reproducible bond scission events at doses on the order of several MGy. With the objective to mitigate the impact of radiation damage events on valid structure determination, it is essential to correctly understand the radiation chemistry mechanisms at play. OH-cleavage from tyrosine residues is regularly cited as amongst the most available damage pathways in protein crystals at 100 K, despite a lack of widespread reports of this phenomenon in protein crystal radiation damage studies. Furthermore, no clear mechanism for phenolic C—O bond cleavagemore » in tyrosine has been reported, with the tyrosyl radical known to be relatively robust and long-lived in both aqueous solutions and the solid state. Here, the initial findings of Tyr –OH group damage in a myrosinase protein crystal have been reviewed. Consistent with that study, at increasing doses, clear electron density loss was detectable local to Tyr –OH groups. A systematic investigation performed on a range of protein crystal damage series deposited in the Protein Data Bank has established that Tyr –OH electron density loss is not generally a dominant damage pathway in protein crystals at 100 K. Full Tyr aromatic ring displacement is here proposed to account for instances of observable Tyr –OH electron density loss, with the original myrosinase data shown to be consistent with such a damage model. Also presented are systematic analysis of the effects of other environmental factors, including solvent accessibility and proximity to disulfide bonds or hydrogen bond interactions. Residues in known active sites showed enhanced sensitivity to radiation-induced disordering, as has previously been reported.« less

Local Bonding Influence on the Band Edge and Band Gap Formation in Quaternary Chalcopyrites.

PubMed

Miglio, Anna; Heinrich, Christophe P; Tremel, Wolfgang; Hautier, Geoffroy; Zeier, Wolfgang G

2017-09-01

Quaternary chalcopyrites have shown to exhibit tunable band gaps with changing anion composition. Inspired by these observations, the underlying structural and electronic considerations are investigated using a combination of experimentally obtained structural data, molecular orbital considerations, and density functional theory. Within the solid solution Cu 2 ZnGeS 4- x Se x , the anion bond alteration parameter changes, showing larger bond lengths for metal-selenium than for metal-sulfur bonds. The changing bonding interaction directly influences the valence and conduction band edges, which result from antibonding Cu-anion and Ge-anion interactions, respectively. The knowledge of the underlying bonding interactions at the band edges can help design properties of these quaternary chalcopyrites for photovoltaic and thermoelectric applications.

An ab initio investigation of possible intermediates in the reaction of the hydroxyl and hydroperoxyl radicals

NASA Technical Reports Server (NTRS)

Jackels, C. F.

1985-01-01

Ab initio quantum chemical techniques are used to investigate covalently-bonded and hydrogen-bonded species that may be important intermediates in the reaction of hydroxyl and hydroperoxyl radicals. Stable structures of both types are identified. Basis sets of polarized double zeta quality and large scale configuration interaction wave functions are utilized. Based on electronic energies, the covalently bonded HOOOH species is 26.4 kcal/mol more stable than the OH and HO2 radicals. Similarly, the hydrogen bonded HO---HO2 species has an electronic energy 4.7 kcal/mol below that of the component radicals, after correction is made for the basis set superposition error. The hydrogen bonded form is planar, possesses one relatively normal hydrogen bond, and has the lowest energy 3A' and 1A' states that are essentially degenerate. The 1A" and 3A" excited states produced by rotation of the unpaired OH electron into the molecular plane are very slightly bound.

The Structure and Bonding State for Fullerene-Like Carbon Nitride Films with High Hardness Formed by Electron Cyclotron Resonance Plasma Sputtering

NASA Astrophysics Data System (ADS)

Kamata, Tomoyuki; Niwa, Osamu; Umemura, Shigeru; Hirono, Shigeru

2012-12-01

We studied pure carbon films and carbon nitride (CN) films by using electron cyclotron resonance (ECR) sputtering. The main feature of this method is high density ion irradiation during deposition, which enables the pure carbon films to have fullerene-like (FL) structures without nitrogen incorporation. Furthermore, without substrate heating, the ECR sputtered CN films exhibited an enhanced FL microstructure and hardness comparable to that of diamond at intermediate nitrogen concentration. This microstructure consisted of bent and cross-linked graphene sheets where layered areas remarkably decreased due to increased sp3 bonding. Under high nitrogen concentration conditions, the CN films demonstrated extremely low hardness because nitrile bonding not only decreased the covalent-bonded two-dimensional hexagonal network but also annihilated the bonding there. By evaluating lattice images obtained by transmission electron microscopy and the bonding state measured by X-ray photoelectron spectroscopy, we classified the ECR sputtered CN films and offered phase diagram and structure zone diagram.

Probing the electronic structures of [Cu2(mu-XR2)]n+ diamond cores as a function of the bridging X atom (X = N or P) and charge (n = 0, 1, 2).

PubMed

Harkins, Seth B; Mankad, Neal P; Miller, Alexander J M; Szilagyi, Robert K; Peters, Jonas C

2008-03-19

A series of dicopper diamond core complexes that can be isolated in three different oxidation states ([Cu2(mu-XR2)]n+, where n = 0, 1, 2 and X = N or P) is described. Of particular interest is the relative degree of oxidation of the respective copper centers and the bridging XR2 units, upon successive oxidations. These dicopper complexes feature terminal phosphine and either bridging amido or phosphido donors, and as such their metal-ligand bonds are highly covalent. Cu K-edge, Cu L-edge, and P K-edge spectroscopies, in combination with solid-state X-ray structures and DFT calculations, provides a complementary electronic structure picture for the entire set of complexes that tracks the involvement of a majority of ligand-based redox chemistry. The electronic structure picture that emerges for these inorganic dicopper diamond cores shares similarities with the Cu2(mu-SR)2 CuA sites of cytochrome c oxidases and nitrous oxide reductases.

Low-lying singlet states of carotenoids having 8-13 conjugated double bonds as determined by electronic absorption spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo; Koyama, Yasushi; Nagae, Hiroyoshi; Nishio, Tomohiro; Hashimoto, Hideki; Zhang, Jian-Ping

2005-07-01

Electronic absorption spectra were recorded at room temperature in solutions of carotenoids having different numbers of conjugated double bonds, n = 8-13, including a spheroidene derivatives, neurosporene, spheroidene, lycopene, anhydrorhodovibrin and spirilloxanthin. The vibronic states of 1Bu+(v=0-4), 2Ag-(v=0-3), 3Ag- (0) and 1Bu- (0) were clearly identified. The arrangement of the four electronic states determined by electronic absorption spectroscopy was identical to that determined by measurement of resonance Raman excitation profiles [K. Furuichi et al., Chem. Phys. Lett. 356 (2002) 547] for carotenoids in crystals.

ULTRAFAST CHEMISTRY: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics

NASA Astrophysics Data System (ADS)

Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud

2005-05-01

Time-resolved infrared (IR) and Raman spectroscopy elucidates molecular structure evolution during ultrafast chemical reactions. Following vibrational marker modes in real time provides direct insight into the structural dynamics, as is evidenced in studies on intramolecular hydrogen transfer, bimolecular proton transfer, electron transfer, hydrogen bonding during solvation dynamics, bond fission in organometallic compounds and heme proteins, cis-trans isomerization in retinal proteins, and transformations in photochromic switch pairs. Femtosecond IR spectroscopy monitors the site-specific interactions in hydrogen bonds. Conversion between excited electronic states can be followed for intramolecular electron transfer by inspection of the fingerprint IR- or Raman-active vibrations in conjunction with quantum chemical calculations. Excess internal vibrational energy, generated either by optical excitation or by internal conversion from the electronic excited state to the ground state, is observable through transient frequency shifts of IR-active vibrations and through nonequilibrium populations as deduced by Raman resonances.

A new pseudopolymorph of diphenic acid and 4,4‧-bipyridine co-crystal: Structural and theoretical study

NASA Astrophysics Data System (ADS)

Soleimannejad, Janet; Nazarnia, Esfandiar; Stoeckli-Evans, Helen

2014-11-01

A new pseudopolymorph (B; tetragonal, I41/acd) of the cocrystal biphenyl-2,2‧-dicarboxylic acid (diphenic acid) and 4,4‧-bipyridine was synthesized. Its solid-state structure and supramolecular synthons responsible for extending the supramolecular network have been compared with those of the previously reported polymorph (A; triclinic, P1bar). DFT calculations at the B3LYP/6-311G++ (2d,2p) level have been performed. Energies of the intermolecular hydrogen bonds in the crystal structure were calculated and their electronic aspects were investigated by NBO and AIM analysis.

First principles Study on Transparent High-Tc Superconductivity in hole-doped Delafossite CuAlO2

NASA Astrophysics Data System (ADS)

Nakanishi, Akitaka; Katayama-Yoshida, Hiroshi

2012-02-01

The CuAlO2 is the transparent p-type conductor without any intentional doping. Transparent superdoncutivity and high thermoelectric power are suggested in p-type CuAlO2 [1]. Katayama-Yoshida et al. proposed that it may cause a strong electron-phonon interaction and a superconductivity. But, the calculation of superconducting critical temperature Tc is not performed. We performed the first principles calculation about the Tc of hole-doped CuAlO2 by shifting the Fermi level rigidly. In lightly hole-doped CuAlO2, the Fermi level is located at Cu and O anti-bonding band. The electrons of this band strongly interact with the A1L1 phonon mode because the direction of O-Cu-O dumbbell is parallel to the oscillation direction of the A1L1 phonon mode. As a result, Tc of lightly hole-doped CuAlO2 is about 50 K. We also discuss the materials design to enhance the Tc based on the charge-excitation-induced negative effective U system.[4pt] [1] H. Katayama-Yoshida, T. Koyanagi, H. Funashima, H. Harima, A. Yanase: Solid State Communication 126 (2003) 135. [0pt] [2] A. Nakanishi and H. Katayama-Yoshida: Solid State Communication, in printing. (arXiv:1107.2477v3

Exploring the color of transition metal ions in irregular coordination geometries: new colored inorganic oxides based on the spiroffite structure, Zn(2-x)M(x)Te3O8 (M = Co, Ni, Cu).

PubMed

Tamilarasan, S; Sarma, Debajit; Bhattacharjee, S; Waghmare, U V; Natarajan, S; Gopalakrishnan, J

2013-05-20

We describe the synthesis, crystal structures, and optical absorption spectra of transition metal-substituted spiroffite derivatives, Zn(2-x)M(x)Te3O8 (M(II) = Co, Ni, Cu; 0 < x ≤ 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620 °C. Reitveld refinement of the crystal structures from powder X-ray diffraction (XRD) data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/M(II)-O bonds (1.898-2.236 Å) and one longer Zn/M(II)-O bond (2.356-2.519 Å). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn(2-x)M(x)Te3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/M(II)-O chromophores. We could not however prepare the fully substituted M2Te3O8 (M(II) = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn(2-x)M(x)Te3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions.

Novel ethylenediamine-gallium phosphate containing 6-fold coordinated gallium atoms with unusual four equatorial Ga–N bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Torre-Fernández, Laura; Espina, Aránzazu; Khainakov, Sergei A.

2014-07-01

A novel ethylenediamine-gallium phosphate, formulated as Ga(H{sub 2}NCH{sub 2}CH{sub 2}NH{sub 2}){sub 2}PO{sub 4}·2H{sub 2}O, was synthesized under hydrothermal conditions. The crystal structure, including hydrogen positions, was determined using single-crystal X-ray diffraction data (monoclinic, a=9.4886(3) Å, b=6.0374(2) Å, c=10.2874(3) Å, and β=104.226(3)°, space group Pc) and the bulk was characterized by chemical (Ga–P–C–H–N) and thermal analysis (TG–MS and DSC), including activation energy data of its thermo-oxidative degradation, powder X-ray diffraction (PXRD), solid-state nuclear magnetic resonance (SS-NMR) measurements, and transmission electron microscopy (TEM, SAED/NBD, and STEM BF-EDX). The crystal structure is built up of infinite zig-zag chains running along the c-axis, formedmore » by vertex-shared (PO{sub 4}) and (GaO{sub 2}N{sub 4}) polyhedra. The new compound is characterized by unusual four equatorial Ga–N bonds coming from two nonequivalent ethylenediamine molecules and exhibits strong blue emission at 430 nm (λ{sub ex}=350 nm) in the solid state at room temperature. - Graphical abstract: Single crystals of a new ethylenediamine-gallium phosphate, Ga(H{sub 2}NCH{sub 2}CH{sub 2}NH{sub 2}){sub 2}PO{sub 4}·2H{sub 2}O, were obtained and the structural features presented. This structure is one of the scarce examples of GaPO with Ga–N bonds reported. - Highlights: • A novel ethylenediamine-gallium phosphate was hydrothermally synthesized. • The new compound is characterized by unusual four equatorial Ga–N bonds. • Void-volume analysis shows cages and channels with sizes ideally suited to accommodate small molecules. • The new compound exhibits strong blue emission.« less

Molecular Functionalization of Graphene Oxide for Next-Generation Wearable Electronics.

PubMed

Zarrin, Hadis; Sy, Serubbabel; Fu, Jing; Jiang, Gaopeng; Kang, Keunwoo; Jun, Yun-Seok; Yu, Aiping; Fowler, Michael; Chen, Zhongwei

2016-09-28

Acquiring reliable and efficient wearable electronics requires the development of flexible electrolyte membranes (EMs) for energy storage systems with high performance and minimum dependency on the operating conditions. Herein, a freestanding graphene oxide (GO) EM is functionalized with 1-hexyl-3-methylimidazolium chloride (HMIM) molecules via both covalent and noncovalent bonds induced by esterification reactions and electrostatic πcation-π stacking, respectively. Compared to the commercial polymeric membrane, the thin HMIM/GO membrane demonstrates not only slightest performance sensitivity to the operating conditions but also a superior hydroxide conductivity of 0.064 ± 0.0021 S cm(-1) at 30% RH and room temperature, which was 3.8 times higher than that of the commercial membrane at the same conditions. To study the practical application of the HMIM/GO membranes in wearable electronics, a fully solid-state, thin, flexible zinc-air battery and supercapacitor are made exhibiting high battery performance and capacitance at low humidified and room temperature environment, respectively, favored by the bonded HMIM molecules on the surface of GO nanosheets. The results of this study disclose the strong potential of manipulating the chemical structure of GO to work as a lightweight membrane in wearable energy storage devices, possessing highly stable performance at different operating conditions, especially at low relative humidity and room temperature.

Two-Center/Three-Electron Sigma Half-Bonds in Main Group and Transition Metal Chemistry.

PubMed

Berry, John F

2016-01-19

First proposed in a classic Linus Pauling paper, the two-center/three-electron (2c/3e) σ half-bond challenges the extremes of what may or may not be considered a chemical bond. Two electrons occupying a σ bonding orbital and one electron occupying the antibonding σ* orbital results in bond orders of ∼0.5 that are characteristic of metastable and exotic species, epitomized in the fleetingly stable He2(+) ion. In this Account, I describe the use of coordination chemistry to stabilize such fugacious three-electron bonded species at disparate ends of the periodic table. A recent emphasis in the chemistry of metal-metal bonds has been to prepare compounds with extremely short metal-metal distances and high metal-metal bond orders. But similar chemistry can be used to explore metal-metal bond orders less than one, including 2c/3e half-bonds. Bimetallic compounds in the Ni2(II,III) and Pd2(II,III) oxidation states were originally examined in the 1980s, but the evidence collected at that time suggested that they did not contain 2c/3e σ bonds. Both classes of compounds have been re-examined using EPR spectroscopy and modern computational methods that show the unpaired electron of each compound to occupy a M-M σ* orbital, consistent with 2c/3e Ni-Ni and Pd-Pd σ half-bonds. Elsewhere on the periodic table, a seemingly unrelated compound containing a trigonal bipyramidal Cu3S2 core caused a stir, leaving prominent theorists at odds with one another as to whether the compound contains a S-S bond. Due to my previous experience with 2c/3e metal-metal bonds, I suggested that the Cu3S2 compound could contain a 2c/3e S-S σ half-bond in the previously unknown oxidation state of S2(3-). By use of the Cambridge Database, a number of other known compounds were identified as potentially containing S2(3-) ligands, including a noteworthy set of cyclopentadienyl-supported compounds possessing diamond-shaped Ni2E2 units with E = S, Se, and Te. These compounds were subjected to extensive studies using X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, density functional theory, and wave function-based computational methods, as well as chemical oxidation and reduction. The compounds contain E-E 2c/3e σ half-bonds and unprecedented E2(3-) "subchalcogenide" ligands, ushering in a new oxidation state paradigm for transition metal-chalcogen chemistry.

The Chemical Bond and Solid-state Physics

ERIC Educational Resources Information Center

Phillips, James C.

1970-01-01

Proposes a new scale of ionicity, with which the ionic character of bonding in crystals can be predicted and measured. This new scale of ionicity has led to improved understanding of such crystalline properties as lattice structure, heats of formation, elastic constants, and nonlinear optical properties. Bibliography. (LC)

NMR Investigations of Noncovalent Carbon Tetrel Bonds. Computational Assessment and Initial Experimental Observation.

PubMed

Southern, Scott A; Bryce, David L

2015-12-10

Group IV tetrel elements may act as tetrel bond donors, whereby a region of positive electrostatic potential (σ-hole) interacts with a Lewis base. The results of calculations of NMR parameters are reported for a series of model compounds exhibiting tetrel bonding from a methyl carbon to the oxygen or nitrogen atoms in various functional groups. The (13)C chemical shift (δiso) and the (1c)J((13)C,Y) coupling (Y = (17)O, (15)N) across the tetrel bond are recorded as a function of geometry. The sensitivity of the NMR parameters to the noncovalent interaction is demonstrated via an increase in δiso and in |(1c)J((13)C,Y)| as the tetrel bond shortens. Gauge-including projector-augmented wave density functional theory (DFT) calculations of δiso are reported for crystals that exhibit tetrel bonding in the solid state. Experimental δiso values for solid sarcosine and its tetrel-bonded salts corroborate the computational findings. This work offers new insights into tetrel bonding and facilitates the incorporation of tetrel bonds as restraints in NMR crystallographic structure refinement.

Conformational state of β-hydroxynaphthylamides: Barriers for the rotation of the amide group around CN bond and dynamics of the morpholine ring

NASA Astrophysics Data System (ADS)

Kozlecki, Tomasz; Tolstoy, Peter M.; Kwocz, Agnieszka; Vovk, Mikhail A.; Kochel, Andrzej; Polowczyk, Izabela; Tretyakov, Peter Yu.; Filarowski, Aleksander

2015-10-01

Three β-hydroxynaphthylamides (morpholine, pyrrolidine and dimethylamine derivatives) have been synthesized and their conformational state was analyzed by NMR, X-ray and DFT calculations. In aprotic solution the molecules contain intramolecular OHO hydrogen bonds, which change into intermolecular ones in solid state. The energy barriers for the amide group rotation around the CN bond were estimated from the line shape analysis of 1H and 13C NMR signals. A tentative correlation between the barrier height and the strength of OHO bond was proposed. Calculations of the potential energy profiles for the rotations around CC and CN bonds were done. In case of morpholine derivative experimental indications of additional dynamics: chair-chair 'ring flip' in combination with the twisting around CC bond were obtained and confirmed by quantum chemistry calculations.

A comparative study of the hydrogen-bonding patterns and prototropism in solid 2-thiocytosine (potential antileukemic agent) and cytosine, as studied by 1H-14N NQDR and QTAIM/ DFT.

PubMed

Latosińska, Jolanta N; Seliger, Janez; Zagar, Veselko; Burchardt, Dorota V

2012-01-01

A potential antileukemic and anticancer agent, 2-thiocytosine (2-TC), has been studied experimentally in the solid state by (1)H-(14)N NMR-NQR double resonance (NQDR) and theoretically by the quantum theory of atoms in molecules (QTAIM)/density functional theory (DFT). Eighteen resonance frequencies on (14)N were detected at 180 K and assigned to particular nitrogen sites (-NH(2), -N=, and -NH-) in 2-thiocytosine. Factors such as the nonequivalence of molecules (connected to the duplication of sites) and possible prototropic tautomerism (capable of modifying the type of site due to proton transfer) were taken into account during frequency assignment. The result of replacing oxygen with sulfur, which leads to changes in the intermolecular interaction pattern and molecular aggregation, is discussed. This study demonstrates the advantages of combining NQDR and DFT to extract detailed information on the H-bonding properties of crystals with complex H-bonding networks. Solid-state properties were found to have a profound impact on the stabilities and reactivities of both compounds.

Reflections on the value of electron microscopy in the study of heterogeneous catalysts

PubMed Central

2017-01-01

Electron microscopy (EM) is arguably the single most powerful method of characterizing heterogeneous catalysts. Irrespective of whether they are bulk and multiphasic, or monophasic and monocrystalline, or nanocluster and even single-atom and on a support, their structures in atomic detail can be visualized in two or three dimensions, thanks to high-resolution instruments, with sub-Ångstrom spatial resolutions. Their topography, tomography, phase-purity, composition, as well as the bonding, and valence-states of their constituent atoms and ions and, in favourable circumstances, the short-range and long-range atomic order and dynamics of the catalytically active sites, can all be retrieved by the panoply of variants of modern EM. The latter embrace electron crystallography, rotation and precession electron diffraction, X-ray emission and high-resolution electron energy-loss spectra (EELS). Aberration-corrected (AC) transmission (TEM) and scanning transmission electron microscopy (STEM) have led to a revolution in structure determination. Environmental EM is already playing an increasing role in catalyst characterization, and new advances, involving special cells for the study of solid catalysts in contact with liquid reactants, have recently been deployed. PMID:28265196

Bond-order potential for magnetic body-centered-cubic iron and its transferability

NASA Astrophysics Data System (ADS)

Lin, Yi-Shen; Mrovec, M.; Vitek, V.

2016-06-01

We derived and thoroughly tested a bond-order potential (BOP) for body-centered-cubic (bcc) magnetic iron that can be employed in atomistic calculations of a broad variety of crystal defects that control structural, mechanical, and thermodynamic properties of this technologically important metal. The constructed BOP reflects correctly the mixed nearly free electron and covalent bonding arising from the partially filled d band as well as the ferromagnetism that is actually responsible for the stability of the bcc structure of iron at low temperatures. The covalent part of the cohesive energy is determined within the tight-binding bond model with the Green's function of the Schrödinger equation determined using the method of continued fractions terminated at a sufficient level of the moments of the density of states. This makes the BOP an O (N ) method usable for very large numbers of particles. Only d d bonds are included explicitly, but the effect of s electrons on the covalent energy is included via their screening of the corresponding d d bonds. The magnetic part of the cohesive energy is included using the Stoner model of itinerant magnetism. The repulsive part of the cohesive energy is represented, as in any tight-binding scheme, by an empirical formula. Its functional form is physically justified by studies of the repulsion in face-centered-cubic (fcc) solid argon under very high pressure where the repulsion originates from overlapping s and p closed-shell electrons just as it does from closed-shell s electrons in transition metals squeezed into the ion core under the influence of the large covalent d bonding. Testing of the transferability of the developed BOP to environments significantly different from those of the ideal bcc lattice was carried out by studying crystal structures and magnetic states alternative to the ferromagnetic bcc lattice, vacancies, divacancies, self-interstitial atoms (SIAs), paths continuously transforming the bcc structure to different less symmetric structures and phonons. The results of these calculations are compared with either experiments or calculations based on the density functional theory (DFT), and they all show very good agreement. Importantly, the lowest energy configuration of SIAs agrees with DFT calculations that show that it is an exception within bcc transition metals controlled by magnetism. Moreover, the migration energy of interstitials is significantly lower than that of vacancies, which is essential for correct analysis of the effects of irradiation. Finally, the core structure and glide of ½ <111 > screw dislocations that control the plastic flow in single crystals of bcc metals was explored. The results fully agree with available DFT based studies and with experimental observations of the slip geometry of bcc iron at low temperatures.

Quantum chemistry study on the open end of single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Hou, Shimin; Shen, Ziyong; Zhao, Xingyu; Xue, Zengquan

2003-05-01

Geometrical and electronic structures of open-ended single-walled carbon nanotubes (SWCNTs) are calculated using density functional theory (DFT) with hybrid functional (B3LYP) approximation. Due to different distances between carbon atoms along the edge, reconstruction occurs at the open end of the (4,4) armchair SWCNT, i.e., triple bonds are formed in the carbon atom pairs at the mouth; however, for the (6,0) zigzag SWCNT, electrons in dangling bonds still remain at 'no-bonding' states. The ionization potential (IP) of both (4,4) and (6,0) SWCNTs is increased by their negative intrinsic dipole moments, and localized electronic states existed at both of their open ends.

Frontiers of More than Moore in Bioelectronics and the Required Metrology Needs

NASA Astrophysics Data System (ADS)

Guiseppi-Elie, Anthony; Kotanen, Christian; Wilson, A. Nolan

2011-11-01

Silicon's intersection with biology is a premise inherent in Moore's prediction. Distinct from biologically inspired molecular logic and storage devices (more Moore) are the integration of solid state electronic devices with the soft condensed state of the body (more than Moore). Developments in biomolecular recognition events per sq. cm parallel those of Moore's Law. However, challenges continue in the area of "More than Moore". Two grand challenge problems must be addressed—the biocompatibility of synthetic materials with the myriad of tissue types within the human body and the interfacing of solid state micro- and nano-electronic devices with the electronics of biological systems. Electroconductive hydrogels have been developed as soft, condensed, biomimetic but otherwise inherently electronically conductive materials to address the challenge of interfacing solid state devices with the electronics of the body, which is predominantly ionic. Nano-templated interfaces via the oriented immobilization of single walled carbon nanotubes (SWCNTs) onto metallic electrodes have engendered reagentless, direct electron transfer between biological redox enzymes and solid state electrodes. In addressing these challenges, metrology needs and opportunities are found in such widely diverse areas as single molecule counting and addressing, sustainable power requirements such as the development of implantable biofuel cells for the deployment of implantable biochips, and new manufacturing paradigms to address plura-biology needs on solid state devices.

Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods.

PubMed

Siskos, Michael G; Choudhary, M Iqbal; Gerothanassis, Ioannis P

2017-03-07

The exact knowledge of hydrogen atomic positions of O-H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i) density functional theory (DFT) calculations after a structure has been determined by X-ray from single crystals or from powders; (ii) ¹H-NMR chemical shifts as constraints in DFT calculations, and (iii) use of root-mean-square deviation between experimentally determined and DFT calculated ¹H-NMR chemical shifts considering the great sensitivity of ¹H-NMR shielding to hydrogen bonding properties.

ISDRS 2016 special issue foreword

NASA Astrophysics Data System (ADS)

Iliadis, Agis A.; Akturk, Akin; Tompkins, Randy P.

2017-10-01

This 8th ISDRS Special Issue of Solid-State Electronics contains manuscripts presented at the 2016 International Semiconductor Device Research Symposium (ISDRS 2016) that was held at the Hyatt Regency Hotel, in Bethesda, Maryland, on December 7-9, 2016. A total of 32 manuscripts were submitted, which were sent out for review by both the ISDRS Guest Editors, Agis Iliadis, Akin Akturk, Randy Tompkins, and the Solid-State Electronics Editor, Alex Zaslavsky. This ISDRS Special Issue of Solid-State Electronics contains the manuscripts selected through this rigorous review process.

Innovative design and material solutions of thermal contact layers for high heat flux applications in fusion devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Federici, G.; Matera, R.; Chiocchio, S.

1994-11-01

One difficulty associated with the design and development of sacrificial plasma facing components that have to handle the high heat and particle fluxes in ITER is achieving the necessary contact conductance between the plasma protection material and the high-conductivity substrate in contact with the coolant. This paper presents a novel bond idea which is proposed as one of the options for the sacrificial energy dump targets located at the bottom of the divertor legs. The bonded joint in this design concept provides thermal and electrical contact between the armour and the cooled sub-structure while promoting remote, in-situ maintenance repair andmore » an easy replaceability of the armour part without disturbing the cooling pipes or rewelding neutron irradiated materials. To provide reliable and demountable adhesion, the bond consists of a metal alloy, treated in the semi-solid phase so that it leads to a fine dispersion of a globular solid phase into a liquid matrix (rheocast process). This thermal bond layer would normally operate in the solid state but could be brought reversibly to the semi-solid state during the armour replacement simply by heating it slightly above its solidus temperature. Material and design options are discussed in this paper. Possible methods of installation and removal are described, and lifetime considerations are addressed. In order to validate this concept within the ITER time-frame, a R&D programme must be rapidly implemented.« less

Tautomeric and ionisation forms of dopamine and tyramine in the solid state

NASA Astrophysics Data System (ADS)

Cruickshank, Laura; Kennedy, Alan R.; Shankland, Norman

2013-11-01

Crystallisation of the phenylethylamine neurotransmitter dopamine from basic aqueous solution yielded the 3-phenoxide Zwitterionic tautomer, despite this being a minority form in the solution state. In the crystal structure, dopamine has a dimeric [OCCOH]2 hydrogen bonded catechol motif that expands through Nsbnd H⋯O interactions to give a 2-dimensional sheet of classical hydrogen bonds. These sheets are further interconnected by Nsbnd H⋯π interactions. The structurally related base tyramine crystallises under similar conditions as a hemihydrate with all four possible species of tyramine present (cationic, anionic, Zwitterionic and neutral) in the crystal structure. Single crystal X-ray diffraction studies at 121 and 293 K showed dynamic hydrogen atom disorder for the phenol/phenoxide group, suggesting that the tyramine speciation observed arises from a solid-state process.

Organic solid state optical switches and method for producing organic solid state optical switches

DOEpatents

Wasielewski, M.R.; Gaines, G.L.; Niemczyk, M.P.; Johnson, D.G.; Gosztola, D.J.; O`Neil, M.P.

1993-01-01

This invention consists of a light-intensity dependent molecular switch comprised of a compound which shuttles an electron or a plurality of electrons from a plurality of electron donors to an electron acceptor upon being stimulated with light of predetermined wavelengths, and a method for making said compound.

Effect of Bonding Temperature on Interfacial Reaction and Mechanical Properties of Diffusion-Bonded Joint Between Ti-6Al-4V and 304 Stainless Steel Using Nickel as an Intermediate Material

NASA Astrophysics Data System (ADS)

Thirunavukarasu, Gopinath; Kundu, Sukumar; Mishra, Brajendra; Chatterjee, Subrata

2014-04-01

An investigation was carried out on the solid-state diffusion bonding between Ti-6Al-4V (TiA) and 304 stainless steel (SS) using pure nickel (Ni) of 200- μm thickness as an intermediate material prepared in vacuum in the temperature range from 973 K to 1073 K (700 °C to 800 °C) in steps of 298 K (25 °C) using uniaxial compressive pressure of 3 MPa and 60 minutes as bonding time. Scanning electron microscopy images, in backscattered electron mode, had revealed existence of layerwise Ti-Ni-based intermetallics such as either Ni3Ti or both Ni3Ti and NiTi at titanium alloy-nickel (TiA/Ni) interface, whereas nickel-stainless steel (Ni/SS) diffusion zone was free from intermetallic phases for all joints processed. Chemical composition of the reaction layers was determined in atomic percentage by energy dispersive spectroscopy and confirmed by X-ray diffraction study. Room-temperature properties of the bonded joints were characterized using microhardness evaluation and tensile testing. The maximum hardness value of ~800 HV was observed at TiA/Ni interface for the bond processed at 1073 K (800 °C). The hardness value at Ni/SS interface for all the bonds was found to be ~330 HV. Maximum tensile strength of ~206 MPa along with ~2.9 pct ductility was obtained for the joint processed at 1023 K (750 °C). It was observed from the activation study that the diffusion rate at TiA/Ni interface is lesser than that at the Ni/SS interface. From microhardness profile, fractured surfaces and fracture path, it was demonstrated that failure of the joints was initiated and propagated apparently at the TiA/Ni interface near Ni3Ti intermetallic phase.

Two-electron bond-orbital model, 1

NASA Technical Reports Server (NTRS)

Huang, C.; Moriarty, J. A.; Sher, A.; Breckenridge, R. A.

1975-01-01

Harrison's one-electron bond-orbital model of tetrahedrally coordinated solids was generalized to a two-electron model, using an extension of the method of Falicov and Harris for treating the hydrogen molecule. The six eigenvalues and eigenstates of the two-electron anion-cation Hamiltonian entering this theory can be found exactly general. The two-electron formalism is shown to provide a useful basis for calculating both non-magnetic and magnetic properties of semiconductors in perturbation theory. As an example of the former, expressions for the electric susceptibility and the dielectric constant were calculated. As an example of the latter, new expressions for the nuclear exchanges and pseudo-dipolar coefficients were calculated. A simple theoretical relationship between the dielectric constant and the exchange coefficient was also found in the limit of no correlation. These expressions were quantitatively evaluated in the limit of no correlation for twenty semiconductors.

Enhanced van der Waals epitaxy via electron transfer enabled interfacial dative bond formation

DOE PAGES

Xie, Weiyu; Lu, Toh -Ming; Wang, Gwo -Ching; ...

2017-11-14

Enhanced van der Waals (vdW) epitaxy of semiconductors on a layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe 2 is a vdW layeredmaterial, first-principles calculations reveal that the bond strength at a CdTe-NbSe 2 interface is five times as large as that of vdW interactions at a CdTe-graphene interface. Finally, the unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at a CdTe surface to metallic nonbonding NbSe 2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

Enhanced van der Waals epitaxy via electron transfer enabled interfacial dative bond formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xie, Weiyu; Lu, Toh -Ming; Wang, Gwo -Ching

Enhanced van der Waals (vdW) epitaxy of semiconductors on a layered vdW substrate is identified as the formation of dative bonds. For example, despite that NbSe 2 is a vdW layeredmaterial, first-principles calculations reveal that the bond strength at a CdTe-NbSe 2 interface is five times as large as that of vdW interactions at a CdTe-graphene interface. Finally, the unconventional chemistry here is enabled by an effective net electron transfer from Cd dangling-bond states at a CdTe surface to metallic nonbonding NbSe 2 states, which is a necessary condition to activate the Cd for enhanced binding with Se.

Fundamental aspects of recoupled pair bonds. I. Recoupled pair bonds in carbon and sulfur monofluoride

NASA Astrophysics Data System (ADS)

Dunning, Thom H.; Xu, Lu T.; Takeshita, Tyler Y.

2015-01-01

The number of singly occupied orbitals in the ground-state atomic configuration of an element defines its nominal valence. For carbon and sulfur, with two singly occupied orbitals in their 3P ground states, the nominal valence is two. However, in both cases, it is possible to form more bonds than indicated by the nominal valence—up to four bonds for carbon and six bonds for sulfur. In carbon, the electrons in the 2s lone pair can participate in bonding, and in sulfur the electrons in both the 3p and 3s lone pairs can participate. Carbon 2s and sulfur 3p recoupled pair bonds are the basis for the tetravalence of carbon and sulfur, and 3s recoupled pair bonds enable sulfur to be hexavalent. In this paper, we report generalized valence bond as well as more accurate calculations on the a4Σ- states of CF and SF, which are archetypal examples of molecules that possess recoupled pair bonds. These calculations provide insights into the fundamental nature of recoupled pair bonds and illustrate the key differences between recoupled pair bonds formed with the 2s lone pair of carbon, as a representative of the early p-block elements, and recoupled pair bonds formed with the 3p lone pair of sulfur, as a representative of the late p-block elements.

A Comparative Study of Gold Bonding via Electronic Spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Ruohan

The bonding and electrostatic properties of gold containing molecules are highly influenced by relativistic effects. To understand this facet on bonding, a series of simple diatomic AuX (X=F, Cl, O and S) molecules, where upon bond formation the Au atom donates or accepts electrons, was investigated and discussed in this thesis. First, the optical field-free, Stark, and Zeeman spectroscopic studies have been performed on AuF and AuCl. The simple polar bonds between Au and typical halogens (i.e. F and Cl) can be well characterized by the electronic structure studies and the permanent electric dipole moments, mu el. The spectroscopic parameters have been precisely determined for the [17.7]1, [17.8]0+ and X1Sigma + states of AuF, and the [17.07]1, [17.20]0+ and X1Sigma+ states of AuCl. The mu el have been determined for ground and excited states of AuF and AuCl. The results from the hyperfine analysis and Stark measurement support the assignments that the [17.7]1 and [17.8]0+ states of AuF are the components of a 3pi state. Similarly, the analysis demonstrated the [19.07]1 and [19.20]0+ states are the components of the 3pi state of AuCl. Second, my study focused on AuO and AuS because the bonding between gold and sulfur/oxygen is a key component to numerous established and emerging technologies that have applications as far ranging as medical imaging, catalysis, electronics, and material science. The high-resolution spectra were record and analyzed to obtain the geometric and electronic structural data for the ground and excited states. The electric dipole moment, muel , and the magnetic dipole moment, mum, has been the precisely measured by applying external static electric and magnetic fields. muel and mum are used to give insight into the unusual complex bonding in these molecules. In addition to direct studies on the gold-containing molecules, other studies of related molecules are included here as well. These works contain the pure rotation measurement of PtC, the hyperfine and Stark spectroscopic studies of PtF, and the Stark and Zeeman spectroscopic studies of MgH and MgD. Finally, a perspective discussion and conclusion will summarize the results of AuF, AuCl, AuO, and AuS from this work (bond lengths, dipole moment, etc.). The highly quantitative information derived from this work is the foundation of a chemical description of matter and essential for kinetic energy manipulation via Stark and Zeeman interactions. This data set also establishes a synergism with computation chemists who are developing new methodologies for treating relativistic effects and electron correlation.

Influence of drying restraint on physical and mechanical properties of nanofibrillated cellulose films

Treesearch

Carlos Baez; John Considine; Robert Rowlands

2014-01-01

Nanofibrillated cellulose (NFC) is a renewable and biodegradable fibril that possesses high strength and stiffness resulting from high level hydrogen bonding. Films made from NFC shrink and distort as they transition from a wet state (20 wt% solids) to a state of moisture equilibrium (90 wt% solids at 50 % RH, 23 °C). Material distortions are driven by development of...

PREFACE Surface Modifications of Diamond and Related Materials (Session D, E-MRS Spring Meeting)

NASA Astrophysics Data System (ADS)

Nebel, Christoph E.

2010-11-01

This special issue contains selected papers which were presented at the E-MRS Symposium BIOMATERIALS, SENSORS & SURFACES, D: 'Surface modifications of diamond and related materials' which was held on 7-9 June 2010 in Strasbourg (France). With about 54 oral and poster presentations given from teams all over the world it was a very interesting, dense and lively meeting. The symposium focused on chemical modifications applied to graft surfaces of diamond, nano-diamond particles, diamond-like carbon, graphene, graphite and carbon nano-tubes with linker molecular layers for realization of bio-sensors, bio-markers, separation techniques, and switchable chemical links. Presented techniques span spontaneous bonding to photo-chemical attachment, electrochemical modifications, to Suzuki-coupling of aryl molecules. Special attention was drawn to mechanisms driving bonding kinetics such as electron transfer reactions, hydrogen cleavage reactions by nucleophilic molecules and growths schemas which vary from correlated two-dimensional chain reactions to three-dimensional cross polymerization. Hydrogen terminations, surface defects, surface roughness and atomic arrangements of surface carbon atoms were of interest to elucidate bonding mechanisms. In addition, bonding stability, either of linker molecules or of complex functionalized surfaces with DNA, proteins and enzymes was discussed by several speakers as well as details of the electronic interfaces between solid transducers and bio-layers. Here the characterization of surface and interface defect densities, of Fermi level pinning and of electron transfer rates was a major topic. Miniaturization of sensor area and application of new detection schemas was discussed. Diamond nano-particles which are increasingly used as biomarkers in drug delivery experiments also attracted attention. The organizers express our gratitude to the international members of the scientific committee who actively contributed to ensure an attractive program in proposing invited speakers. Finally, our symposium would not have been successful without the strong involvement and implication of the EMRS headquarter especially P Siffert, T Lippert, S Schoeffter and C Kocher. They will all find here our sincere thanks. Christoph E Nebel (Chair) Fraunhofer-Institute for Applied Solid State Physics (IAF), Germany Takako Nakamura National Institute of Advanced Industrial Science and Technology (AIST), Japan Philippe Bergonzo CEA-LIST, France John Foord University of Oxford, United Kingdom Kian-Ping Loh National University of Singapore, Singapore

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammells, Anthony F.

2005-09-27

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

Solid state oxygen anion and electron mediating membrane and catalytic membrane reactors containing them

DOEpatents

Schwartz, Michael; White, James H.; Sammels, Anthony F.

2000-01-01

This invention relates to gas-impermeable, solid state materials fabricated into membranes for use in catalytic membrane reactors. This invention particularly relates to solid state oxygen anion- and electron-mediating membranes for use in catalytic membrane reactors for promoting partial or full oxidation of different chemical species, for decomposition of oxygen-containing species, and for separation of oxygen from other gases. Solid state materials for use in the membranes of this invention include mixed metal oxide compounds having the brownmillerite crystal structure.

Ab initio molecular crystal structures, spectra, and phase diagrams.

PubMed

Hirata, So; Gilliard, Kandis; He, Xiao; Li, Jinjin; Sode, Olaseni

2014-09-16

Conspectus Molecular crystals are chemists' solids in the sense that their structures and properties can be understood in terms of those of the constituent molecules merely perturbed by a crystalline environment. They form a large and important class of solids including ices of atmospheric species, drugs, explosives, and even some organic optoelectronic materials and supramolecular assemblies. Recently, surprisingly simple yet extremely efficient, versatile, easily implemented, and systematically accurate electronic structure methods for molecular crystals have been developed. The methods, collectively referred to as the embedded-fragment scheme, divide a crystal into monomers and overlapping dimers and apply modern molecular electronic structure methods and software to these fragments of the crystal that are embedded in a self-consistently determined crystalline electrostatic field. They enable facile applications of accurate but otherwise prohibitively expensive ab initio molecular orbital theories such as Møller-Plesset perturbation and coupled-cluster theories to a broad range of properties of solids such as internal energies, enthalpies, structures, equation of state, phonon dispersion curves and density of states, infrared and Raman spectra (including band intensities and sometimes anharmonic effects), inelastic neutron scattering spectra, heat capacities, Gibbs energies, and phase diagrams, while accounting for many-body electrostatic (namely, induction or polarization) effects as well as two-body exchange and dispersion interactions from first principles. They can fundamentally alter the role of computing in the studies of molecular crystals in the same way ab initio molecular orbital theories have transformed research practices in gas-phase physical chemistry and synthetic chemistry in the last half century. In this Account, after a brief summary of formalisms and algorithms, we discuss applications of these methods performed in our group as compelling illustrations of their unprecedented power in addressing some of the outstanding problems of solid-state chemistry, high-pressure chemistry, or geochemistry. They are the structure and spectra of ice Ih, in particular, the origin of two peaks in the hydrogen-bond-stretching region of its inelastic neutron scattering spectra, a solid-solid phase transition from CO2-I to elusive, metastable CO2-III, pressure tuning of Fermi resonance in solid CO2, and the structure and spectra of solid formic acid, all at the level of second-order Møller-Plesset perturbation theory or higher.

Synthesis, X-ray structure, magnetic resonance, and DFT analysis of a soluble copper(II) phthalocyanine lacking C-H bonds.

PubMed

Moons, Hans; Łapok, Łukasz; Loas, Andrei; Van Doorslaer, Sabine; Gorun, Sergiu M

2010-10-04

The synthesis, crystal structure, and electronic properties of perfluoro-isopropyl-substituted perfluorophthalocyanine bearing a copper atom in the central cavity (F(64)PcCu) are reported. While most halogenated phthalocyanines do not exhibit long-term order sufficient to form large single crystals, this is not the case for F(64)PcCu. Its crystal structure was determined by X-ray analysis and linked to the electronic properties determined by electron paramagnetic resonance (EPR). The findings are corroborated by density functional theory (DFT) computations, which agree well with the experiment. X-band continuous-wave EPR spectra of undiluted F(64)PcCu powder, indicate the existence of isolated metal centers. The electron-withdrawing effect of the perfluoroalkyl (R(f)) groups significantly enhances the complexes solubility in organic solvents like alcohols, including via their axial coordination. This coordination is confirmed by X-band (1)H HYSCORE experiments and is also seen in the solid state via the X-ray structure. Detailed X-band CW-EPR, X-band Davies and Mims ENDOR, and W-band electron spin-echo-detected EPR studies of F(64)PcCu in ethanol allow the determination of the principal g values and the hyperfine couplings of the metal, nitrogen, and fluorine nuclei. Comparison of the g and metal hyperfine values of F(64)PcCu and other PcCu complexes in different matrices reveals a dominant effect of the matrix on these EPR parameters, while variations in the ring substituents have only a secondary effect. The relatively strong axial coordination occurs despite the diminished covalency of the C-N bonds and potentially weakening Jahn-Teller effects. Surprisingly, natural abundance (13)C HYSCORE signals could be observed for a frozen ethanol solution of F(64)PcCu. The (13)C nuclei contributing to the HYSCORE spectra could be identified as the pyrrole carbons by means of DFT. Finally, (19)F ENDOR and easily observable paramagnetic NMR were found to relate well to the DFT computations, revealing negligible isotropic hyperfine (Fermi contact) contributions. The single-site isolation in solution and solid state and the relatively strong coordination of axial ligands, both attributed to the introduction of R(f) groups, are features important for materials and catalyst design.

Measuring Conformational Dynamics of Single Biomolecules Using Nanoscale Electronic Devices

NASA Astrophysics Data System (ADS)

Akhterov, Maxim V.; Choi, Yongki; Sims, Patrick C.; Olsen, Tivoli J.; Gul, O. Tolga; Corso, Brad L.; Weiss, Gregory A.; Collins, Philip G.

2014-03-01

Molecular motion can be a rate-limiting step of enzyme catalysis, but motions are typically too quick to resolve with fluorescent single molecule techniques. Recently, we demonstrated a label-free technique that replaced fluorophores with nano-electronic circuits to monitor protein motions. The solid-state electronic technique used single-walled carbon nanotube (SWNT) transistors to monitor conformational motions of a single molecule of T4 lysozyme while processing its substrate, peptidoglycan. As lysozyme catalyzes the hydrolysis of glycosidic bonds, two protein domains undergo 8 Å hinge bending motion that generates an electronic signal in the SWNT transistor. We describe improvements to the system that have extended our temporal resolution to 2 μs . Electronic recordings at this level of detail directly resolve not just transitions between open and closed conformations but also the durations for those transition events. Statistical analysis of many events determines transition timescales characteristic of enzyme activity and shows a high degree of variability within nominally identical chemical events. The high resolution technique can be readily applied to other complex biomolecules to gain insights into their kinetic parameters and catalytic function.

Electronic excited state paths of Stone-Wales rearrangement in pyrene: roles of conical intersections.

PubMed

Yamazaki, Kaoru; Niitsu, Naoyuki; Nakamura, Kosuke; Kanno, Manabu; Kono, Hirohiko

2012-11-26

We investigated the reaction paths of Stone-Wales rearrangement (SWR), i.e., π/2 rotation of two carbon atoms with respect to the midpoint of the bond, in graphene and carbon nanotube quantum chemically. Our particular attention is focused on the roles of electronic excitations and conical intersections (CIs) in the reaction mechanism. We used pyrene as a model system. The reaction paths were determined by constructing potential energy surfaces at the MS-CASPT2//SA-CASSCF level of theory. We found that there are no CIs involved in SWR when both of C-C bond cleavage and formation occur simultaneously (concerted mechanism). In contrast, for the reaction path with stepwise cleavage and formation of C-C bonds, C-C bond breaking and making processes proceed through two CIs. When SWR starts from the ground (S(0)) state, the concerted and stepwise paths have an equivalent reaction barrier ΔE(‡) (9.5-9.6 eV). For the reaction path starting from excited states, only the stepwise mechanism is energetically preferable. This path contains a nonadabatic transition between the S(1) and S(0) states via a CI associated with the first stage of C-C bond cleavage and has ΔE(‡) as large as in the S(0) paths. We confirmed that the main active molecular orbitals and electron configurations for the low-lying electronic states of larger nanocarbons are the same as those in pyrene. This result suggests the importance of the nonadiabatic transitions through CIs in the photochemical reactions in large nanocarbons.

Optical characterisation of hydroxide catalysed bonds applied to phosphate glass

NASA Astrophysics Data System (ADS)

Lacaille, Grégoire; Mangano, Valentina; van Veggel, Anna-Maria A.; Killow, Christian J.; MacKay, Peter E.; Rowan, Sheila; Hough, James

2017-10-01

We apply the Hydroxide Catalysis Bonding (HCB) technique to phosphate glass and measure the reflectivity and Light Induced Damage Threshold (LITD) of the newly formed interface. HCB is a room temperature, high performing process which was designed for astronomical research glass assemblies and played a key role in the detection of gravitational waves, a breakthrough in contemporary science. The bonds have numerous assets including mechanical strength, stability, no outgassing and resistance to contamination which are of high interest in the precision optics industry. However only little research has been done on their optical properties and mostly on silica based materials. In this paper, we use HCB to bond phosphate glass at room temperature with the goal of designing composite components for solid state laser gain media. We change the solution parameters to identify how they influence the final properties of the bonds: the LIDT at 1535 nm in long pulse regime and the reflectivity at 532 nm are investigated. The measurement of the incidence dependent reflectance allows estimating the thickness and refractive index of the bond in a non destructive process. The best performing set of parameters yields a LIDT of 1.6 GW/cm2 (16 J/cm2) and a reflectivity below 0.03 % which makes it suitable for use in high power lasers. The bond thickness is derived both from Scanning Electron Microscopy and the reflectivity measurements and is in the range of 50-150 nm depending on the parameters. Finally, the bonds survive cutting and polishing which is promising for manufacturing purpose.

Metal-Metal Bonds and Metal Carbon Bonds in the Chemistry of Molybdenum and Tungsten Alkoxides.

DTIC Science & Technology

1983-02-07

properties. For example, the lanthanide elements and aluminum form an extensive series of isopropoxides of formula MAI3 (OPr i)12 which are volatile solids or...coordination is imposed. !E 2 RO RO RO-_ 0 1_-OR ROe MV’*’ I ’%OR RO RRO (2) The ethoxides and methoxides of titanium (+4) adopt a tetrameric structure in the...solid state, II, whereby each metal atom achieves an octahedral environment. In benzene solution, the titanium ethoxide dissoci- ates to trimers, while

1H, 13C, 15N NMR analysis of sildenafil base and citrate (Viagra) in solution, solid state and pharmaceutical dosage forms.

PubMed

Wawer, Iwona; Pisklak, Maciej; Chilmonczyk, Zdzisław

2005-08-10

Sildenafil citrate (SC) (Viagra) and sildenafil base in pure form are easily and unequivocally characterized by multinuclear NMR spectroscopy. Analysis of chemical shifts indicates that: (i) N6-H forms intramolecular hydrogen bonds, (ii) N25 is protonated in the salt and (iii) intermolecular OH...N hydrogen bonds involving N2 and N4 are present in the solid sildenafil citrate. 13C CPMAS NMR method has been proposed for the identification and quantitation of Viagra in its pharmaceutical formulations.

On the roles of close shell interactions in the structure of acyl-substituted hydrazones: An experimental and theoretical approach

NASA Astrophysics Data System (ADS)

Saeed, Aamer; Ifzan Arshad, M.; Bolte, Michael; Fantoni, Adolfo C.; Delgado Espinoza, Zuly Y.; Erben, Mauricio F.

2016-03-01

The 2-(phenyl-hydrazono)-succinic acid dimethyl ester compound was synthesized by reacting phenylhydrazine with dimethylacetylene dicarboxylate at room temperature and characterized by elemental analysis, infrared, Raman, 1H and 13C NMR spectroscopies and mass spectrometry. Its solid state structure was determined by X-ray diffraction methods. The X-ray structure determination corroborates that the molecule is present in the crystal as the hydrazone tautomer, probably favored by a strong intramolecular N-H···Odbnd C hydrogen bond occurring between the carbonyl (-Cdbnd O) and the hydrazone -Cdbnd N-NH- groups. A substantial fragment of the molecular skeleton is planar due to an extended π-bonding delocalization. The topological analysis of the electron densities (Atom in Molecule, AIM) allows characterization of intramolecular N-H···O interaction, that can be classified as a resonant assisted hydrogen bond (RAHB). Moreover, the Natural Bond Orbital population analysis confirms that a strong hyperconjugative lpO1 → σ*(N2-H) remote interaction between the C2dbnd O1 and N2-H groups takes place. Periodic system electron density and topological analysis have been applied to characterize the intermolecular interactions in the crystal. Weak intermolecular interactions determine the crystal packing, and the prevalence of non-directional dispersive contributions are inferred on topological grounds. The IR spectrum of the crystalline compound was investigated by means of density functional theory calculations carried out with periodic boundary conditions on the crystal, showing excellent agreement between theory and the experiments. The vibrational assignment is complemented with the analysis of the Raman spectrum.

Transferability of electronic structure of four energetic materials by using single crystal and high resolution X-ray diffraction experiments

NASA Astrophysics Data System (ADS)

Chen, Yu-Sheng

The electronic structures of four energetic materials, trinitrodiazapentalene (C6H3N5O6, TNDAP), beta-1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (C4H8N8O8, beta-HMX), 1,3,3-trinitroazetidine (C3H4N4O6, TNAZ), and hexahydro-1,3,5-trinitro-1,3,5-s-triazine (C3H6N6O6, RDX), have been analyzed using Hansen-Coppens multipole refinements, using high resolution X-ray diffraction data collected at low temperature, as well as from theoretical calculated structure factors from the solid state phase using density functional theory (DFT), plus B3LYP level theory, and the 6-31G* basis set. However, when comparing both the deformation density and the electrostatic potentials from the theoretical results in TNDAP and TNAZ, they disagree with the experimental results. Therefore, those results have been deposited in appendices A4 and A6, for future reference. In HMX and RDX the theoretical results are in good agreement with experimental results. The physical properties derived from the electronic structure in these four energetic materials, such as multipole populations, the values of the electron density and its Laplacian of the electron density at the bond critical points, have also been calculated using "Atoms in Molecules" (AIM) theory both from the solid state phase calculation, and the experiment, as well as directly calculated from the free molecule in the gas phase. The electron density and the magnitude of its Laplacian from the gas phase are always larger than for the solid state phase calculation and the experiment. This may be due to the packing effect. The transferability of the experimental electronic structure of the NO 2 groups from HMX to TNDAP, TNAZ and RDX are also presented here. Even though the major populated multipoles are robust (small e.s.d.'s), these are few in number, compared with other lower populated multipoles for which the populations span a larger range. Since the deformation electron density distributions are reconstructed using linear combinations of the multipoles, it is necessary to give more degrees of freedom in the refinements. Therefore, those electron density distributions which have a wider range of the multipole populations should not be fixed in the refinements. Utilizing the same coordinate system setup in the multipole refinements of the functional groups, this system can be used as a starting point for solving the charge distribution of a larger system.

A survey of current solid state star tracker technology

NASA Astrophysics Data System (ADS)

Armstrong, R. W.; Staley, D. A.

1985-12-01

This paper is a survey of the current state of the art in design of star trackers for spacecraft attitude determination systems. Specific areas discussed are sensor technology, including the current state-of-the-art solid state sensors and techniques of mounting and cooling the sensor, analog image preprocessing electronics performance, and digital processing hardware and software. Three examples of area array solid state star tracker development are presented - ASTROS, developed by the Jet Propulsion Laboratory, the Retroreflector Field Tracker (RFT) by Ball Aerospace, and TRW's MADAN. Finally, a discussion of solid state line arrays explores the possibilities for one-dimensional imagers which offer simplified scan control electronics.

21 CFR 1005.23 - Bonds.

Code of Federal Regulations, 2010 CFR

2010-04-01

... IMPORTATION OF ELECTRONIC PRODUCTS Bonding and Compliance Procedures § 1005.23 Bonds. The bond required under... governing its admission into the commerce of the United States upon demand of the District Director of Customs and containing a provision for the performance of any action necessary to bring the product into...

Solid-state NMR and IR for the analysis of pharmaceutical solids: polymorphs of fosinopril sodium.

PubMed

Brittain, H G; Morris, K R; Bugay, D E; Thakur, A B; Serajuddin, A T

1993-01-01

The two polymorphic modifications of fosinopril sodium have been characterized as to their differences in melting behaviour, powder X-ray diffraction patterns, Fourier transform infrared spectra (FTIR), and solid-state 31P- and 13C-NMR spectra. The polymorphs were found to be enantiotropically related based upon melting point, heat of fusion, and solution mediated transformation data. Analysis of the solid-state FTIR and 13C-NMR data indicated that the environment of the acetal side chain of fosinopril sodium differed in two polymorphs, and that there might be cis-trans isomerization about the C6-N peptide bond. These conformational differences are postulated as the origin of the observed polymorphism.

Energy States of Molecules

ERIC Educational Resources Information Center

Hollenberg, J. Leland

1970-01-01

Discusses molecular spectroscopy arising from transitions within rotational, vibrational, and electronic energy states. Using quantum mechanical formuli, the author describes how these spectroscopic methods can be used to determine internuclear distances, bond energies, bond angles, dipole moments, and other details. Concludes with a selected…

Special Issue of Solid-State Electronics, dedicated to EUROSOI-ULIS 2016

NASA Astrophysics Data System (ADS)

Sverdlov, Viktor; Selberherr, Siegfried

2017-02-01

The current special issue of Solid-State Electronics includes 29 extended papers presented at the 2016 Second Joint International EUROSOI Workshop and International Conference on Ultimate Integration on Silicon (EUROSOI-ULIS 2016) held in Wien, Austria, on January 25-27, 2016. The papers entering to the special issue have been selected by the EUROSOI-ULIS 2016 Technical Program Committee based on the excellence of abstracts submitted and presentations delivered at the conference. In order to comply with the high standards of Solid-State Electronics the manuscripts went through the standard reviewing procedure.

Hydrothermal preparation of blue molybdenum bronze nanoribbons: structural changes in mother crystals, related to solid-state conversion and crystallite splitting to nanomorphology

NASA Astrophysics Data System (ADS)

Nishida, Takamasa; Eda, Kazuo

2018-02-01

Hydrothermal syntheses of alkali-metal blue molybdenum bronze nanoribbons, which are expected to exhibit unique properties induced by a combined effect of extrinsic and intrinsic low-dimensionalities, from hydrated-alkali-metal molybdenum bronzes were investigated. Nanoribbons grown along the quasi-one-dimensional (1D) conductive direction of Cs0.3MoO3, which is difficult to prepare by the conventional methods, were first synthesized. The nanomorphology formation is achieved by a solid-state conversion (or crystallite splitting) and subsequent crystallite growth, and the structural changes of the starting material related to the conversion were first observed by powder X-ray diffraction and scanning transmission electron microscopy as a result of finely tuned reaction system and preparation conditions. The structural changes were analyzed by model simulations and were attributed to the structural modulations that were concerned with the intralayer packing disorder and with two-dimensional long-range ordered structure, formed in MoO3 sheets of the hydrated molybdenum bronze. Moreover, the modulations were related to displacement defects of the Mo-O framework units generated along the [100] direction in the hydrated molybdenum bronze. Then, it was suggested that the solid-state conversion into blue molybdenum bronze and the crystallite splitting to nanomorphology were initiated by the breaking of the Mo-O-Mo bonds at the defects. [Figure not available: see fulltext.

Experimental and theoretical distribution of electron density and thermopolimerization in crystals of Ph3Sb(O2CCH=CH2)2 complex

NASA Astrophysics Data System (ADS)

Fukin, Georgy K.; Samsonov, Maxim A.; Arapova, Alla V.; Mazur, Anton S.; Artamonova, Tatiana O.; Khodorkovskiy, Mikhail A.; Vasilyev, Aleksander V.

2017-10-01

In this paper we present the results of a high-resolution single crystal X-ray diffraction experiment of a triphenylantimony diacrylate (Ph3Sb(O2CCH=CH2)2 (1)) and a subsequent charge density study based on a topological analysis according to quantum theory of atoms in molecules (QTAIM) together with density functional theory (DFT) calculation of isolated molecule. The QTAIM was used to investigate nature of the chemical bonds and molecular graph of Ph3Sb(O2CCH=CH2)2 complex. The molecular graph shows that only in one acrylate group there is an evidence of bonding between antimony and carbonyl oxygen atom in terms of the presence of a bond path. Thus the molecular graph for this class of compounds does not provide a definitive picture of the chemical bonding and should be complemented with other descriptors, such as and a source function (SF), noncovalent interaction (NCI) index and delocalization index (DI). Moreover the realization of π…π interactions between double bonds of acrylate groups in adjacent molecules allowed us to carry out a thermopolimerization reaction in crystals of Ph3Sb(O2CCH=CH2)2 complex and to determine a probable structure of polymer by solid state CP/MAS 13C NMR.

Structure and vibrational analysis of methyl 3-amino-2-butenoate.

PubMed

Berenji, Ali Reza; Tayyari, Sayyed Faramarz; Rahimizadeh, Mohammad; Eshghi, Hossein; Vakili, Mohammad; Shiri, Ali

2013-02-01

The molecular structure and vibrational spectra of methyl 3-(amino)-2-butenoate (MAB) and its deuterated analogous, D(3)MAB, were investigated using density functional theory (DFT) calculations. The geometrical parameters and harmonic vibrational wavenumbers of MAB and D(3)MAB were obtained at the B3LYP/6-311++G(d,p) level. The calculated vibrational wavenumbers were compared with the corresponding experimental results. The assignment of the IR and Raman spectra of MAB and D(3)MAB was facilitated by calculating the anharmonic wavenumbers at the B3LYP/6-311G(d,p) level as well as recording and calculating the MAB spectra in CCl(4) solution. The assigned normal modes were compared with a similar molecule, 4-amino-3-penten-2-one (APO). The theoretical results were in good agreement with the experimental data. All theoretical and experimental results indicate that substitution of a methyl group with a methoxy group considerably weakens the intramolecular hydrogen bond and reduces the π-electron delocalization in the chelated ring system. The IR spectra also indicate that in the solid state, MAB is not only engaged in an intramolecular hydrogen bond, but also forms an intermolecular hydrogen bond. However, the intermolecular hydrogen bond will be removed in dilute CCl(4) solution. Copyright © 2012 Elsevier B.V. All rights reserved.

Photosynthesis. Electronic structure of the oxygen-evolving complex in photosystem II prior to O-O bond formation.

PubMed

Cox, Nicholas; Retegan, Marius; Neese, Frank; Pantazis, Dimitrios A; Boussac, Alain; Lubitz, Wolfgang

2014-08-15

The photosynthetic protein complex photosystem II oxidizes water to molecular oxygen at an embedded tetramanganese-calcium cluster. Resolving the geometric and electronic structure of this cluster in its highest metastable catalytic state (designated S3) is a prerequisite for understanding the mechanism of O-O bond formation. Here, multifrequency, multidimensional magnetic resonance spectroscopy reveals that all four manganese ions of the catalyst are structurally and electronically similar immediately before the final oxygen evolution step; they all exhibit a 4+ formal oxidation state and octahedral local geometry. Only one structural model derived from quantum chemical modeling is consistent with all magnetic resonance data; its formation requires the binding of an additional water molecule. O-O bond formation would then proceed by the coupling of two proximal manganese-bound oxygens in the transition state of the cofactor. Copyright © 2014, American Association for the Advancement of Science.

First principles study of the electronic and magnetic structures and bonding properties of UCoC2 ternary, characteristic of C-C units

NASA Astrophysics Data System (ADS)

Matar, Samir F.

2013-03-01

The electronic structure of UCoC2, a di-carbide with the C-C units is examined from ab initio with an assessment of the properties of chemical bonding. The energy-volume equation of state shows large anisotropy effects due to C-C alignment along tetragonal c-axis leading to high linear incompressibility. Relevant features of selective bonding of uranium and cobalt with carbon at two different Wyckoff sites and strong C-C interactions are remarkable. The vibrational frequencies for C⋯C stretching modes indicate closer behavior to aliphatic C-C rather than Cdbnd C double bond. A ferromagnetic ground state is proposed from the calculations.

Organic solid state switches incorporating porphyrin compounds and method for producing organic solid state optical switches

DOEpatents

Wasielewski, Michael R.; Gaines, George L.; Niemczyk, Mark P.; Johnson, Douglas G.; Gosztola, David J.; O'Neil, Michael P.

1996-01-01

A light-intensity dependent molecular switch comprised of a compound which shuttles an electron or a plurality of electrons from a plurality of electron donors to an electron acceptor upon being stimulated with light of predetermined wavelengths, said donors selected from porphyrins and other compounds, and a method for making said compound.

Analysis of Solid State Bonding in the Extrusion Process of Magnesium Alloys --Numerical Prediction and Experimental Verification

NASA Astrophysics Data System (ADS)

Alharthi, Nabeel H.

The automotive industry developments focused on increasing fuel efficiency are accomplished by weight reduction of vehicles, which consequently results in less negative environmental impact. Usage of low density materials such as Magnesium alloys is an approach to replace heavier structural components. One of the challenges in deformation processing of Magnesium is its low formability attributed to the hexagonal close packed (hcp) crystal structure. The extrusion process is one of the most promising forming processes for Magnesium because it applies a hydrostatic compression state of stress during deformation resulting in improved workability. Many researchers have attempted to fully understand solid state bonding during deformation in different structural materials such as Aluminum, Copper and other metals and alloys. There is a lack of sufficient understanding of the extrusion welding in these materials as well as very limited knowledge on this subject for hollow profiles made from Magnesium alloys. The weld integrity and the characteristic of the welding microstructure are generally unknown. In this dissertation three related research projects are investigated by using different tools such as microstructure characterization, mechanical testing, thermo-mechanical physical simulation and finite element numerical modeling. Project 1: Microstructure characterization supported by mechanical testing of the extrusion welding regions in Magnesium alloy AM30 extrudate. The microstructure characterization was conducted using Light Optical Microscopy (LOM), in addition to LOM the electron backscattered diffraction (EBSD) technique was implemented to characterize in depth the deformed and welded microstructure. Project 2: Finite element numerical simulation of AM30 extrudate to model different process parameters and their influence on localized state variables such as strain, strain rate, temperature and normal pressure within the weld zone. Project 3: Physical simulation of the extrusion welding by using Gleeble 3500 thermo-mechanical simulator to create deformation welds in Magnesium alloy AM30 samples in compression test under various temperatures and strain rates conditions. Based on the obtained results from the performed research projects and literature review, a new qualitative criterion of extrusion welding has been introduced as contribution to the field. The criterion and its analysis have provided better understanding of material response to processing parameters and assisted in selecting the processing windows for good practices in the extrusion process. In addition, the new approach contributed to better understanding and evaluating the quality of the solid state bonding of Mg alloy. Accordingly, the criteria help to avoiding formation of potential mechanical and metallurgical imperfections.

Ab initio modeling of complex amorphous transition-metal-based ceramics.

PubMed

Houska, J; Kos, S

2011-01-19

Binary and ternary amorphous transition metal (TM) nitrides and oxides are of great interest because of their suitability for diverse applications ranging from high-temperature machining to the production of optical filters or electrochromic devices. However, understanding of bonding in, and electronic structure of, these materials represents a challenge mainly due to the d electrons in their valence band. In the present work, we report ab initio calculations of the structure and electronic structure of ZrSiN materials. We focus on the methodology needed for the interpretation and automatic analysis of the bonding structure, on the effect of the length of the calculation on the convergence of individual quantities of interest and on the electronic structure of materials. We show that the traditional form of the Wannier function center-based algorithm fails due to the presence of d electrons in the valence band. We propose a modified algorithm, which allows one to analyze bonding structure in TM-based systems. We observe an appearance of valence p states of TM atoms in the electronic spectra of such systems (not only ZrSiN but also NbO(x) and WAuO), and examine the importance of the p states for the character of the bonding as well as for facilitating the bonding analysis. The results show both the physical phenomena and the computational methodology valid for a wide range of TM-based ceramics.

Soft X-ray emission spectroscopy of liquids and lithium batterymaterials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Augustsson, Andreas

2004-01-01

Lithium ion insertion into electrode materials is commonly used in rechargeable battery technology. The insertion implies changes in both the crystal structure and the electronic structure of the electrode material. Side-reactions may occur on the surface of the electrode which is exposed to the electrolyte and form a solid electrolyte interface (SEI). The understanding of these processes is of great importance for improving battery performance. The chemical and physical properties of water and alcohols are complicated by the presence of strong hydrogen bonding. Various experimental techniques have been used to study geometrical structures and different models have been proposed tomore » view the details of how these liquids are geometrically organized by hydrogen bonding. However, very little is known about the electronic structure of these liquids, mainly due to the lack of suitable experimental tools. In this thesis examples of studies of lithium battery electrodes and liquid systems using soft x-ray emission spectroscopy will be presented. Monochromatized synchrotron radiation has been used to accomplish selective excitation, in terms of energy and polarization. The electronic structure of graphite electrodes has been studied, before and after lithium intercalation. Changes in the electronic structure upon lithiation due to transfer of electrons into the graphite π-bands have been observed. Transfer of electrons in to the 3d states of transition metal oxides upon lithiation have been studied, through low energy excitations as dd- and charge transfer-excitations. A SEI was detected on cycled graphite electrodes. By the use of selective excitation different carbon sites were probed in the SEI. The local electronic structure of water, methanol and mixtures of the two have been examined using a special liquid cell, to separate the liquid from the vacuum in the experimental chamber. Results from the study of liquid water showed a strong influence on the 3a1 molecular orbital and orbital mixing between water molecules upon hydrogen bonding. Apart from the four-hydrogen-bonding structure in water, a structure where one hydrogen bond is broken could be separated and identified. The soft x-ray emission study of methanol showed the existence of ring and chain formations in the liquid phase and the dominating structures are formed of 6 and 8 molecules. Upon mixing of the two liquids, a segregation at the molecular level was found and the formation of new structures, which could explain the unexpected low increase of the entropy.« less

Fundamental aspects of recoupled pair bonds. I. Recoupled pair bonds in carbon and sulfur monofluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunning, Thom H., E-mail: thdjr@uw.edu; Xu, Lu T.; Takeshita, Tyler Y.

2015-01-21

The number of singly occupied orbitals in the ground-state atomic configuration of an element defines its nominal valence. For carbon and sulfur, with two singly occupied orbitals in their {sup 3}P ground states, the nominal valence is two. However, in both cases, it is possible to form more bonds than indicated by the nominal valence—up to four bonds for carbon and six bonds for sulfur. In carbon, the electrons in the 2s lone pair can participate in bonding, and in sulfur the electrons in both the 3p and 3s lone pairs can participate. Carbon 2s and sulfur 3p recoupled pairmore » bonds are the basis for the tetravalence of carbon and sulfur, and 3s recoupled pair bonds enable sulfur to be hexavalent. In this paper, we report generalized valence bond as well as more accurate calculations on the a{sup 4}Σ{sup −} states of CF and SF, which are archetypal examples of molecules that possess recoupled pair bonds. These calculations provide insights into the fundamental nature of recoupled pair bonds and illustrate the key differences between recoupled pair bonds formed with the 2s lone pair of carbon, as a representative of the early p-block elements, and recoupled pair bonds formed with the 3p lone pair of sulfur, as a representative of the late p-block elements.« less

New solid state forms of antineoplastic 5-fluorouracil with anthelmintic piperazine

NASA Astrophysics Data System (ADS)

Moisescu-Goia, C.; Muresan-Pop, M.; Simon, V.

2017-12-01

The aim of the present study was to asses the formation of solid forms between the 5-fluorouracil chemotherapy drug and the anthelmintic piperazine. Two new solid forms of antineoplastic agent 5-fluorouracil with anthelmintic piperazine were obtained by liquid assisted ball milling and slurry crystallization methods. The Nsbnd H hydrogen bonding donors and C = O hydrogen bonding acceptors of 5-fluorouracil allow to form co-crystals with other drugs delivering improved properties for medical applications, as proved for other compounds of pharmaceutical interest. Both new solid forms were investigated using X-ray powder diffraction (XRD), differential thermal analysis (DTA) and Fourier transform infrared (FTIR) spectroscopy. The XRD results show that by both methods were successfully synthesized new solid forms of 5-fluorouracil with piperazine. According to FTIR results the form prepared by lichid assisted grinding process was obtained as co-crystal and the other one, prepared by slurry method, resulted as a salt.

QSPR analysis of the partitioning of vaporous chemicals in a water-gas phase system and the water solubility of liquid and solid chemicals on the basis of fragment and physicochemical similarity and hybot descriptors.

PubMed

Raevsky, O; Andreeva, E; Raevskaja, O; Skvortsov, V; Schaper, K

2005-01-01

QSPR analyses of the solubility in water of 558 vapors, 786 liquids and 2045 solid organic neutral chemicals and drugs are presented. Simultaneous consideration of H-bond acceptor and donor factors leads to a good description of the solubility of vapors and liquids. A volume-related term was found to have an essential negative contribution to the solubility of liquids. Consideration of polarizability, H-bond acceptor and donor factors and indicators for a few functional groups, as well as the experimental solubility values of structurally nearest neighbors yielded good correlations for liquids. The application of Yalkowsky's "General Solubility Equation" to 1063 solid chemicals and drugs resulted in a correlation of experimental vs calculated log S values with only modest statistical criteria. Two approaches to derive predictive models for solubility of solid chemicals and drugs were tested. The first approach was based on the QSPR for liquids together with indicator variables for different functional groups. Furthermore, a calculation of enthalpies for intermolecular complexes in crystal lattices, based on new H-bond potentials, was carried out for the better consideration of essential solubility- decreasing effects in the solid state, as compared with the liquid state. The second approach was based on a combination of similarity considerations and traditional QSPR. Both approaches lead to high quality predictions with average absolute errors on the level of experimental log S determination.

Rationalizing the photophysical properties of BODIPY laser dyes via aromaticity and electron-donor-based structural perturbations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Waddell, Paul G.; Liu, Xiaogang; Zhao, Teng

2015-05-01

The absorption and fluorescence properties of six boron dipyrromethene (BODIPY) laser dyes with simple non-aromatic substituents are rationalized by relating them to observable structural perturbations within the molecules of the dyes. An empirical relationship involving the structure and the optical properties is derived using a combination of single-crystal X-ray diffraction data, quantum chemical calculations and electronic constants: i.e. the tendency of the pyrrole bond lengths towards aromaticity and the UV-vis absorption and fluorescence wavelengths correlating with the electron-donor properties of the substituents. The effect of molecular conformation on the solid-state optical properties of the dyes is also discussed. The findingsmore » in this study also demonstrate the usefulness and limitations of using crystal structure data to develop structure-property relationships in this class of optical materials, contributing to the growing effort to design optoelectronic materials with tunable properties via molecular engineering.« less

Load regulating expansion fixture

DOEpatents

Wagner, Lawrence M.; Strum, Michael J.

1998-01-01

A free standing self contained device for bonding ultra thin metallic films, such as 0.001 inch beryllium foils. The device will regulate to a predetermined load for solid state bonding when heated to a bonding temperature. The device includes a load regulating feature, whereby the expansion stresses generated for bonding are regulated and self adjusting. The load regulator comprises a pair of friction isolators with a plurality of annealed copper members located therebetween. The device, with the load regulator, will adjust to and maintain a stress level needed to successfully and economically complete a leak tight bond without damaging thin foils or other delicate components.

Halogen bonding in solution: thermodynamics and applications.

PubMed

Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

2013-02-21

Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

Water nanodroplet thermodynamics: quasi-solid phase-boundary dispersivity.

PubMed

Zhang, Xi; Sun, Peng; Huang, Yongli; Ma, Zengsheng; Liu, Xinjuan; Zhou, Ji; Zheng, Weitao; Sun, Chang Q

2015-04-23

It has long been puzzling that water nanodroplets undergo simultaneously "supercooling" at freezing and "superheating" at melting. Recent progress (Sun et al. J. Phys. Chem. Lett. 2013, 4, 2565, 3238) enables us to resolve this anomaly from the perspective of hydrogen bond (O:H-O) specific heat disparity. A superposition of the specific heat ηx(T) curves for the H-O bond (x = H) and the O:H nonbond (x = L) defines two intersecting temperatures that form the ice/quasi-solid/liquid phase boundaries. Molecular undercoordination (with fewer than four nearest neighbors in the bulk) stretches the ηH(T) curve by raising the Debye temperature ΘDH through H-O bond shortening and phonon stiffening. The ηH(T) stretching is coupled with the ηL(T) depressing because of the Coulomb repulsion between electron pairs on oxygen ions. The extent of dispersion varies with the size of a droplet that prefers a core-shell structure configuration-the bulk interior and the skin. Understandings may open an effective way of dealing with the thermodynamic behavior of water droplets and bubbles from the perspective of O:H-O bond cooperativity.

Modeling and experimental evaluation of the diffusion bonding of the oxide dispersion strengthened steel PM2000

NASA Astrophysics Data System (ADS)

Sittel, Wiebke; Basuki, Widodo W.; Aktaa, Jarir

2015-10-01

A modeling based optimization process of the solid state diffusion bonding is presented for joining ferritic oxide dispersion strengthened steels PM2000. An optimization study employing varying bonding temperatures and pressures results in almost the same strength and toughness of the bonded compared to the as received material. TEM investigations of diffusion bonded samples show a homogeneous distribution of oxide particles at the bonding seam similar to that in the bulk. Hence, no loss in strength or creep resistance due to oxide particle agglomeration is found, as verified by the mechanical properties observed for the joint.

Investigation of strain effect on electronic, chemical bonding, magnetic and phonon properties of ScNiBi: a DFT study

NASA Astrophysics Data System (ADS)

Bano, Amreen; Gaur, N. K.

2018-04-01

In this paper, we have investigated the electronic band structure, magnetic state, chemical bonding and phonon properties of intermetallic compound ScNiBi (SNB) under the effect of strain using first-principles calculations. Our results showed that at 0% strain, SNB appears to be semiconducting with 0.22 eV energy gap. As the amount of strain increases over the system, the energy gap disappears and metallic character with ionic bonding appears. Covalent bonding at 0% lattice strain is observed between Bi-6p and Ni-3{d}{z2} orbitals with small contribution of Sc-3d states, with increasing strain, this bonding becomes ionic as SNB becomes a metal. From density of states (DoS), similar occupancy of energy states in the same energy range is observed in both spin channels, i.e. spin up and spin down. Hence, no spin polarization is found. From magnetic susceptibility as a function of temperature, we conclude that magnetic state of SNB is paramagnetic. Also, from phonon dispersion curves, we find that with increasing lattice strain, the frequency gap between acoustic phonon branches and optical phonon branches reduced and instability with negative frequencies at Γ are observed.

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Westlake, Brittany C.; Brennaman, Kyle M.; Concepcion, Javier J.

2011-05-24

The simultaneous, concerted transfer of electrons and protons—electron-proton transfer (EPT)—is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectralmore » measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H⁺ is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck–Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated ⁺H–B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.« less

Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes.

PubMed

Westlake, Brittany C; Brennaman, M Kyle; Concepcion, Javier J; Paul, Jared J; Bettis, Stephanie E; Hampton, Shaun D; Miller, Stephen A; Lebedeva, Natalia V; Forbes, Malcolm D E; Moran, Andrew M; Meyer, Thomas J; Papanikolas, John M

2011-05-24

The simultaneous, concerted transfer of electrons and protons--electron-proton transfer (EPT)--is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4'-biphenylphenol. Femtosecond transient absorption spectral measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H(+) is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck-Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated (+)H ─ B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.

Chemical reactions and morphological stability at the Cu/Al2O3 interface.

PubMed

Scheu, C; Klein, S; Tomsia, A P; Rühle, M

2002-10-01

The microstructures of diffusion-bonded Cu/(0001)Al2O3 bicrystals annealed at 1000 degrees C at oxygen partial pressures of 0.02 or 32 Pa have been studied with various microscopy techniques ranging from optical microscopy to high-resolution transmission electron microscopy. The studies revealed that for both oxygen partial pressures a 20-35 nm thick interfacial CuAlO2 layer formed, which crystallises in the rhombohedral structure. However, the CuAlO2 layer is not continuous, but interrupted by many pores. In the samples annealed in the higher oxygen partial pressure an additional reaction phase with a needle-like structure was observed. The needles are several millimetres long, approximately 10 microm wide and approximately 1 microm thick. They consist of CuAlO2 with alternating rhombohedral and hexagonal structures. Solid-state contact angle measurements were performed to derive values for the work of adhesion. The results show that the adhesion is twice as good for the annealed specimen compared to the as-bonded sample.

Electron correlation in real time.

PubMed

Sansone, Giuseppe; Pfeifer, Thomas; Simeonidis, Konstantinos; Kuleff, Alexander I

2012-02-01

Electron correlation, caused by the interaction among electrons in a multielectron system, manifests itself in all states of matter. A complete theoretical description of interacting electrons is challenging; different approximations have been developed to describe the fundamental aspects of the correlation that drives the evolution of simple (few-electron systems in atoms/molecules) as well as complex (multielectron wave functions in atoms, molecules, and solids) systems. Electron correlation plays a key role in the relaxation mechanisms that characterize excited states of neutral or ionized atoms and molecules populated by absorption of extreme ultraviolet (XUV) or X-ray radiation. The dynamics of these states can lead to different processes such as Fano resonance and Auger decay in atoms or interatomic Coulombic decay or charge migration in molecules and clusters. Many of these relaxation mechanisms are ubiquitous in nature and characterize the interaction of complex systems, such as biomolecules, adsorbates on surfaces, and hydrogen-bonded clusters, with XUV light. These mechanisms evolve typically on the femtosecond (1 fs=10(-15) s) or sub-femtosecond timescale. The experimental availability of few-femtosecond and attosecond (1 as=10(-18) s) XUV pulses achieved in the last 10 years offers, for the first time, the opportunity to excite and probe in time these dynamics giving the possibility to trace and control multielectron processes. The generation of ultrashort XUV radiation has triggered the development and application of spectroscopy techniques that can achieve time resolution well into the attosecond domain, thereby offering information on the correlated electronic motion and on the correlation between electron and nuclear motion. A deeper understanding of how electron correlation works could have a large impact in several research fields, such as biochemistry and biology, and trigger important developments in the design and optimization of electronic devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic structure of layered ferroelectric high-k titanate Pr2Ti2O7

NASA Astrophysics Data System (ADS)

Atuchin, V. V.; Gavrilova, T. A.; Grivel, J.-C.; Kesler, V. G.; Troitskaia, I. B.

2012-11-01

The spectroscopic parameters and electronic structure of binary titanate Pr2Ti2O7 have been studied by IR-, Raman and X-ray photoelectron spectroscopy (XPS) for the powder sample prepared by solid state synthesis. The spectral features of valence band and all constituent element core levels have been considered. The Auger parameters of titanium and oxygen in Pr2Ti2O7 have been determined as αTi=872.8 and αO=1042.3 eV. Variations of cation-anion bond ionicity have been discussed using binding energy differences ΔTi=(BE O 1s-BE Ti 2p3/2)=71.6 eV and ΔPr=BE(Pr 3d5/2)-BE(O 1s)=403.8 eV as key parameters in comparison with those of other titanium- and praseodymium-bearing oxides.

Electronic cooling via interlayer Coulomb coupling in multilayer epitaxial graphene

PubMed Central

Mihnev, Momchil T.; Tolsma, John R.; Divin, Charles J.; Sun, Dong; Asgari, Reza; Polini, Marco; Berger, Claire; de Heer, Walt A.; MacDonald, Allan H.; Norris, Theodore B.

2015-01-01

In van der Waals bonded or rotationally disordered multilayer stacks of two-dimensional (2D) materials, the electronic states remain tightly confined within individual 2D layers. As a result, electron–phonon interactions occur primarily within layers and interlayer electrical conductivities are low. In addition, strong covalent in-plane intralayer bonding combined with weak van der Waals interlayer bonding results in weak phonon-mediated thermal coupling between the layers. We demonstrate here, however, that Coulomb interactions between electrons in different layers of multilayer epitaxial graphene provide an important mechanism for interlayer thermal transport, even though all electronic states are strongly confined within individual 2D layers. This effect is manifested in the relaxation dynamics of hot carriers in ultrafast time-resolved terahertz spectroscopy. We develop a theory of interlayer Coulomb coupling containing no free parameters that accounts for the experimentally observed trends in hot-carrier dynamics as temperature and the number of layers is varied. PMID:26399955

δ-Deuterium Isotope Effects as Probes for Transition-State Structures of Isoprenoid Substrates

PubMed Central

2015-01-01

The biosynthetic pathways to isoprenoid compounds involve transfer of the prenyl moiety in allylic diphosphates to electron-rich (nucleophilic) acceptors. The acceptors can be many types of nucleophiles, while the allylic diphosphates only differ in the number of isoprene units and stereochemistry of the double bonds in the hydrocarbon moieties. Because of the wide range of nucleophilicities of naturally occurring acceptors, the mechanism for prenyltransfer reactions may be dissociative or associative with early to late transition states. We have measured δ-secondary kinetic isotope effects operating through four bonds for substitution reactions with dimethylallyl derivatives bearing deuterated methyl groups at the distal (C3) carbon atom in the double bond under dissociative and associative conditions. Computational studies with density functional theory indicate that the magnitudes of the isotope effects correlate with the extent of bond formation between the allylic moiety and the electron-rich acceptor in the transition state for alkylation and provide insights into the structures of the transition states for associative and dissociative alkylation reactions. PMID:24665882

Organic solid state switches incorporating porphyrin compounds and method for producing organic solid state optical switches

DOEpatents

Wasielewski, M.R.; Gaines, G.L.; Niemczyk, M.P.; Johnson, D.G.; Gosztola, D.J.; O`Neil, M.P.

1996-07-23

A light-intensity dependent molecular switch comprised of a compound which shuttles an electron or a plurality of electrons from a plurality of electron donors to an electron acceptor upon being stimulated with light of predetermined wavelengths, said donors selected from porphyrins and other compounds, and a method for making said compound are disclosed. 4 figs.

Electronic state and optical response in a hydrogen-bonded molecular conductor

NASA Astrophysics Data System (ADS)

Naka, Makoto; Ishihara, Sumio

2018-06-01

Motivated by recent experimental studies of hydrogen-bonded molecular conductors κ -X 3(Cat-EDT-TTF) 2[X =H , D], interplays of protons and correlated electrons, and their effects on magnetic, dielectric, and optical properties, are studied theoretically. We introduce a model Hamiltonian for κ -X 3(Cat-EDT-TTF) 2, in which molecular dimers are connected by hydrogen bonds. Ground-state phase diagram and optical conductivity spectra are examined by using the mean-field approximation and the exact diagonalization method in finite-size cluster. Three types of the competing electronic and protonic phases, charge density wave phase, polar charge-ordered phase, and antiferromagnetic dimer-Mott insulating phase are found. Observed softening of the interdimer excitation due to the electron-proton coupling implies reduction of the effective electron-electron repulsion, i.e., "Hubbard U ," due to the quantum proton motion. Contrastingly, the intradimer charge excitation is hardened due to the proton-electron coupling. Implications of the theoretical calculations to the recent experimental results in κ -X 3(Cat-EDT-TTF) 2 are discussed.

Parasitic oscillation suppression in solid state lasers using absorbing thin films

DOEpatents

Zapata, L.E.

1994-08-02

A thin absorbing film is bonded onto at least certain surfaces of a solid state laser gain medium. An absorbing metal-dielectric multilayer film is optimized for a broad range of incidence angles, and is resistant to the corrosive/erosive effects of a coolant such as water, used in the forced convection cooling of the film. Parasitic oscillations hamper the operation of solid state lasers by causing the decay of stored energy to amplified rays trapped within the gain medium by total and partial internal reflections off the gain medium facets. Zigzag lasers intended for high average power operation require the ASE absorber. 16 figs.

Parasitic oscillation suppression in solid state lasers using absorbing thin films

DOEpatents

Zapata, Luis E.

1994-01-01

A thin absorbing film is bonded onto at least certain surfaces of a solid state laser gain medium. An absorbing metal-dielectric multilayer film is optimized for a broad range of incidence angles, and is resistant to the corrosive/erosive effects of a coolant such as water, used in the forced convection cooling of the film. Parasitic oscillations hamper the operation of solid state lasers by causing the decay of stored energy to amplified rays trapped within the gain medium by total and partial internal reflections off the gain medium facets. Zigzag lasers intended for high average power operation require the ASE absorber.

Communication: Visualization and spectroscopy of defects induced by dehydrogenation in individual silicon nanocrystals

NASA Astrophysics Data System (ADS)

Kislitsyn, Dmitry A.; Mills, Jon M.; Kocevski, Vancho; Chiu, Sheng-Kuei; DeBenedetti, William J. I.; Gervasi, Christian F.; Taber, Benjamen N.; Rosenfield, Ariel E.; Eriksson, Olle; Rusz, Ján; Goforth, Andrea M.; Nazin, George V.

2016-06-01

We present results of a scanning tunneling spectroscopy (STS) study of the impact of dehydrogenation on the electronic structures of hydrogen-passivated silicon nanocrystals (SiNCs) supported on the Au(111) surface. Gradual dehydrogenation is achieved by injecting high-energy electrons into individual SiNCs, which results, initially, in reduction of the electronic bandgap, and eventually produces midgap electronic states. We use theoretical calculations to show that the STS spectra of midgap states are consistent with the presence of silicon dangling bonds, which are found in different charge states. Our calculations also suggest that the observed initial reduction of the electronic bandgap is attributable to the SiNC surface reconstruction induced by conversion of surface dihydrides to monohydrides due to hydrogen desorption. Our results thus provide the first visualization of the SiNC electronic structure evolution induced by dehydrogenation and provide direct evidence for the existence of diverse dangling bond states on the SiNC surfaces.

Role of 5f electrons in the structural stability of light actinide (Th-U) mononitrides under pressure.

PubMed

Modak, P; Verma, Ashok K

2016-03-28

Pressure induced structural sequences and their mechanism for light actinide (Th-U) mononitrides were studied as a function of 5f-electron number using first-principles total energy and electronic structure calculations. Zero pressure lattice constants, bulk module and C11 elastic module vary systematically with 5f-electron number implying its direct role on crystal binding. There is a critical 5f-electron number below which the system makes B1-B2 and above it B1-R3̄m-B2 structural sequence under pressure. Also, the B1-B2 transition pressure increases with increasing 5f-electron number whereas an opposite trend is obtained for the B1-R3̄m transition pressure. The ascending of N p anti-bonding states through the Fermi level at high pressure is responsible for the structural instability of the system. Above the critical 5f-electron number in the system a narrow 5f-band occurs very close to the Fermi level which allows the system to lower its symmetry via band Jahn-Teller type lattice distortion and the system undergoes a B1-R3̄m phase transition. However, below the critical 5f-electron number this mechanism is not favorable due to a lack of sufficient 5f-state occupancy and thus the system undergoes a B1-B2 phase transition like other ionic solids.

Charge transfer complex between 2,3-diaminopyridine with chloranilic acid. Synthesis, characterization and DFT, TD-DFT computational studies

NASA Astrophysics Data System (ADS)

Al-Ahmary, Khairia M.; Habeeb, Moustafa M.; Al-Obidan, Areej H.

2018-05-01

New charge transfer complex (CTC) between the electron donor 2,3-diaminopyridine (DAP) with the electron acceptor chloranilic (CLA) acid has been synthesized and characterized experimentally and theoretically using a variety of physicochemical techniques. The experimental work included the use of elemental analysis, UV-vis, IR and 1H NMR studies to characterize the complex. Electronic spectra have been carried out in different hydrogen bonded solvents, methanol (MeOH), acetonitrile (AN) and 1:1 mixture from AN-MeOH. The molecular composition of the complex was identified to be 1:1 from Jobs and molar ratio methods. The stability constant was determined using minimum-maximum absorbances method where it recorded high values confirming the high stability of the formed complex. The solid complex was prepared and characterized by elemental analysis that confirmed its formation in 1:1 stoichiometric ratio. Both IR and NMR studies asserted the existence of proton and charge transfers in the formed complex. For supporting the experimental results, DFT computations were carried out using B3LYP/6-31G(d,p) method to compute the optimized structures of the reactants and complex, their geometrical parameters, reactivity parameters, molecular electrostatic potential map and frontier molecular orbitals. The analysis of DFT results strongly confirmed the high stability of the formed complex based on existing charge transfer beside proton transfer hydrogen bonding concordant with experimental results. The origin of electronic spectra was analyzed using TD-DFT method where the observed λmax are strongly consisted with the computed ones. TD-DFT showed the contributed states for various electronic transitions.

Probing Fe-V Bonding in a C3-Symmetric Heterobimetallic Complex.

PubMed

Greer, Samuel M; McKay, Johannes; Gramigna, Kathryn M; Thomas, Christine M; Stoian, Sebastian A; Hill, Stephen

2018-04-30

Direct metal-metal bonding of two distinct first-row transition metals remains relatively unexplored compared to their second- and third-row heterobimetallic counterparts. Herein, a recently reported Fe-V triply bonded species, [V( i PrNPPh 2 ) 3 FeI] (1; Kuppuswamy, S.; Powers, T. M.; Krogman, J. P.; Bezpalko, M. W.; Foxman, B. M.; Thomas, C. M. Vanadium-iron complexes featuring metal-metal multiple bonds. Chem. Sci. 2013, 4, 3557-3565), is investigated using high-frequency electron paramagnetic resonance, field- and temperature-dependent 57 Fe nuclear gamma resonance (Mössbauer) spectroscopy, and high-field electron-electron double resonance detected nuclear magnetic resonance. From the use of this suite of physical methods, we have assessed the electronic structure of 1. These studies allow us to establish the effective g̃ tensors as well as the Fe/V electro-nuclear hyperfine interaction tensors of the spin S = 1 / 2 ground state. We have rationalized these tensors in the context of ligand field theory supported by quantum chemical calculations. This theoretical analysis suggests that the S = 1 / 2 ground state originates from a single unpaired electron predominately localized on the Fe site.

Diffusion Bonding of Microduplex Stainless Steel and Ti Alloy with and without Interlayer: Interface Microstructure and Strength Properties

NASA Astrophysics Data System (ADS)

Kundu, S.; Sam, S.; Mishra, B.; Chatterjee, S.

2014-01-01

The interface microstructure and strength properties of solid state diffusion bonding of microduplex stainless steel (MDSS) to Ti alloy (TiA) with and without a Ni alloy (NiA) intermediate material were investigated at 1173 K (900 °C) for 0.9 to 5.4 ks in steps of 0.9 ks in vacuum. The effects of bonding time on the microstructure of the bonded joint have been analyzed by light optical microscopy and scanning electron microscopy in the backscattered mode. In the direct bonded joints of MDSS and TiA, the layer-wise σ phase and the λ + FeTi phase mixture were observed at the bond interface when the joint was processed for 2.7 ks and above holding times. However, when NiA was used as an intermediate material, the results indicated that TiNi3, TiNi, and Ti2Ni are formed at the NiA-TiA interface, and the irregular shaped particles of Fe22Mo20Ni45Ti13 have been observed within the TiNi3 intermetallic layer. The stainless steel-NiA interface is free from intermetallics and the layer of austenitic phase was observed at the stainless steel side. A maximum tensile strength of ~520 MPa, shear strength of ~405 MPa, and impact toughness of ~18 J were obtained for the directly bonded joint when processed for 2.7 ks. However, when nickel base alloy was used as an intermediate material in the same materials, the bond tensile and shear strengths increase to ~640 and ~479 MPa, respectively, and the impact toughness to ~21 J when bonding was processed for 4.5 ks. Fracture surface observations in scanning electron microscopy using energy dispersive spectroscopy demonstrate that in MDSS-TiA joints, failure takes place through the FeTi + λ phase when bonding was processed for 2.7 ks; however, failure takes place through σ phase for the diffusion joints processed for 3.6 ks and above processing times. However, in MDSS-NiA-TiA joints, the fracture takes place through NiTi2 layer at the NiA-TiA interface for all bonding times.

Real-space identification of intermolecular bonding with atomic force microscopy.

PubMed

Zhang, Jun; Chen, Pengcheng; Yuan, Bingkai; Ji, Wei; Cheng, Zhihai; Qiu, Xiaohui

2013-11-01

We report a real-space visualization of the formation of hydrogen bonding in 8-hydroxyquinoline (8-hq) molecular assemblies on a Cu(111) substrate, using noncontact atomic force microscopy (NC-AFM). The atomically resolved molecular structures enable a precise determination of the characteristics of hydrogen bonding networks, including the bonding sites, orientations, and lengths. The observation of bond contrast was interpreted by ab initio density functional calculations, which indicated the electron density contribution from the hybridized electronic state of the hydrogen bond. Intermolecular coordination between the dehydrogenated 8-hq and Cu adatoms was also revealed by the submolecular resolution AFM characterization. The direct identification of local bonding configurations by NC-AFM would facilitate detailed investigations of intermolecular interactions in complex molecules with multiple active sites.

Super-pnicogen bonding in the radical anion of the fluorophosphine dimer

NASA Astrophysics Data System (ADS)

Setiawan, Dani; Cremer, Dieter

2016-10-01

The LUMO of the pnicogen-bonded fluoro-phosphine dimer has PP bonding character. Radical anion and dianion form relatively strong pnicogen bonds with some covalent character where however the dianion turns out to be a second order transition state. The binding energy of (FPH 2)2- is 30.4 kcal/mol (CCSD(T)/aug-cc-pVTZ; CASPT2(5,8): 30.7 kcal/mol) and the bond strength order measured with the local PP bond stretching force constant increases from 0.055 for the neutral dimer to 0.187 thus revealing that the stabilization of the radical anion is to a large extend a result of one-electron six-center delocalization. Pnicogen-bonded complexes have a stabilizing electron affinity.

Calix

PubMed

Frkanec; Visnjevac; Kojic-Prodic; Zinic

2000-02-04

Chiral calix[4]arene derivatives with four O-(N-acetyl-PhgOMe), (1), (Phg denotes R-phenylglycine), or O-(N-acetyl-LeuOMe) (2) strands have been synthesised. Both compounds exist in chloroform in stable cone conformations with a noncovalently organised cavity at the lower rim that is formed by circular interstrand amidic hydrogen bonds. Such organisation affects both the selectivity and extraction/transport properties of 1 and 2 toward metal cations. Calix[4]arene derivatives with one OCH2COPhgOMe strand (3), two OCH2COPhgOMe strands (5) and with 1,3-OMe-2,4-(O-CH2COPhgOMe) substituents (4) at the lower rim have also been prepared. For 3, a conformation stabilised by a circular hydrogen-bond arrangement is found in chloroform, while 4 exists as a time-averaged C2 conformation with two intramolecular NH ...OCH3 hydrogen bonds. Compound 5 has a unique hydrogen-bonding motif in solution and in the solid state with two three-centred NH-.. O and two OH...O hydrogen bonds at the lower rim. This motif keeps 5 in the flattened cone conformation in chloroform. The X-ray structure analysis of 1 revealed a molecular structure with C2 symmetry; this structure is organised in infinite chains by intra- and intermolecular H bonds. The solid-state and solution structures of the [1-Na]ClO4 complex are identical, C4 symmetric cone conformations.

Theoretical studies of damage to 3'-uridine monophosphate induced by electron attachment.

PubMed

Zhang, Ru Bo; Zhang, Ke; Eriksson, Leif A

2008-01-01

Low-energy electrons (LEE) are well known to induce nucleic acid damage. However, the damage mechanisms related to charge state and structural features remain to be explored in detail. In the present work, we have investigated the N1-glycosidic and C3'-O(P) bond ruptures of 3'-UMP (UMP=uridine monophosphate) and the protonated form 3'-UMPH with -1 and zero charge, respectively, based on hybrid density functional theory (DFT) B3 LYP together with the 6-31+G(d,p) basis set. The glycosidic bond breakage reactions of the 3'UMP and 3'UMPH electron adducts are exothermic in both cases, with barrier heights of 19-20 kcal mol(-1) upon inclusion of bulk solvation. The effects of the charge state on the phosphate group are marginal, but the C2'-OH group destabilizes the transition structure of glycosidic bond rupture of 3'-UMPH in the gas phase by approximately 5.0 kcal mol(-1). This is in contrast with the C3'-O(P) bond ruptures induced by LEE in which the charge state on the phosphate influences the barrier heights and reaction energies considerably. The barrier towards C3'-O(P) bond dissociation in the 3'UMP electron adduct is higher in the gas phase than the one corresponding to glycosidic bond rupture and is dramatically influenced by the C2'-OH group and bulk salvation, which decreases the barrier to 14.7 kcal mol(-1). For the C3'-O(P) bond rupture of the 3'UMPH electron adduct, the reaction is exothermic and the barrier is even lower, 8.2 kcal mol(-1), which is in agreement with recent results for 3'-dTMPH and 5'-dTMPH (dTMPH=deoxythymidine monophosphate). Both the Mulliken atomic charges and unpaired-spin distribution play significant roles in the reactions.

Acoustic backing in 3-D integration of CMUT with front-end electronics.

PubMed

Berg, Sigrid; Rønnekleiv, Arne

2012-07-01

Capacitive micromachined ultrasonic transducers (CMUTs) have shown promising qualities for medical imaging. However, there are still some problems to be investigated, and some challenges to overcome. Acoustic backing is necessary to prevent SAWs excited in the surface of the silicon substrate from affecting the transmit pattern from the array. In addition, echoes resulting from bulk waves in the substrate must be removed. There is growing interest in integrating electronic circuits to do some of the beamforming directly below the transducer array. This may be easier to achieve for CMUTs than for traditional piezoelectric transducers. We will present simulations showing that the thickness of the silicon substrate and thicknesses and acoustic properties of the bonding material must be considered, especially when designing highfrequency transducers. Through simulations, we compare the acoustic properties of 3-D stacks bonded with three different bonding techniques; solid-liquid interdiffusion (SLID) bonding, direct fusion bonding, and anisotropic conductive adhesives (ACA). We look at a CMUT array with a center frequency of 30 MHz and three silicon wafers underneath, having a total silicon thickness of 100 μm. We find that fusion bonding is most beneficial if we want to prevent surface waves from damaging the array response, but SLID and ACA are also promising if bonding layer thicknesses can be reduced.

Particle design using a 4-fluid-nozzle spray-drying technique for sustained release of acetaminophen.

PubMed

Chen, Richer; Okamoto, Hirokazu; Danjo, Kazumi

2006-07-01

We prepared matrix particles of acetaminophen (Act) with chitosan (Cht) as a carrier using a newly developed 4-fluid-nozzle spray dryer. Cht dissolves in acid solutions and forms a gel, but it does not dissolve in alkaline solutions. Therefore, we tested the preparation of controlled release matrix particles using the characteristics of this carrier. Act and Cht mixtures in prescribed ratios were dissolved in an acid solution. We evaluated the matrix particles by preparing a solid dispersion using a 4-fluid-nozzle spray dryer. Observation of the particle morphology by scanning electron microscopy (SEM) revealed that the particles from the spray drying process had atomized to several microns, and that they had become spherical. We investigated the physicochemical properties of the matrix particles by powder X-ray diffraction, differential scanning calorimetry, and dissolution rate analyses with a view to clarifying the effects of crystallinity on the dissolution rate. The powder X-ray diffraction peaks and the heat of the Act fusion in the spray-dried samples decreased with the increase of the carrier content, indicating that the drug was amorphous. These results indicate that the system formed a solid dispersion. Furthermore, we investigated the interaction between the drug and carrier using FT-IR analysis. The FT-IR spectroscopy for the Act solid dispersions suggested that the Act carboxyl group and the Cht amino group formed a hydrogen bond. In addition, the measurement results of the 13C CP/MAS solid-state NMR, indicated that a hydrogen bond had been formed between the Act carbonyl group and the Cht amino group. In the Act-Cht system, the 4-fluid-nozzle spray-dried preparation with a mixing ratio of 1 : 5 obtained a sustained release preparation in all pH test solutions.

Electronic structure and bonding of intergranular glassy films in polycrystalline Si3 N4 : Ab initio studies and classical molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Rulis, P.; Chen, J.; Ouyang, L.; Ching, W.-Y.; Su, X.; Garofalini, S. H.

2005-06-01

The electronic structure and bonding of a realistic model of an intergranular glassy film (IGF) was studied with multiple computational methods. The model has a Si-O-N glassy region sandwiched between crystalline basal planes of β-Si3N4 and contains a total of 798 atoms. It was constructed with periodic boundary conditions via classical molecular dynamics (MD) techniques using an accurate multibody atomic potential. The model was then further relaxed by the VASP (Vienna ab initio simulation package) program. It is shown that the VASP-relaxed structure reduces the total energy from the MD-relaxed structure by only 47.38eV , validating the accuracy of the multiatom potential used. The calculated electronic structure shows the IGF model to be an insulator with a sizable gap of almost 3eV . Quasidefectlike states can be identified near the band edges arising from the more strained Si-N and Si-O bonds at the interface. Calculation of the Mulliken effective charge and bond order values indicates that the bonds in the glassy region and at the interface can be enhanced and weakened by distortions in the bond length and bond angle. The states at the top of the valence band are derived mostly from the crystalline part of the Si-N bonding while the states at the bottom of the conduction band are dominated by the Si-O bonding in the glassy region. Calculation of the electrostatic potential across the interface shows an average band offset of about 1.5eV between the crystalline β-Si3N4 and the glassy Si-O-N region which could be related to the space charge model for IGF.

Correlation between valence electronic structure and magnetic properties in RCo5 (R = rare earth) intermetallic compound

NASA Astrophysics Data System (ADS)

Zhi-Qin, Xue; Yong-Quan, Guo

2016-06-01

The magnetisms of RCo5 (R = rare earth) intermetallics are systematically studied with the empirical electron theory of solids and molecules (EET). The theoretical moments and Curie temperatures agree well with experimental ones. The calculated results show strong correlations between the valence electronic structure and the magnetic properties in RCo5 intermetallic compounds. The moments of RCo5 intermetallics originate mainly from the 3d electrons of Co atoms and 4f electrons of rare earth, and the s electrons also affect the magnetic moments by the hybridization of d and s electrons. It is found that moment of Co atom at 2c site is higher than that at 3g site due to the fact that the bonding effect between R and Co is associated with an electron transformation from 3d electrons into covalence electrons. In the heavy rare-earth-based RCo5 intermetallics, the contribution to magnetic moment originates from the 3d and 4f electrons. The covalence electrons and lattice electrons also affect the Curie temperature, which is proportional to the average moment along the various bonds. Project supported by the National Natural Science Foundation of China (Grant No. 11274110).

Measurements of electron detection efficiencies in solid state detectors.

NASA Technical Reports Server (NTRS)

Lupton, J. E.; Stone, E. C.

1972-01-01

Detailed laboratory measurement of the electron response of solid state detectors as a function of incident electron energy, detector depletion depth, and energy-loss discriminator threshold. These response functions were determined by exposing totally depleted silicon surface barrier detectors with depletion depths between 50 and 1000 microns to the beam from a magnetic beta-ray spectrometer. The data were extended to 5000 microns depletion depth using the results of previously published Monte Carlo electron calculations. When the electron counting efficiency of a given detector is plotted as a function of energy-loss threshold for various incident energies, the efficiency curves are bounded by a smooth envelope which represents the upper limit to the detection efficiency. These upper limit curves, which scale in a simple way, make it possible to easily estimate the electron sensitivity of solid-state detector systems.

Electron Doping a Kagome Spin Liquid

NASA Astrophysics Data System (ADS)

Kelly, Zachary; Gallagher, Miranda; McQueen, Tyrel

In 1987, Anderson proposed that charge doping a material with the resonating valance bond (RVB) state would yield a superconducting state. Ever since, there has been a search for these RVB containing spin liquid materials and their charge doped counterparts. Studies on the most promising spin liquid candidate, Herbertsmithite, ZnCu3(OH)6Cl2, a two dimensional kagomé lattice, show evidence of fractionalized excitations and a gapped ground state. In this work, we report the synthesis and characterization of a newly synthesized electron doped spin liquid, ZnLixCu3(OH)6Cl2 from x = 0 to x = 1.8 (3 / 5 th per Cu2+). Despite heavy doping, the series remains insulating and the magnetism is systematically suppressed. We have done extensive structural studies of the doped series to determine the effect of the intercalated atoms on the structure, and whether these structural differences induce strong localization effects that suppress the metallic and superconducting states. Other doped spin liquid candidates are also being explored to understand if this localization is system dependent or systemic to all doped spin liquid systems. NSF, Division of Materials Research (DMR), Solid State Chemistry (SSMC), CAREER Grant under Award No. DMR- 1253562, Institute for Quantum Matter under Grant No.DE-FG02- 08ER46544, and the David and Lucile Packard Foundation.

The near ultraviolet photodissociation dynamics of 2- and 3-substituted thiophenols: Geometric vs. electronic structure effects

NASA Astrophysics Data System (ADS)

Marchetti, Barbara; Karsili, Tolga N. V.; Cipriani, Maicol; Hansen, Christopher S.; Ashfold, Michael N. R.

2017-07-01

The near ultraviolet spectroscopy and photodissociation dynamics of two families of asymmetrically substituted thiophenols (2- and 3-YPhSH, with Y = F and Me) have been investigated experimentally (by H (Rydberg) atom photofragment translational spectroscopy) and by ab initio electronic structure calculations. Photoexcitation in all cases populates the 11ππ* and/or 11πσ* excited states and results in S-H bond fission. Analyses of the experimentally obtained total kinetic energy release (TKER) spectra yield the respective parent S-H bond strengths, estimates of ΔE(A ˜ -X ˜ ), the energy splitting between the ground (X ˜ ) and first excited (A ˜ ) states of the resulting 2-(3-)YPhS radicals, and reveal a clear propensity for excitation of the C-S in-plane bending vibration in the radical products. The companion theory highlights roles for both geometric (e.g., steric effects and intramolecular H-bonding) and electronic (i.e., π (resonance) and σ (inductive)) effects in determining the respective parent minimum energy geometries, and the observed substituent and position-dependent trends in S-H bond strength and ΔE(A ˜ -X ˜ ). 2-FPhSH shows some clear spectroscopic and photophysical differences. Intramolecular H-bonding ensures that most 2-FPhSH molecules exist as the syn rotamer, for which the electronic structure calculations return a substantial barrier to tunnelling from the photoexcited 11ππ* state to the 11πσ* continuum. The 11ππ* ← S0 excitation spectrum of syn-2-FPhSH thus exhibits resolved vibronic structure, enabling photolysis studies with a greater parent state selectivity. Structure apparent in the TKER spectrum of the H + 2-FPhS products formed when exciting at the 11ππ* ← S0 origin is interpreted by assuming unintended photoexcitation of an overlapping resonance associated with syn-2-FPhSH(v33 = 1) molecules. The present data offer tantalising hints that such out-of-plane motion influences non-adiabatic coupling in the vicinity of a conical intersection (between the 11πσ* and ground state potentials at extended S-H bond lengths) and thus the electronic branching in the eventual radical products.

Formation of Annular Protofibrillar Assembly by Cysteine Tripeptide: Unraveling the Interactions with NMR, FTIR, and Molecular Dynamics.

PubMed

Banerji, Biswadip; Chatterjee, Moumita; Pal, Uttam; Maiti, Nakul C

2017-07-06

Both hydrogen-bonding and hydrophobic interactions play a significant role in molecular assembly, including self-assembly of proteins and peptides. In this study, we report the formation of annular protofibrillar structure (diameter ∼500 nm) made of a newly synthesized s-benzyl-protected cysteine tripeptide, which was primarily stabilized by hydrogen-bonding and hydrophobic interactions. Atomic force microscopy and field emission scanning electron microscopy analyses found small oligomers (diameter ∼60 nm) to bigger annular (outer diameter ∼300 nm; inner diameter, 100 nm) and protofibrillar structures after 1-2 days of incubation. Rotating-frame Overhauser spectroscopic (ROESY) analysis revealed the presence of several nonbonded proton-proton interactions among the residues, such as amide protons with methylene group, aromatic protons with tertiary butyl group, and methylene protons with tertiary butyl group. These added significant stability to bring the peptides closer to form a well-ordered assembled structure. Hydrogen-deuterium exchange NMR measurement further suggested that two individual amide protons among the three amide groups were strongly engaged with the adjacent tripeptide via H-bond interaction. However, the remaining amide proton was found to be exposed to solvent and remained noninteracting with other tripeptide molecules. In addition to chemical shift values, a significant change in amide bond vibrations of the tripeptide was found due to the formation of the self-assembled structure. The amide I mode of vibrations involving two amide linkages appeared at 1641 and 1695 cm -1 in the solid state. However, in the assembled state, the stretching band at 1695 cm -1 became broad and slightly shifted to ∼1689 cm -1 . On the contrary, the band at 1641 cm -1 shifted to 1659 cm -1 and indicated that the -C═O bond associated with this vibration became stronger in the assembled state. These changes in Fourier transform infrared spectroscopy frequency clearly indicated changes in the amide backbone conformation and the associated hydrogen-bonding pattern due to the formation of the assembled structure. In addition to hydrogen bonding, molecular dynamics simulation indicated that the number of π-π interactions also increased with increasing number of tripeptides participated in the self-assembly process. Combined results envisaged a cross β-sheet assembly unit consisting of four intermolecular hydrogen bonds. Such noncovalent peptide assemblies glued by hydrogen-bonding and other weak forces may be useful in developing nanocapsule and related materials.

Reversible Electrochemical Lithium-Ion Insertion into the Rhenium Cluster Chalcogenide-Halide Re6Se8Cl2.

PubMed

Bruck, Andrea M; Yin, Jiefu; Tong, Xiao; Takeuchi, Esther S; Takeuchi, Kenneth J; Szczepura, Lisa F; Marschilok, Amy C

2018-05-07

The cluster-based material Re 6 Se 8 Cl 2 is a two-dimensional ternary material with cluster-cluster bonding across the a and b axes capable of multiple electron transfer accompanied by ion insertion across the c axis. The Li/Re 6 Se 8 Cl 2 system showed reversible electron transfer from 1 to 3 electron equivalents (ee) at high current densities (88 mA/g). Upon cycling to 4 ee, there was evidence of capacity degradation over 50 cycles associated with the formation of an organic solid-electrolyte interface (between 1.45 and 1 V vs Li/Li + ). This investigation highlights the ability of cluster-based materials with two-dimensional cluster bonding to be used in applications such as energy storage, showing structural stability and high rate capability.

Solid-state and solution /sup 13/C NMR in the conformational analysis of methadone-hydrochloride and related narcotic analgesics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sumner, S.C.J.

1986-01-01

Solid state and solution /sup 13/C NMR have been used to study the conformations of the racemic mixtures and single enantiomers of methadone hydrochloride, alpha and beta methadol hydrochloride, and alpha and beta acetylmethadol hydrochloride. The NMR spectra acquired for the compounds as solids, and in polar and nonpolar solvents are compared, in order to determine the conformation of the molecules in solution. To determine the reliability of assigning solution conformations by comparing solution and solid state chemical shift data, three bond coupling constants measured in solution are compared with those calculated from X-ray data. The conformations of the racemicmore » mixture and plus enantiomer of methadone hydrochloride have been shown to be very similar in the solid state, where minor differences in conformation can be seen by comparing NMR spectra obtained for the solids. Also shown is that the molecules of methadone hydrochloride have conformations in polar and in nonpolar solvents which are very similar to the conformation of the molecules in the solid state.« less

Peculiar bonding associated with atomic doping and hidden honeycombs in borophene

NASA Astrophysics Data System (ADS)

Lee, Chi-Cheng; Feng, Baojie; D'angelo, Marie; Yukawa, Ryu; Liu, Ro-Ya; Kondo, Takahiro; Kumigashira, Hiroshi; Matsuda, Iwao; Ozaki, Taisuke

2018-02-01

Engineering atomic-scale structures allows great manipulation of physical properties and chemical processes for advanced technology. We show that the B atoms deployed at the centers of honeycombs in boron sheets, borophene, behave as nearly perfect electron donors for filling the graphitic σ bonding states without forming additional in-plane bonds by first-principles calculations. The dilute electron density distribution owing to the weak bonding surrounding the center atoms provides easier atomic-scale engineering and is highly tunable via in-plane strain, promising for practical applications, such as modulating the extraordinarily high thermal conductance that exceeds the reported value in graphene. The hidden honeycomb bonding structure suggests an unusual energy sequence of core electrons that has been verified by our high-resolution core-level photoelectron spectroscopy measurements. With the experimental and theoretical evidence, we demonstrate that borophene exhibits a peculiar bonding structure and is distinctive among two-dimensional materials.

Stable Chloro- and Bromoxenate Cage Anions; [X3(XeO3)3]3- and [X4(XeO3)4]4- (X = Cl or Br).

PubMed

Goettel, James T; Haensch, Veit G; Schrobilgen, Gary J

2017-06-28

The number of isolable compounds which contain different noble-gas-element bonds is limited for xenon and even more so for krypton. Examples of Xe-Cl bonds are rare, and prior to this work, no Xe-Br bonded compound had been isolated in macroscopic quantities. The syntheses, isolation, and characterization of the first compounds to contain Xe-Br bonds and their chlorine analogues are described in the present work. The reactions of XeO 3 with [N(CH 3 ) 4 ]Br and [N(C 2 H 5 ) 4 ]Br have provided two bromoxenate salts, [N(C 2 H 5 ) 4 ] 3 [Br 3 (XeO 3 ) 3 ] and [N(CH 3 ) 4 ] 4 [Br 4 (XeO 3 ) 4 ], in which the cage anions have Xe-Br bond lengths that range from 3.0838(3) to 3.3181(8) Å. The isostructural chloroxenate anions (Xe-Cl bond lengths, 2.9316(2) to 3.101(4) Å) were synthesized by analogy with their bromine analogues. The bromo- and chloroxenate salts are stable in the atmosphere at room temperature and were characterized in the solid state by Raman spectroscopy and low-temperature single-crystal X-ray diffraction, and in the gas phase by quantum-chemical calculations. They are the only known examples of cage anions that contain a noble-gas element. The Xe-Br and Xe-Cl bonds are very weakly covalent and can be viewed as σ-hole interactions, similar to those encountered in halogen bonding. However, the halogen atoms in these cases are valence electron lone pair donors, and the σ* Xe-O orbitals are lone pair acceptors.

Valence State Driven Site Preference in the Quaternary Compound Ca5MgAgGe5: An Electron-Deficient Phase with Optimized Bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ponou, Simeon; Lidin, Sven; Zhang, Yuemei

The quaternary phase Ca5Mg0.95Ag1.05(1)Ge5 (3) was synthesized by high-temperature solid-state techniques, and its crystal structure was determined by single-crystal diffraction methods in the orthorhombic space group Pnma – Wyckoff sequence c12 with a = 23.1481(4) Å, b = 4.4736(1) Å, c = 11.0128(2) Å, V = 1140.43(4) Å3, Z = 4. The crystal structure can be described as linear intergrowths of slabs cut from the CaGe (CrB-type) and the CaMGe (TiNiSi-type; M = Mg, Ag) structures. Hence, 3 is a hettotype of the hitherto missing n = 3 member of the structure series with the general formula R2+nT2X2+n, previously describedmore » with n = 1, 2, and 4. The member with n = 3 was predicted in the space group Cmcm – Wyckoff sequence f5c2. The experimental space group Pnma (in the nonstandard setting Pmcn) corresponds to a klassengleiche symmetry reduction of index two of the predicted space group Cmcm. This transition originates from the switching of one Ge and one Ag position in the TiNiSi-related slab, a process that triggers an uncoupling of each of the five 8f sites in Cmcm into two 4c sites in Pnma. The Mg/Ag site preference was investigated using VASP calculations and revealed a remarkable example of an intermetallic compound for which the electrostatic valency principle is a critical structure-directing force. The compound is deficient by one valence electron according to the Zintl concept, but LMTO electronic structure calculations indicate electronic stabilization and overall bonding optimization in the polyanionic network. Other stability factors beyond the Zintl concept that may account for the electronic stabilization are discussed.« less

Structural, optical, and spin properties of hydrogenated amorphous silicon-germanium alloys

NASA Astrophysics Data System (ADS)

Stutzmann, M.; Street, R. A.; Tsai, C. C.; Boyce, J. B.; Ready, S. E.

1989-07-01

We report on a detailed study of structural and electronic properties of hydrogenated amorphous silicon-germanium alloys deposited by rf glow discharge from SiH4 and GeH4 in a diode reactor. The chemical composition of the alloys is related to the deposition conditions, with special emphasis on preferential incorporation of Ge into the solid phase and on the role of inert dilutant gases. Hydrogen bonding in the alloys is investigated with nuclear magnetic resonance and vibrational (Raman and infrared) spectroscopy. The optical properties of a-SiGe:H samples deposited under optimal conditions are analyzed with the help of subgap absorption measurements and band-tail luminescence for the entire range of alloy composi-tions. A large part of the article describes an investigation of the electron-spin-resonance response of undoped alloys. The spin density associated with dangling bond defects localized on Si and Ge atoms has been measured as a function of alloy composition for optimized material. In addition, the dependence of the two defect densities on the detailed deposition conditions (rf power, substrate temperature, and dilution) has been determined in a systematic way for alloys deposited from a plasma with a fixed SiH4/GeH4ratio. The results of this study, especially the preferential creation of Ge dangling bonds, are discussed in the context of our structural data. Furthermore, spin resonance is employed to investigate the light-induced degradation (Staebler-Wronski effect) of a-SiGe:H. Finally, the changes of the spin-resonance spectra of a-Si0.7 Ge0.3 :H upon substitutional doping with phosphorus and boron have been obtained experimentally, and are used to construct a model for the electronic density of states in this material.

Mo-Mo Quintuple Bond is Highly Reactive in H-H, C-H, and O-H σ-Bond Cleavages Because of the Polarized Electronic Structure in Transition State.

PubMed

Chen, Yue; Sakaki, Shigeyoshi

2017-04-03

The recently reported high reactivity of the Mo-Mo quintuple bond of Mo 2 (N ∧ N) 2 (1) {N ∧ N = μ-κ 2 -CH[N(2,6-iPr 2 C 6 H 3 )] 2 } in the H-H σ-bond cleavage was investigated. DFT calculations disclosed that the H-H σ-bond cleavage by 1 occurs with nearly no barrier to afford the cis-dihydride species followed by cis-trans isomerization to form the trans-dihydride product, which is consistent with the experimental result. The O-H and C-H bond cleavages by 1 were computationally predicted to occur with moderate (ΔG° ⧧ = 9.0 kcal/mol) and acceptable activation energies (ΔG° ⧧ = 22.5 kcal/mol), respectively, suggesting that the Mo-Mo quintuple bond can be applied to various σ-bond cleavages. In these σ-bond cleavage reactions, the charge-transfer (CT Mo→XH ) from the Mo-Mo quintuple bond to the X-H (X = H, C, or O) bond and that (CT XH→Mo ) from the X-H bond to the Mo-Mo bond play crucial roles. Though the HOMO (dδ-MO) of 1 is at lower energy and the LUMO + 2 (dδ*-MO) of 1 is at higher energy than those of RhCl(PMe 3 ) 2 (LUMO and LUMO + 1 of 1 are not frontier MO), the H-H σ-bond cleavage by 1 more easily occurs than that by the Rh complex. Hence, the frontier MO energies are not the reason for the high reactivity of 1. The high reactivity of 1 arises from the polarization of dδ-type MOs of the Mo-Mo quintuple bond in the transition state. Such a polarized electronic structure enhances the bonding overlap between the dδ-MO of the Mo-Mo bond and the σ*-antibonding MO of the X-H bond to facilitate the CT Mo→XH and reduce the exchange repulsion between the Mo-Mo bond and the X-H bond. This polarized electronic structure of the transition state is similar to that of a frustrated Lewis pair. The easy polarization of the dδ-type MOs is one of the advantages of the metal-metal multiple bond, because such polarization is impossible in the mononuclear metal complex.

The excited-state intramolecular proton transfer in Nsbnd H-type dye molecules with a seven-membered-ring intramolecular hydrogen bond: A theoretical insight

NASA Astrophysics Data System (ADS)

Yuan, Huijuan; Feng, Songyan; Wen, Keke; Guo, Xugeng; Zhang, Jinglai

2018-02-01

Excited-state intramolecular proton transfer (ESIPT) reactions of a series of N(R)sbnd H ⋯ N-type seven-membered-ring hydrogen-bonding compounds were explored by employing density functional theory/time-dependent density functional theory calculations with the PBE0 functional. Our results indicate that the absorption and emission spectra predicted theoretically match very well the experimental findings. Additionally, as the electron-withdrawing strength of R increases, the intramolecular H-bond of the Nsbnd S1 form gradually enhances, and the forward energy barrier along the ESIPT reaction gradually decreases. For compound 4, its ESIPT reaction is found to be a barrierless process due to the involvement of a strong electron-withdrawing COCF3 group. It is therefore a reasonable presumption that the ESIPT efficiency of these N(R)sbnd H ⋯ N-type seven-membered-ring H-bonding systems can be improved when a strong electron-withdrawing group in R is introduced.

Control of concerted two bond versus single bond dissociation in CH(3)Co(CO)(4) via an intermediate state using pump-dump laser pulses.

PubMed

Ambrosek, David; González, Leticia

2007-10-07

Wavepacket propagations on ab initio multiconfigurational two-dimensional potential energy surfaces for CH(3)Co(CO)(4) indicate that after irradiation to the lowest first and second electronic excited states, concerted dissociation of CH(3) and the axial CO ligand takes place. We employ a pump-dump sequence of pulses with appropriate frequencies and time delays to achieve the selective breakage of a single bond by controlling the dissociation angle. The pump and dump pulse sequence exploits the unbound surface where dissociation occurs in a counterintuitive fashion; stretching of one bond in an intermediate state enhances the single dissociation of the other bond.

Selective bond breaking mediated by state specific vibrational excitation in model HOD molecule through optimized femtosecond IR pulse: a simulated annealing based approach.

PubMed

Shandilya, Bhavesh K; Sen, Shrabani; Sahoo, Tapas; Talukder, Srijeeta; Chaudhury, Pinaki; Adhikari, Satrajit

2013-07-21

The selective control of O-H/O-D bond dissociation in reduced dimensionality model of HOD molecule has been explored through IR+UV femtosecond pulses. The IR pulse has been optimized using simulated annealing stochastic approach to maximize population of a desired low quanta vibrational state. Since those vibrational wavefunctions of the ground electronic states are preferentially localized either along the O-H or O-D mode, the femtosecond UV pulse is used only to transfer vibrationally excited molecule to the repulsive upper surface to cleave specific bond, O-H or O-D. While transferring from the ground electronic state to the repulsive one, the optimization of the UV pulse is not necessarily required except specific case. The results so obtained are analyzed with respect to time integrated flux along with contours of time evolution of probability density on excited potential energy surface. After preferential excitation from [line]0, 0> ([line]m, n> stands for the state having m and n quanta of excitations in O-H and O-D mode, respectively) vibrational level of the ground electronic state to its specific low quanta vibrational state ([line]1, 0> or [line]0, 1> or [line]2, 0> or [line]0, 2>) by using optimized IR pulse, the dissociation of O-D or O-H bond through the excited potential energy surface by UV laser pulse appears quite high namely, 88% (O-H ; [line]1, 0>) or 58% (O-D ; [line]0, 1>) or 85% (O-H ; [line]2, 0>) or 59% (O-D ; [line]0, 2>). Such selectivity of the bond breaking by UV pulse (if required, optimized) together with optimized IR one is encouraging compared to the normal pulses.

Determination of interfacial states in solid heterostructures using a variable-energy positron beam

DOEpatents

Asoka kumar, Palakkal P. V.; Lynn, Kelvin G.

1993-01-01

A method and means is provided for characterizing interfacial electron states in solid heterostructures using a variable energy positron beam to probe the solid heterostructure. The method includes the steps of directing a positron beam having a selected energy level at a point on the solid heterostructure so that the positron beam penetrates into the solid heterostructure and causes positrons to collide with the electrons at an interface of the solid heterostructure. The number and energy of gamma rays emitted from the solid heterostructure as a result of the annihilation of positrons with electrons at the interface are detected. The data is quantified as a function of the Doppler broadening of the photopeak about the 511 keV line created by the annihilation of the positrons and electrons at the interface, preferably, as an S-parameter function; and a normalized S-parameter function of the data is obtained. The function of data obtained is compared with a corresponding function of the Doppler broadening of the annihilation photopeak about 511 keV for a positron beam having a second energy level directed at the same material making up a portion of the solid heterostructure. The comparison of these functions facilitates characterization of the interfacial states of electrons in the solid heterostructure at points corresponding to the penetration of positrons having the particular energy levels into the interface of the solid heterostructure. Accordingly, the invention provides a variable-energy non-destructive probe of solid heterostructures, such as SiO.sub.2 /Si, MOS or other semiconductor devices.

Determination of interfacial states in solid heterostructures using a variable-energy positron beam

DOEpatents

Asokakumar, P.P.V.; Lynn, K.G.

1993-04-06

A method and means is provided for characterizing interfacial electron states in solid heterostructures using a variable energy positron beam to probe the solid heterostructure. The method includes the steps of directing a positron beam having a selected energy level at a point on the solid heterostructure so that the positron beam penetrates into the solid heterostructure and causes positrons to collide with the electrons at an interface of the solid heterostructure. The number and energy of gamma rays emitted from the solid heterostructure as a result of the annihilation of positrons with electrons at the interface are detected. The data is quantified as a function of the Doppler broadening of the photopeak about the 511 keV line created by the annihilation of the positrons and electrons at the interface, preferably, as an S-parameter function; and a normalized S-parameter function of the data is obtained. The function of data obtained is compared with a corresponding function of the Doppler broadening of the annihilation photopeak about 511 keV for a positron beam having a second energy level directed at the same material making up a portion of the solid heterostructure. The comparison of these functions facilitates characterization of the interfacial states of electrons in the solid heterostructure at points corresponding to the penetration of positrons having the particular energy levels into the interface of the solid heterostructure. Accordingly, the invention provides a variable-energy non-destructive probe of solid heterostructures, such as SiO[sub 2]/Si, MOS or other semiconductor devices.

Coherent photoluminescence excitation spectroscopy of semicrystalline polymeric semiconductors

NASA Astrophysics Data System (ADS)

Silva, Carlos; Grégoire, Pascal; Thouin, Félix

In polymeric semiconductors, the competition between through-bond (intrachain) and through-space (interchain) electronic coupling determines two-dimensional spatial coherence of excitons. The balance of intra- and interchain excitonic coupling depends very sensitively on solid-state microstructure of the polymer film (polycrystalline, semicrystalline with amorphous domains, etc.). Regioregular poly(3-hexylthiophene) has emerged as a model material because its photoluminescence (PL) spectral lineshape reveals intricate information on the magnitude of excitonic coupling, the extent of energetic disorder, and on the extent to which the disordered energy landscape is correlated. I discuss implementation of coherent two-dimensional electronic spectroscopy. We identify cross peaks between 0-0 and 0-1 excitation peaks, and we measure their time evolution, which we interpret within the context of a hybrid HJ aggregate model. By measurement of the homogeneous linewidth in diverse polymer microstructures, we address the nature of optical transitions within such hynbrid aggregate model. These depend strongly on sample processing, and I discuss the relationship between microstructure, steady-state absorption and PL spectral lineshape, and 2D coherent PL excitation spectral lineshapes.

Theoretical Studies of Solids under Extreme Conditions.

DTIC Science & Technology

1983-12-01

properties of solids at low temperature. 5. Electron-phonon- magnon interactions. 6. Many body interactions in solids and at solid surfaces. - -a’ ELEC;TN4...and D. S. Marynick. 27. Trip to Louisiana State University to consult with Professor J. Callaway on electron-phonon- magnon interactions and set up to

rac-4-(2-Meth-oxy-phen-yl)-2,6-dimethyl-cyclo-hex-3-ene-carb-oxy-lic acid.

PubMed

Xie, Songwen; Fowler, Brian P; Deyo, Sara M; Pink, Maren

2010-05-29

The title compound, C(16)H(20)O(3), was synthesized to study the hydrogen-bonding inter-actions of the two enanti-omers in the solid state. Inter-molecular O-H⋯O hydrogen bonds produce centrosymmetric R(2) (2)(8) rings which dimerize the two chiral enanti-omers together through their carboxyl groups.

Structural and electronic properties of U{sub n}O{sub m} (n=1-3,m=1-3n) clusters: A theoretical study using screened hybrid density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Yu; Liu, Haitao; Zhang, Ping, E-mail: zhang-ping@iapcm.ac.cn

The structural and electronic properties of small uranium oxide clusters U{sub n}O{sub m} (n=1-3, m=1-3n) are systematically studied within the screened hybrid density functional theory. It is found that the formation of U–O–U bondings and isolated U–O bonds are energetically more stable than U–U bondings. As a result, no uranium cores are observed. Through fragmentation studies, we find that the U{sub n}O{sub m} clusters with the m/n ratio between 2 and 2.5 are very stable, hinting that UO{sub 2+x} hyperoxides are energetically stable. Electronically, we find that the O-2p states always distribute in the deep energy range, and the U-5fmore » states always distribute at the two sides of the Fermi level. The U-6d states mainly hybridize with the U-5f states in U-rich clusters, while hybridizing with O-2p states in O-rich clusters. Our work is the first one on the screened hybrid density functional theory level studying the atomic and electronic properties of the actinide oxide clusters.« less

A unifying approach to lattice dynamical and electronic properties of solids

NASA Astrophysics Data System (ADS)

Falter, C.

1988-06-01

A unified analysis of lattice dynamical and electronic properties of solids with special emphasis on the interaction between electrons and phonons is presented. The article is roughly divided into two parts reflecting different points of view. The density response of the electrons provides the link between these parts. In the first part, the microscopic theory in terms of the density response in crystals is discussed. Relations are pointed out between the density response approach and the density functional theory. The latter is used for a representation of the exchange-correlation interaction and the microscopic force constants. Relevant methods, as recently proposed by various authors for the calculation of the density response in inhomogeneous solids are discussed. Particular attention is paid to the development of a renormalized response description. Applications of this method to lattice dynamical and electronic properties are presented. In the second part an alternative physical concept, the quasi-ion approach, is outlined. This concept is shown to provide a microscopic basis for electronic charge localization in crystals and proves the importance of the correlation between crystal symmetry and many-body effects. Is is derived that within linear response theory an appropriate decomposition of the valence charge density leads uniquely to a spatially localized density contribution at the individual ion which follows its motion rigidly. The composite consisting of this partial density and the ion core is taken to be an individual entity, denoted as quasi-ion, from which the crystal is built up. In a certain sense this is a generalization of Ziman's concept of neutral pseudo-atoms being approximately valid in simple metals. New insight into the bonding mechanism and charge relaxation processes is shown to follow from this concept. In particular, we discuss the covalent, ionic and metallic bonding mechanisms, using the localized picture provided by the partial densities, on the same basis. The quasi-ion approach is also applied to the calculation of phonon-induced charge density redistributions and to the construction of a simplified formulation of microscopic lattice dynamics. Investigations of the phonon dispersion for different bonding types are given within a rigid quasi-ion model and extensions of this model are outlined. Among other things, these calculations indicate that bonding dynamics of (covalent) molecules and crystals can be described by relative rotations of the quasi-ions under the condition of rotational invariance of the system. Finally, possible applications of the quasi-ion concept to an approximate formulation of anharmonic lattice dynamics and the interaction between electrons and phonons are discussed. A numerical investigation of this interaction is presented and compared with the results from the rigid-ion model. As a consequence of the quasi-ion concept a consistent calculation of the phonon dispersion, the electronic band structure and the electron-phonon interaction becomes possible.

Ceramic-to-metal bonding for pressure transducers

NASA Technical Reports Server (NTRS)

Mackenzie, J. D.

1984-01-01

A solid-state diffusion technique involving the placement of a gold foil between INCONEL X-750 and a machinable glass-ceramic "MACOR" was shown to be successful in bonding these two materials. This technique was selected after an exhaustive literature search on ceramic-metal bonding methods. Small expansion mismatch between the Inconel and the MACOR resulted in fracture of the MACOR when the bonded body was subjected to tensile stress of 535 psi. The bonded parts were submitted to a cyclic loading test in an air atmosphere at 1 Hz from 0 to 60 KPa. Failure was observed after 700,000 cycles at 650 C. Ceramic-Inconel bonding was not achieved with this method for boron nitride and silica glass.

Environment-dependent conformation investigation of 3-amino-1,2,4-triazole (3-AT): Raman Spectroscopy and density functional theory

NASA Astrophysics Data System (ADS)

Meng, Shuang; Zhao, Yanying; Xue, Jiadan; Zheng, Xuming

2018-02-01

In the paper, diverse tautomers of 3-amino-1,2,4-triazole (3AT) in solid and polar solvent have been explored by FT-IR, FT-Raman and 488 nm Raman experiments combing with quantum chemical theoretical calculation using PCM solvent model and normal mode analysis. The vibrational spectra prefer the 3-amino-1,2,4-2H-triazole (2H-3AT) dimer in solid, while in a polar solvent 3AT is apt to the 3-amino-1,2,4-2H-triazole (2H-3AT) monomer. The significant wavenumber difference and Raman intensity patterns in solid and different solvents are induced by hydrogen bond perturbation along > NH ⋯ N ≤ hydrogen bonds on five-membered N-heterocyclic ring. The ground state proton transfer reaction mechanism along the five-membered N-heterocyclic ring is supported by intermolecular hydrogen bonding between 3AT and protonic solvent molecules.

Monolithic solid-state lasers for spaceflight

NASA Astrophysics Data System (ADS)

Krainak, Michael A.; Yu, Anthony W.; Stephen, Mark A.; Merritt, Scott; Glebov, Leonid; Glebova, Larissa; Ryasnyanskiy, Aleksandr; Smirnov, Vadim; Mu, Xiaodong; Meissner, Stephanie; Meissner, Helmuth

2015-02-01

A new solution for building high power, solid state lasers for space flight is to fabricate the whole laser resonator in a single (monolithic) structure or alternatively to build a contiguous diffusion bonded or welded structure. Monolithic lasers provide numerous advantages for space flight solid-state lasers by minimizing misalignment concerns. The closed cavity is immune to contamination. The number of components is minimized thus increasing reliability. Bragg mirrors serve as the high reflector and output coupler thus minimizing optical coatings and coating damage. The Bragg mirrors also provide spectral and spatial mode selection for high fidelity. The monolithic structure allows short cavities resulting in short pulses. Passive saturable absorber Q-switches provide a soft aperture for spatial mode filtering and improved pointing stability. We will review our recent commercial and in-house developments toward fully monolithic solid-state lasers.

Load regulating expansion fixture

DOEpatents

Wagner, L.M.; Strum, M.J.

1998-12-15

A free standing self contained device for bonding ultra thin metallic films, such as 0.001 inch beryllium foils is disclosed. The device will regulate to a predetermined load for solid state bonding when heated to a bonding temperature. The device includes a load regulating feature, whereby the expansion stresses generated for bonding are regulated and self adjusting. The load regulator comprises a pair of friction isolators with a plurality of annealed copper members located therebetween. The device, with the load regulator, will adjust to and maintain a stress level needed to successfully and economically complete a leak tight bond without damaging thin foils or other delicate components. 1 fig.

High-throughput design and optimization of fast lithium ion conductors by the combination of bond-valence method and density functional theory

NASA Astrophysics Data System (ADS)

Xiao, Ruijuan; Li, Hong; Chen, Liquan

2015-09-01

Looking for solid state electrolytes with fast lithium ion conduction is an important prerequisite for developing all-solid-state lithium secondary batteries. By combining the simulation techniques in different levels of accuracy, e.g. the bond-valence (BV) method and the density functional theory (DFT), a high-throughput design and optimization scheme is proposed for searching fast lithium ion conductors as candidate solid state electrolytes for lithium rechargeable batteries. The screening from more than 1000 compounds is performed through BV-based method, and the ability to predict reliable tendency of the Li+ migration energy barriers is confirmed by comparing with the results from DFT calculations. β-Li3PS4 is taken as a model system to demonstrate the application of this combination method in optimizing properties of solid electrolytes. By employing the high-throughput DFT simulations to more than 200 structures of the doping derivatives of β-Li3PS4, the effects of doping on the ionic conductivities in this material are predicted by the BV calculations. The O-doping scheme is proposed as a promising way to improve the kinetic properties of this materials, and the validity of the optimization is proved by the first-principles molecular dynamics (FPMD) simulations.

Characterization and biological studies on Co(II), Ni(II) and Cu(II) complexes of carbohydrazones ending by pyridyl ring.

PubMed

Abu El-Reash, G M; El-Gammal, O A; Ghazy, S E; Radwan, A H

2013-03-01

The chelating behavior of ligands based on carbohydrazone core modified with pyridine end towards Co(II), Ni(II) and Cu(II) ions have been examined. The ligands derived from the condensation of carbohydrazide with 2-acetylpyridine (H(2)APC) and 4-acetylpyridine (H(2)APEC). The (1)H NMR, IR data and the binding energy calculations of H(2)APC revealed the presence of two stereoisomers syn and anti in the solid state and in the solution. The (1)H NMR, IR data and the binding energy calculations confirmed the presence of H(2)APEC in one keto form only in the solid state and in the solution. The spectroscopic data confirmed that H(2)APC behaves as a monobasic pentadentate in Co(II) and Cu(II) complexes and as mononegative tetradentate in Ni(II) complex. On the other hand, H(2)APEC acts as a mononegative tridentate in Co(II) complex, neutral tridentate in Ni(II) complex and neutral bidentate in Cu(II) complex. The electronic spectra and the magnetic measurements of complexes as well as the ESR of the copper complexes suggested the octahedral geometry. The bond length and bond angles were evaluated by DFT method using material studio program. The thermal behavior and the kinetic parameters of degradation were determined using Coats-Redfern and Horowitz-Metzger methods. The antioxidant (DDPH and ABTS methods), anti-hemolytic and in vitro Ehrlich ascites of the compounds have been screened. Copyright © 2012 Elsevier B.V. All rights reserved.

Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

NASA Astrophysics Data System (ADS)

Marin, Timothy W.; Janik, Ireneusz; Bartels, David M.; Chipman, Daniel M.

2017-05-01

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381 °C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. Using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.

Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

DOE PAGES

Marin, Timothy W.; Janik, Ireneusz; Bartels, David M.; ...

2017-05-17

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381°C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as themore » water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. As a result, using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.« less

Nuts and Bolts of the Ion Band State Theory

NASA Astrophysics Data System (ADS)

Chubb, Scott R.

2005-12-01

The nuts and bolts of our ion band state theory of low energy nuclear reactions (LENR's) in palladium-deuteride (PdD) and palladium-hydride (PdH) are the electrons that hold together or tear apart the bonds (or lack of bonds) between deuterons (d's) or protons (p's) and the host material. In PdDx and PdHx, this bonding is strongly correlated with loading. In ambient loading conditions (x ≲ 0.6), bonding inhibits ion band state occupation. As x → 1, slight increases and decreases in loading can induce "vibrations" (which have conventionally been thought to occur from phonons) that can induce potential losses or increases of p/d. Naive assumptions about phonons fail to include these losses and increases. These effects can occur because neither H or D has core electrons and because in either PdD or PdH, the electrons near the Fermi energy have negligible overlap with the nucleus of either D or H. In the past, implicitly, we have used these facts to justify our ion band state theory. Here, we present a more formal justification, based on the relationship between H(D) ion band states (IBS's) and H(D) phonons that includes a microscopic picture that explains why occupation of IBS's can occur in PdD and PdH and how this can lead to nuclear reactions.

Carbon under extreme conditions: phase boundaries and electronic properties from first-principles theory.

PubMed

Correa, Alfredo A; Bonev, Stanimir A; Galli, Giulia

2006-01-31

At high pressure and temperature, the phase diagram of elemental carbon is poorly known. We present predictions of diamond and BC8 melting lines and their phase boundary in the solid phase, as obtained from first-principles calculations. Maxima are found in both melting lines, with a triple point located at approximately 850 GPa and approximately 7,400 K. Our results show that hot, compressed diamond is a semiconductor that undergoes metalization upon melting. In contrast, in the stability range of BC8, an insulator to metal transition is likely to occur in the solid phase. Close to the diamond/liquid and BC8/liquid boundaries, molten carbon is a low-coordinated metal retaining some covalent character in its bonding up to extreme pressures. Our results provide constraints on the carbon equation of state, which is of critical importance for devising models of Neptune, Uranus, and white dwarf stars, as well as of extrasolar carbon-rich planets.

Carbon under extreme conditions: Phase boundaries and electronic properties from first-principles theory

DOE PAGES

Correa, Alfredo A.; Bonev, Stanimir A.; Galli, Giulia

2006-01-23

At high pressure and temperature, the phase diagram of elemental carbon is poorly known. We present predictions of diamond and BC8 melting lines and their phase boundary in the solid phase, as obtained from first-principles calculations. Maxima are found in both melting lines, with a triple point located at ≈ 850 GPa and ≈ 7,400 K. Our results show that hot, compressed diamond is a semiconductor that undergoes metalization upon melting. In contrast, in the stability range of BC8, an insulator to metal transition is likely to occur in the solid phase. Close to the diamond/liquid and BC8/liquid boundaries, moltenmore » carbon is a low-coordinated metal retaining some covalent character in its bonding up to extreme pressures. Lastly, our results provide constraints on the carbon equation of state, which is of critical importance for devising models of Neptune, Uranus, and white dwarf stars, as well as of extrasolar carbon-rich planets.« less

Low-lying energy spectrum of the cerium dimer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nikolaev, A. V.; Skobeltsyn Institute of Nuclear Physics, Moscow State University, Vorob'evy Gory 1/2, 119991, Moscow

2011-07-15

The electronic structure of Ce{sub 2} is studied in a valence bond model with two 4f electrons localized at two cerium sites. It is shown that the low-lying energy spectrum of the simplest cerium chemical bond is determined by peculiarities of the occupied 4f states. The model allows for an analytical solution, which is discussed along with the numerical analysis. The energy spectrum is a result of the interplay between the 4f valence bond exchange, the 4f Coulomb repulsion, and the spin-orbit coupling. The calculated ground state is the even {Omega}={Lambda}={Sigma}=0 level, the lowest excitations situated at {approx}30 K aremore » the odd {Omega}={Lambda}={Sigma}=0 state and the {sup 3}6{sub 5} doublet ({Omega}={+-}5,{Lambda}={+-}6,{Sigma}={+-}1). The calculated magnetic susceptibility displays different behavior at high and low temperatures. In the absence of the spin-orbit coupling the ground state is the {sup 3}{Sigma}{sub g}{sup -} triplet. The results are compared with other many-electron calculations and experimental data.« less

Electronic structure and bonding interactions in Ba1- x Sr x Zr0.1Ti0.9O3 ceramics

NASA Astrophysics Data System (ADS)

Mangaiyarkkarasi, Jegannathan; Sasikumar, Subramanian; Saravanan, Olai Vasu; Saravanan, Ramachandran

2017-06-01

An investigation on the precise electronic structure and bonding interactions has been carried out on Ba1- x Sr x Zr0.1Ti0.9O3 (short for BSZT, x = 0, 0.05, 0.07 and 0.14) ceramic systems prepared via high-temperature solid state reaction technique. The influence of Sr doping on the BSZT structure has been examined by characterizing the prepared samples using PXRD, UV-visible spectrophotometry, SEM and EDS. Powder profile refinement of X-ray data confirms that all the synthesized samples have been crystallized in cubic perovskite structure with single phase. Charge density distribution of the BSZT systems has been completely analyzed by the maximum entropy method (MEM). Co-substitution of Sr at the Ba site and Zr at the Ti site into the BaTiO3 structure presents the ionic nature between Ba and O ions and the covalent nature between Ti and O ions, revealed from MEM calculations. Optical band gap values have been evaluated from UV-visible absorption spectra. Particles with irregular shapes and well defined grain boundaries are clearly visualized from SEM images. The phase purity of the prepared samples is further confirmed by EDS qualitative spectral analysis.

Microfluidic multiplexing of solid-state nanopores

NASA Astrophysics Data System (ADS)

Jain, Tarun; Rasera, Benjamin C.; Guerrero, Ricardo Jose S.; Lim, Jong-Min; Karnik, Rohit

2017-12-01

Although solid-state nanopores enable electronic analysis of many clinically and biologically relevant molecular structures, there are few existing device architectures that enable high-throughput measurement of solid-state nanopores. Herein, we report a method for microfluidic integration of multiple solid-state nanopores at a high density of one nanopore per (35 µm2). By configuring microfluidic devices with microfluidic valves, the nanopores can be rinsed from a single fluid input while retaining compatibility for multichannel electrical measurements. The microfluidic valves serve the dual purpose of fluidic switching and electric switching, enabling serial multiplexing of the eight nanopores with a single pair of electrodes. Furthermore, the device architecture exhibits low noise and is compatible with electroporation-based in situ nanopore fabrication, providing a scalable platform for automated electronic measurement of a large number of integrated solid-state nanopores.

Comparisons of NDT Methods to Inspect Cork and Cork filled Epoxy Bands

NASA Technical Reports Server (NTRS)

Lingbloom, Mike

2007-01-01

Sheet cork and cork filled epoxy provide external insulation for the Reusable Solid Rocket Motor (RSRM) on the Nation's Space Transportation System (STS). Interest in the reliability of the external insulation bonds has increased since the Columbia incident. A non-destructive test (NDT) method that will provide the best inspection for these bonds has been under evaluation. Electronic Shearography has been selected as the primary NDT method for inspection of these bond lines in the RSRM production flow. ATK Launch Systems Group has purchased an electronic shearography system that includes a vacuum chamber that is used for evaluation of test parts and custom vacuum windows for inspection of full-scale motors. Although the electronic shearography technology has been selected as the primary method for inspection of the external bonds, other technologies that exist continue to be investigated. The NASA/Marshall Space Flight Center (MSFC) NDT department has inspected several samples for comparison with electronic shearography with various inspections systems in their laboratory. The systems that were evaluated are X-ray backscatter, terahertz imaging, and microwave imaging. The samples tested have some programmed flaws as well as some flaws that occurred naturally during the sample making process. These samples provide sufficient flaw variation for the evaluation of the different inspection systems. This paper will describe and compare the basic functionality, test method and test results including dissection for each inspection technology.

Clumped isotope thermometry in deeply buried sedimentary carbonates: The effects of C-O bond reordering and recrystallization

NASA Astrophysics Data System (ADS)

Passey, B. H.; Shenton, B.; Grossman, E. L.; Henkes, G. A.; Laya, J. C.; Perez-Huerta, A.

2014-12-01

Constraining the thermal histories of sedimentary basins is fundamental to a range of geologic applications including tectonics, petroleum system analysis, and the genesis of ore deposits. Carbonate rocks can serve as archives of basin thermal histories through solid-state reordering of their 13C-18O, or 'clumped isotope', bonds at elevated burial temperatures. Here we present one of the first applied studies of carbonate clumped isotope reordering to explore the diagenetic and thermal histories of exhumed brachiopods, crinoids, cements, and host rock in the Permian Palmarito Formation, Venezuela and the Carboniferous Bird Spring Formation, Nevada, USA. Carbonate components in the Palmarito Formation, buried to ~4 km depth, yield statistically indistinguishable clumped isotope temperatures (T(Δ47)) ranging from 86 to 122 °C. Clumped isotope temperatures of components in the more deeply buried Bird Spring Formation (>5 km), range from ~100 to 165 °C and differ by component type, with brachiopods and pore-filling cements yielding the highest T(Δ47) (mean = 153 and 141 °C, respectively) and crinoids and host rock yielding significantly cooler T(Δ47) (mean = 103 and 114 °C). New high-resolution thermal histories are coupled with kinetic models to predict the extent of solid-state C-O bond reordering during burial and exhumation for both sites. Application of these models suggests that brachiopods in the Palmarito Formation experienced partial bond reordering without complete equilibration of clumped isotopes at maximum burial temperature. In contrast, clumped isotope bonds of brachiopods from the Bird Spring Formation appear to have completely equilibrated at maximum burial temperature, and now reflect blocking temperatures 'locked-in' during cooling. The 40-50 °C cooler clumped isotope temperatures measured in Bird Spring Formation crinoids and host rock can be explained by both recrystallization and cementation during shallow burial and a greater inherent resistance to solid-state reordering than brachiopods.

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy.

PubMed

Guo, Jing; You, Sifan; Wang, Zhichang; Peng, Jinbo; Ma, Runze; Jiang, Ying

2018-05-27

Water/solid interfaces are ubiquitous and play a key role in many environmental, biophysical, and technological processes. Resolving the internal structure and probing the hydrogen-bond (H-bond) dynamics of the water molecules adsorbed on solid surfaces are fundamental issues of water science, which remains a great challenge owing to the light mass and small size of hydrogen. Scanning tunneling microscopy (STM) is a promising tool for attacking these problems, thanks to its capabilities of sub-Ångström spatial resolution, single-bond vibrational sensitivity, and atomic/molecular manipulation. The designed experimental system consists of a Cl-terminated tip and a sample fabricated by dosing water molecules in situ onto the Au(111)-supported NaCl(001) surfaces. The insulating NaCl films electronically decouple the water from the metal substrates, so the intrinsic frontier orbitals of water molecules are preserved. The Cl-tip facilitates the manipulation of the single water molecules, as well as gating the orbitals of water to the proximity of Fermi level (EF) via tip-water coupling. This paper outlines the detailed methods of submolecular resolution imaging, molecular/atomic manipulation, and single-bond vibrational spectroscopy of interfacial water. These studies open up a new route for investigating the H-bonded systems at the atomic scale.

METHOD OF SOLID STATE WELDING

DOEpatents

Storchheim, S.

1958-07-10

An improved method is described for pressure bonding of dissimilar metals, particularly nickel and aluminum. Using ordinary techniques for the pressure bonding of these metals, an alloy zone is usually formed between the metals, and this alloy zone exhibits undesirable brittleness and lack of tensile strengh. Formation of this alloy zone can be inhibited or prevented by heating the metals being bonded to a temperature below the melting point of either of the metals and using very high pressures for short periods of time. In this manner a bond is formed without the formation of the undesirable alloy zone.

Programming Recognition Arrays through Double Chalcogen-Bonding Interactions.

PubMed

Biot, Nicolas; Bonifazi, Davide

2018-04-11

In this work, we have programmed and synthesized a recognition motif constructed around a chalcogenazolo-pyridine scaffold (CGP) that, through the formation of frontal double chalcogen-bonding interactions, associates into dimeric EX-type complexes. The reliability of the double chalcogen-bonding interaction has been shown at the solid-state by X-ray analysis, depicting the strongest recognition persistence for a Te-congener. The high recognition fidelity, chemical and thermal stability and easy derivatization at the 2-position makes CGP a convenient motif for constructing supramolecular architectures through programmed chalcogen-bonding interactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron density determination and bonding in tetragonal binary intermetallics by convergent beam electron diffraction

NASA Astrophysics Data System (ADS)

Sang, Xiahan

Intermetallics offer unique property combinations often superior to those of more conventional solid solution alloys of identical composition. Understanding of bonding in intermetallics would greatly accelerate development of intermetallics for advanced and high performance engineering applications. Tetragonal intermetallics L10 ordered TiAl, FePd and FePt are used as model systems to experimentally measure their electron densities using quantitative convergent beam electron diffraction (QCBED) method and then compare details of the 3d-4d (FePd) and 3d-5d (FePt) electron interactions to elucidate their role on properties of the respective ferromagnetic L10-ordered intermetallics FePd and FePt. A new multi-beam off-zone axis condition QCBED method has been developed to increase sensitivity of CBED patterns to change of structure factors and the anisotropic Debye-Waller (DW) factors. Unprecedented accuracy and precision in structure and DW factor measurements has been achieved by acquiring CBED patterns using beam-sample geometry that ensures strong dynamical interaction between the fast electrons and the periodic potential in the crystalline samples. This experimental method has been successfully applied to diamond cubic Si, and chemically ordered B2 cubic NiAl, tetragonal L10 ordered TiAl and FePd. The accurate and precise experimental DW and structure factors for L10 TiAl and FePd allow direct evaluation of computer calculations using the current state of the art density functional theory (DFT) based electron structure modeling. The experimental electron density difference map of L1 0 TiAl shows that the DFT calculations describe bonding to a sufficient accuracy for s- and p- electrons interaction, e. g., the Al-layer. However, it indicate significant quantitative differences to the experimental measurements for the 3d-3d interactions of the Ti atoms, e.g. in the Ti layers. The DFT calculations for L10 FePd also show that the current DFT approximations insufficiently describe the interaction between Fe-Fe (3d-3d), Fe-Pd (3d-4d) and Pd-Pd (4d-4d) electrons, which indicates the necessity to evaluate applicability of different DFT approximations, and also provides experimental data for the development of new DFT approximation that better describes transition metal based intermetallic systems.

The Quintessential Bond of Modern Science. The Detection and Characterization of Diatomic Gold Sulfide, AuS.

NASA Astrophysics Data System (ADS)

Kokkin, Damian L.; Zhang, Ruohan; Steimle, Timothy; Pearlman, Bradley W.; Wyse, Ian A.; Varberg, Thomas D.

2015-06-01

The gold sulfur bond is becoming ever more important to a vast range of scientific endeavors. We have recorded the electronic spectrum of gas-phase AuS, at vibrational resolution, over the 440-740 nm wavelength range. By application of a synergy of production techniques, hot hollow-cathode sputtering source and cold laser ablation molecular beam source, excitation from both spin components of the inverted ^2Π ground state is possible. Excitation into four different excited electronic states involving approximately 100 red-degraded bands has been observed. The four excited states have been characterized as a^4σ1/2, A^2σ^+1/2, B^2σ^-1/2 and C^2Δ_i. The observed red-degraded vibronic bands where then globally analyzed to determine an accurate set of term energies and vibrational constants for the excited and ground electronic states. The electronic configurations from which these states arise will be discussed.

On the use of atomistic simulations to aid bulk metallic glasses structural elucidation with solid-state NMR.

PubMed

Ferreira, Ary R; Rino, José P

2017-08-24

Solid-state nuclear magnetic resonance (ssNMR) experimental 27 Al metallic shifts reported in the literature for bulk metallic glasses (BMGs) were revisited in the light of state-of-the-art atomistic simulations. In a consistent way, the Gauge-Including Projector Augmented-Wave (GIPAW) method was applied in conjunction with classical molecular dynamics (CMD). A series of Zr-Cu-Al alloys with low Al concentrations were selected as case study systems, for which realistic CMD derived structural models were used for a short- and medium-range order mining. That initial procedure allowed the detection of trends describing changes on the microstructure of the material upon Al alloying, which in turn were used to guide GIPAW calculations with a set of abstract systems in the context of ssNMR. With essential precision and accuracy, the ab initio simulations also yielded valuable trends from the electronic structure point of view, which enabled an overview of the bonding nature of Al-centered clusters as well as its influence on the experimental ssNMR outcomes. The approach described in this work might promote the use of ssNMR spectroscopy in research on glassy metals. Moreover, the results presented demonstrate the possibility to expand the applications of this technique, with deeper insight into nuclear interactions and less speculative assignments.

Evidence for cis Amide Bonds in Peptoid Nanosheets.

PubMed

Hudson, Benjamin C; Battigelli, Alessia; Connolly, Michael D; Edison, John; Spencer, Ryan K; Whitelam, Stephen; Zuckermann, Ronald N; Paravastu, Anant K

2018-05-17

Peptoid nanosheets are supramolecular protein-mimetic materials that form from amphiphilic polypeptoids with aromatic and ionic side chains. Nanosheets have been studied at the nanometer scale, but the molecular structure has been difficult to probe. We report the use of 13 C- 13 C dipolar recoupling solid-state NMR measurements to reveal the configuration of backbone amide bonds selected by 13 C isotopic labeling of adjacent α-carbons. Measurements on the same molecules in the amorphous state and in nanosheets revealed that amide bonds in the center of the amino block of peptoid (NaeNpe) 7 -(NceNpe) 7 (B28) favor the trans configuration in the amorphous state and the cis configuration in the nanosheet. This unexpected result contrasts with previous NMR and theoretical studies of short solvated peptoids. Furthermore, examination of the amide bond at the junction of the two charged blocks within B28 revealed a mixture of both cis and trans configurational states, consistent with the previously predicted brickwork-like intermolecular organization.

Phase stability and electronic structure of UMo2Al20: A first-principles study

NASA Astrophysics Data System (ADS)

Liu, Peng-Chuang; Xian, Ya-Jiang; Wang, Xin; Zhang, Yu-Ting; Zhang, Peng-Cheng

2017-09-01

In this paper, the phase stability of UMo2Al20 was explored using cluster formula in combination with first-principles calculations. Cluster formula analysis uncovered that the compound was composed of two principal clusters, i.e. [Mo-Al12] and [U-Al16]. The electronic interactions between U, Mo and Al atoms in this compound were discussed using elastic property, Bader charges and energy-resolved local bonding analysis, as well as the electronic interactions between Mo and Al atoms in [Mo-Al12] cluster and between U and Al atoms in [U-Al16] cluster. It revealed that UMo2Al20 satisfied the mechanical stability criterion for cubic system, and exhibited near ionic bonding character with weak bonding directionality. The calculations within both standard DFT and HSE frameworks demonstrated that U and Al atoms acted as an electron donor while Mo atoms acted as electron acceptor. The intrinsic stability of UMo2Al20 mainly stemmed from the bonding states of Mo-Al bonds and Al-Al bonds in [Mo-Al12] cluster. These calculations provide a further insight on the CeCr2Al20-type ternary compounds.

Direct local solvent probing by transient infrared spectroscopy reveals the mechanism of hydrogen-bond induced nonradiative deactivation† †Electronic supplementary information (ESI) available: Experimental details, basic photophysics of ADA, transient electronic absorption, additional steady-state and transient IR spectra. See DOI: 10.1039/c7sc00437k Click here for additional data file.

PubMed Central

Dereka, Bogdan

2017-01-01

The fluorescence quenching of organic dyes via H-bonding interactions is a well-known phenomenon. However, the mechanism of this Hydrogen-Bond Induced Nonradiative Deactivation (HBIND) is not understood. Insight into this process is obtained by probing in the infrared the O–H stretching vibration of the solvent after electronic excitation of a dye with H-bond accepting cyano groups. The fluorescence lifetime of this dye was previously found to decrease from 1.5 ns to 110 ps when going from an aprotic solvent to the strongly protic hexafluoroisopropanol (HFP). Prompt strengthening of the H-bond with the dye was identified by the presence of a broad positive O–H band of HFP, located at lower frequency than the O–H band of the pure solvent. Further strengthening occurs within a few picoseconds before the excited H-bonded complex decays to the ground state in 110 ps. The latter process is accompanied by the dissipation of energy from the dye to the solvent and the rise of a characteristic hot solvent band in the transient spectrum. Polarization-resolved measurements evidence a collinear alignment of the nitrile and hydroxyl groups in the H-bonded complex, which persists during the whole excited-state lifetime. Measurements in other fluorinated alcohols and in chloroform/HFP mixtures reveal that the HBIND efficiency depends not only on the strength of the H-bond interactions between the dye and the solvent but also on the ability of the solvent to form an extended H-bond network. The HBIND process can be viewed as an enhanced internal conversion of an excited complex consisting of the dye molecule connected to a large H-bond network. PMID:28970892

Structural, bonding, and electronic properties of the hexagonal ferroelectric and paraelectric phases of LuMnO{sub 3} compound: A density functional theory study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sousa, A. M.; Coutinho, W. S.; Lima, A. F.

2015-02-21

We have investigated the structural, bonding, and electronic properties of both ferroelectric (FE) and paraelectric (PE) phases of the hexagonal LuMnO{sub 3} compound using calculations based on density functional theory. The structural properties have been determined by employing the generalized gradient approximation with Perdew-Burke-Ernzerhof and Wu-Cohen parameterization. The bonding and electronic properties have been treated by recently developed modified Becke-Johnson exchange potential, which succeeded to open a band gap for both PE and FE phases, in agreement with experimental predictions. The Bader’s topological analysis of electronic density showed that the character of the Lu–O axial bonds changes when the crystalmore » exhibits the PE → FE structural transition. This fact is in agreement with experimental findings. The covalent character of the Lu–O bond significantly increases due to orbital hybridization between the Lu 5d{sub z}{sup 2} and O 2p{sub z}-states. This bonding mechanism causes the ferroelectricity in the hexagonal LuMnO{sub 3} compound.« less

Proton transfer and hydrogen bonding in the organic solid state: a combined XRD/XPS/ssNMR study of 17 organic acid-base complexes.

PubMed

Stevens, Joanna S; Byard, Stephen J; Seaton, Colin C; Sadiq, Ghazala; Davey, Roger J; Schroeder, Sven L M

2014-01-21

The properties of nitrogen centres acting either as hydrogen-bond or Brønsted acceptors in solid molecular acid-base complexes have been probed by N 1s X-ray photoelectron spectroscopy (XPS) as well as (15)N solid-state nuclear magnetic resonance (ssNMR) spectroscopy and are interpreted with reference to local crystallographic structure information provided by X-ray diffraction (XRD). We have previously shown that the strong chemical shift of the N 1s binding energy associated with the protonation of nitrogen centres unequivocally distinguishes protonated (salt) from hydrogen-bonded (co-crystal) nitrogen species. This result is further supported by significant ssNMR shifts to low frequency, which occur with proton transfer from the acid to the base component. Generally, only minor chemical shifts occur upon co-crystal formation, unless a strong hydrogen bond is formed. CASTEP density functional theory (DFT) calculations of (15)N ssNMR isotropic chemical shifts correlate well with the experimental data, confirming that computational predictions of H-bond strengths and associated ssNMR chemical shifts allow the identification of salt and co-crystal structures (NMR crystallography). The excellent agreement between the conclusions drawn by XPS and the combined CASTEP/ssNMR investigations opens up a reliable avenue for local structure characterization in molecular systems even in the absence of crystal structure information, for example for non-crystalline or amorphous matter. The range of 17 different systems investigated in this study demonstrates the generic nature of this approach, which will be applicable to many other molecular materials in organic, physical, and materials chemistry.

Unraveling Crystalline Structure of High-Pressure Phase of Silicon Carbonate

NASA Astrophysics Data System (ADS)

Zhou, Rulong; Qu, Bingyan; Dai, Jun; Zeng, Xiao Cheng

2014-03-01

Although CO2 and SiO2 both belong to group-IV oxides, they exhibit remarkably different bonding characteristics and phase behavior at ambient conditions. At room temperature, CO2 is a gas, whereas SiO2 is a covalent solid with rich polymorphs. A recent successful synthesis of the silicon-carbonate solid from the reaction between CO2 and SiO2 under high pressure [M. Santoro et al., Proc. Natl. Acad. Sci. U.S.A. 108, 7689 (2011)] has resolved a long-standing puzzle regarding whether a SixC1-xO2 compound between CO2 and SiO2 exists in nature. Nevertheless, the detailed atomic structure of the SixC1-xO2 crystal is still unknown. Here, we report an extensive search for the high-pressure crystalline structures of the SixC1-xO2 compound with various stoichiometric ratios (SiO2:CO2) using an evolutionary algorithm. Based on the low-enthalpy structures obtained for each given stoichiometric ratio, several generic structural features and bonding characteristics of Si and C in the high-pressure phases are identified. The computed formation enthalpies show that the SiC2O6 compound with a multislab three-dimensional (3D) structure is energetically the most favorable at 20 GPa. Hence, a stable crystalline structure of the elusive SixC1-xO2 compound under high pressure is predicted and awaiting future experimental confirmation. The SiC2O6 crystal is an insulator with elastic constants comparable to typical hard solids, and it possesses nearly isotropic tensile strength as well as extremely low shear strength in the 2D plane, suggesting that the multislab 3D crystal is a promising solid lubricant. These valuable mechanical and electronic properties endow the SiC2O6 crystal for potential applications in tribology and nanoelectronic devices, or as a stable solid-state form for CO2 sequestration.

Charge Trapping Properties of Ge Nanocrystals Grown via Solid-State Dewetting

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnston, Steven; Jadli, I.; Aouassa, M.

2018-05-04

In the present work, we report on the charge trapping properties of Germanium Nanocrystals (Ge NCs) self assembled on SiO2 thin layer for promising applications in next-generation non volatile memory by the means of Deep Level Transient Spectroscopy (DLTS) and high frequency C-V method. The Ge NCs were grown via dewetting phenomenon at solid state by Ultra-High Vacuum (UHV) annealing and passivated with silicon before SiO2 capping. The role of the surface passivation is to reduce the electrical defect density at the Ge NCs-SiO2 interface. The presence of the Ge NCs in the oxide of the MOS capacitors strongly affectsmore » the C-V characteristics and increases the accumulation capacitance, causes a negative flat band voltage (VFB) shift. The DLTS has been used to study the individual Ge NCs as a single point deep level defect in the oxide. DLTS reveals two main features: the first electron traps around 255 K could correspond to dangling bonds at the Si/SiO2 interface and the second, at high-temperature (>300 K) response, could be originated from minority carrier generation in Ge NCs.« less

Electrochemically addressable trisradical rotaxanes organized within a metal–organic framework

DOE PAGES

McGonigal, Paul R.; Deria, Pravas; Hod, Idan; ...

2015-08-17

The organization of trisradical rotaxanes within the channels of a Zr 6-based metal–organic framework (NU-1000) has been achieved postsynthetically by solvent-assisted ligand incorporation. Robust ZrIV–carboxylate bonds are forged between the Zr clusters of NU-1000 and carboxylic acid groups of rotaxane precursors (semirotaxanes) as part of this building block replacement strategy. Ultraviolet–visible–near-infrared (UV-Vis-NIR), electron paramagnetic resonance (EPR), and 1H nuclear magnetic resonance (NMR) spectroscopies all confirm the capture of redox-active rotaxanes within the mesoscale hexagonal channels of NU-1000. Cyclic voltammetry measurements performed on electroactive thin films of the resulting material indicate that redox-active viologen subunits located on the rotaxane components canmore » be accessed electrochemically in the solid state. In contradistinction to previous methods, this strategy for the incorporation of mechanically interlocked molecules within porous materials circumvents the need for de novo synthesis of a metal–organic framework, making it a particularly convenient approach for the design and creation of solid-state molecular switches and machines. In conclusion, the results presented here provide proof-of-concept for the application of postsynthetic transformations in the integration of dynamic molecular machines with robust porous frameworks.« less

Lattice structures and electronic properties of MO/MoSe2 interface from first-principles calculations

NASA Astrophysics Data System (ADS)

Zhang, Yu; Tang, Fu-Ling; Xue, Hong-Tao; Lu, Wen-Jiang; Liu, Jiang-Fei; Huang, Min

2015-02-01

Using first-principles plane-wave calculations within density functional theory, we theoretically studied the atomic structure, bonding energy and electronic properties of the perfect Mo (110)/MoSe2 (100) interface with a lattice mismatch less than 4.2%. Compared with the perfect structure, the interface is somewhat relaxed, and its atomic positions and bond lengths change slightly. The calculated interface bonding energy is about -1.2 J/m2, indicating that this interface is very stable. The MoSe2 layer on the interface has some interface states near the Fermi level, the interface states are mainly caused by Mo 4d orbitals, while the Se atom almost have no contribution. On the interface, Mo-5s and Se-4p orbitals hybridize at about -6.5 to -5.0 eV, and Mo-4d and Se-4p orbitals hybridize at about -5.0 to -1.0 eV. These hybridizations greatly improve the bonding ability of Mo and Se atom in the interface. By Bader charge analysis, we find electron redistribution near the interface which promotes the bonding of the Mo and MoSe2 layer.

Toward the detection of the triatomic negative ion SPN-: Spectroscopy and potential energy surfaces

NASA Astrophysics Data System (ADS)

Trabelsi, Tarek; Hochlaf, Majdi; Francisco, Joseph S.

2018-04-01

High level theoretical calculations using coupled-cluster theory were performed to provide an accurate description of the electronic structure, spectroscopic properties, and stability of the triatomic negative ion comprising S, N, and P. The adiabatic electron affinities (AEAs) and vertical detachment energies (VDEs) of PNS, SPN, PSN, and cyc-PSN were calculated. The predicted AEA and VDE of the linear SPN isomer are large: 2.24 and 3.04 eV, respectively. The potential energy surfaces (PESs) of the lowest-lying electronic states of the SPN- isomer along the PN and SP bond lengths and bond angle were mapped. A set of spectroscopic parameters for SPN-, PNS-, and PSN- in their electronic ground states is obtained from the 3D PESs to help detect these species in the gas phase. The electronic excited state SPN-(12A″) is predicted to be stable with a long lifetime calculated to be 189.7 μs. The formation of SPN- in its electronic ground state through the bimolecular collision between S- + PN and N + PS- is also discussed.

Operando observations of solid-state electrochemical reactions in Li-ion batteries by spatially resolved TEM EELS and electron holography.

PubMed

Yamamoto, Kazuo; Iriyama, Yasutoshi; Hirayama, Tsukasa

2017-02-08

All-solid-state Li-ion batteries having incombustible solid electrolytes are promising energy storage devices because they have significant advantages in terms of safety, lifetime and energy density. Electrochemical reactions, namely, Li-ion insertion/extraction reactions, commonly occur around the nanometer-scale interfaces between the electrodes and solid electrolytes. Thus, transmission electron microscopy (TEM) is an appropriate technique to directly observe such reactions, providing important information for understanding the fundamental solid-state electrochemistry and improving battery performance. In this review, we introduce two types of TEM techniques for operando observations of battery reactions, spatially resolved electron energy-loss spectroscopy in a TEM mode for direct detection of the Li concentration profiles and electron holography for observing the electric potential changes due to Li-ion insertion/extraction reactions. We visually show how Li-ion insertion/extractions affect the crystal structures, electronic structures, and local electric potential during the charge-discharge processes in these batteries. © The Author 2016. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Defects in a nonlinear pseudo one-dimensional solid

NASA Astrophysics Data System (ADS)

Blanchet, Graciela B.; Fincher, C. R., Jr.

1985-03-01

These infrared studies of acetanilide together with the existence of two equivalent structures for the hydrogen-bonded chain suggest the possibility of a topological defect state rather than a Davydov soliton as suggested previously. Acetanilide is an example of a class of one-dimensional materials where solitons are a consequence of a twofold degenerate structure and the nonlinear dynamics of the hydrogen-bonded network.

Characteristics of AFB interfaces of dissimilar crystal composites as components for solid state lasers

NASA Astrophysics Data System (ADS)

Lee, H. C.; Meissner, O. R.; Meissner, H. E.

2005-06-01

Adhesive-free bonded (AFB®) composite crystals have proven to be useful components in diode-pumped solid-state lasers (DPSSL). The combination of a lasing medium of higher index of refraction with laser-inactive cladding layers of lower index results in light- or wave-guided slab architectures. The cladding layers also serve to provide mechanical support, thermal uniformity and a heat sink during laser operation. Therefore, the optical and mechanical properties of these components are of interest for the design of DPSSL, especially at high laser fluencies and output power. We report on process parameters and material attributes that result in stress-free AFB® composites that are resistant to thermally induced failure. Formation of stress-free and durable bonds between two dissimilar materials requires heat-treatment of composites to a temperature high enough to ensure durable bonds and low enough to prevent forming of permanent chemical bonds. The onset temperature for forming permanent bonds at the interface sets the upper limit for heat treatment. This limiting temperature is dependent on the chemical composition, crystallographic orientation, and surface characteristics. We have determined the upper temperature limits for forming stress-free bonds between YAG and sapphire, YAG and GGG, YAG and spinel, spinel and sapphire, spinel and GGG, and sapphire and GGG composites. We also deduce the relative magnitude of thermal expansion coefficients amongst the respective single crystals as αGGG > αsapp_c > αspinel > αYAG > αsapp_a from interferometric analysis.

Chemical Bonding of AlH3 Hydride by Al-L2,3 Electron Energy-Loss Spectra and First-Principles Calculations

PubMed Central

Tatsumi, Kazuyoshi; Muto, Shunsuke; Ikeda, Kazutaka; Orimo, Shin-Ichi

2012-01-01

In a previous study, we used transmission electron microscopy and electron energy-loss (EEL) spectroscopy to investigate dehydrogenation of AlH3 particles. In the present study, we systematically examine differences in the chemical bonding states of Al-containing compounds (including AlH3) by comparing their Al-L2,3 EEL spectra. The spectral chemical shift and the fine peak structure of the spectra were consistent with the degree of covalent bonding of Al. This finding will be useful for future nanoscale analysis of AlH3 dehydrogenation toward the cell. PMID:28816996

Some effects of electron channeling on electron energy loss spectroscopy.

PubMed

Kirkland, Earl J

2005-02-01

As an electron beam (of order 100 keV) travels through a crystalline solid it can be channeled down a zone axis of the crystal to form a channeling peak centered on the atomic columns. The channeling peak can be similar in size to the outer atomic orbitals. Electron energy loss spectroscopy (EELS) measures the losses that the electron experiences as it passes through the solid yielding information about the unoccupied density of states in the solid. The interaction matrix element for this process typically produces dipole selection rules for small angle scattering. In this paper, a theoretical calculation of the EELS cross section in the presence of strong channeling is performed for the silicon L23 edge. The presence of channeling is found to alter both the intensity and selection rules for this EELS signal as a function of depth in the solid. At some depths in the specimen small but significant non-dipole transition components can be produced, which may influence measurements of the density of states in solids.

Construction of a Hierarchical Architecture of Covalent Organic Frameworks via a Postsynthetic Approach.

PubMed

Zhang, Gen; Tsujimoto, Masahiko; Packwood, Daniel; Duong, Nghia Tuan; Nishiyama, Yusuke; Kadota, Kentaro; Kitagawa, Susumu; Horike, Satoshi

2018-02-21

Covalent organic frameworks (COFs) represent an emerging class of crystalline porous materials that are constructed by the assembly of organic building blocks linked via covalent bonds. Several strategies have been developed for the construction of new COF structures; however, a facile approach to fabricate hierarchical COF architectures with controlled domain structures remains a significant challenge, and has not yet been achieved. In this study, a dynamic covalent chemistry (DCC)-based postsynthetic approach was employed at the solid-liquid interface to construct such structures. Two-dimensional imine-bonded COFs having different aromatic groups were prepared, and a homogeneously mixed-linker structure and a heterogeneously core-shell hollow structure were fabricated by controlling the reactivity of the postsynthetic reactions. Solid-state nuclear magnetic resonance (NMR) spectroscopy and transmission electron microscopy (TEM) confirmed the structures. COFs prepared by a postsynthetic approach exhibit several functional advantages compared with their parent phases. Their Brunauer-Emmett-Teller (BET) surface areas are 2-fold greater than those of their parent phases because of the higher crystallinity. In addition, the hydrophilicity of the material and the stepwise adsorption isotherms of H 2 O vapor in the hierarchical frameworks were precisely controlled, which was feasible because of the distribution of various domains of the two COFs by controlling the postsynthetic reaction. The approach opens new routes for constructing COF architectures with functionalities that are not possible in a single phase.

Single and double carbon vacancies in pyrene as first models for graphene defects: A survey of the chemical reactivity toward hydrogen

NASA Astrophysics Data System (ADS)

Nieman, Reed; Das, Anita; Aquino, Adélia J. A.; Amorim, Rodrigo G.; Machado, Francisco B. C.; Lischka, Hans

2017-01-01

Graphene is regarded as one of the most promising materials for nanoelectronics applications. Defects play an important role in modulating its electronic properties and also enhance its chemical reactivity. In this work the reactivity of single vacancies (SV) and double vacancies (DV) in reaction with a hydrogen atom Hr is studied. Because of the complicated open shell electronic structures of these defects due to dangling bonds, multireference configuration interaction (MRCI) methods are being used in combination with a previously developed defect model based on pyrene. Comparison of the stability of products derived from Csbnd Hr bond formation with different carbon atoms of the different polyaromatic hydrocarbons is made. In the single vacancy case the most stable structure is the one where the incoming hydrogen is bound to the carbon atom carrying the dangling bond. However, stable Csbnd Hr bonded structures are also observed in the five-membered ring of the single vacancy. In the double vacancy, most stable bonding of the reactant Hr atom is found in the five-membered rings. In total, Csbnd Hr bonds, corresponding to local energy minimum structures, are formed with all carbon atoms in the different defect systems and the pyrene itself. Reaction profiles for the four lowest electronic states show in the case of a single vacancy a complex picture of curve crossings and avoided crossings which will give rise to a complex nonadiabatic reaction dynamics involving several electronic states.

Synergizing Noncovalent Bonding Interactions in the Self-Assembly of Organic Charge-Transfer Ferroelectrics and Metal-Organic Frameworks

NASA Astrophysics Data System (ADS)

Cao, Dennis

Contemporary supramolecular chemistry---chemistry beyond the molecule---seeks to leverage noncovalent bonding interactions to generate emergent properties and complexity. These aims extend beyond the solution phase and into the solid state, where crystalline organic materials have attracted much attention for their ability to imitate the physical properties of inorganic crystals. This Thesis outlines my efforts to understand the properties of the solid-state materials that are self-assembled with noncovalent bonding motifs which I have helped to realize. In the first five Chapters, I chronicle the development of the lock-arm supramolecular ordering (LASO) paradigm, which is a general molecular design strategy for amplifying the crystallization of charge transfer complexes that revolves around the synergistic action of hydrogen bonding and charge transfer interactions. In an effort to expand upon the LASO paradigm, I identify a two-point halogen-bonding motif which appears to operate orthogonally from the hydrogen bonding and charge transfer interactions. Since some of these single crystalline materials are ferroelectric at room temperature, I discuss the implications of these experimental observations and reconcile them with the centrosymmetric space groups assigned after X-ray crystallographic refinements. I conclude in the final two Chapters by recording my endeavors to control the assembly of metal-organic frameworks (MOFs) with noncovalent bonding interactions between [2]catenane-bearing struts. First of all, I describe the formation of syndiotactic pi-stacked 2D MOF layers before highlighting a two-component MOF that assembles with a magic number ratio of components that is independent of the molar proportions present in the crystallization medium.

Atomic solid state energy scale: Universality and periodic trends in oxidation state

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pelatt, Brian D.; Kokenyesi, Robert S.; Ravichandran, Ram

2015-11-15

The atomic solid state energy (SSE) scale originates from a plot of the electron affinity (EA) and ionization potential (IP) versus band gap (E{sub G}). SSE is estimated for a given atom by assessing an average EA (for a cation) or an average IP (for an anion) for binary inorganic compounds having that specific atom as a constituent. Physically, SSE is an experimentally-derived average frontier orbital energy referenced to the vacuum level. In its original formulation, 69 binary closed-shell inorganic semiconductors and insulators were employed as a database, providing SSE estimates for 40 elements. In this contribution, EA and IPmore » versus E{sub G} are plotted for an additional 92 compounds, thus yielding SSE estimates for a total of 64 elements from the s-, p-, d-, and f-blocks of the periodic table. Additionally, SSE is refined to account for its dependence on oxidation state. Although most cations within the SSE database are found to occur in a single oxidation state, data are available for nine d-block transition metals and one p-block main group metal in more than one oxidation state. SSE is deeper in energy for a higher cation oxidation state. Two p-block main group non-metals within the SSE database are found to exist in both positive and negative oxidation states so that they can function as a cation or anion. SSEs for most cations are positioned above −4.5 eV with respect to the vacuum level, and SSEs for all anions are positioned below. Hence, the energy −4.5 eV, equal to the hydrogen donor/acceptor ionization energy ε(+/−) or equivalently the standard hydrogen electrode energy, is considered to be an absolute energy reference for chemical bonding in the solid state. - Highlights: • Atomic solid-state energies are estimated for 64 elements from experimental data. • The relationship between atomic SSEs and oxidation state is assessed. • Cations are positioned above and absolute energy of −4.5 eV and anions below.« less

Novel 3D metallic boron nitride containing only sp2 bonds

NASA Astrophysics Data System (ADS)

Wang, Hao; Zhang, Wei; Huai, Ping

2017-09-01

As the closest isoelectronic analogue of carbon, boron nitride (BN) shares a similar structure with carbon from 1D nanotubes, 2D nanosheets, and 3D diamond structures. However, most BN structures are insulators, which limits their application. In this work, under the inspiration of the sp2 hybridized carbon honeycomb, we propose a hexagonal phase of BN consisting of only sp2 bonds, which exhibits intriguingly intrinsic metallicity. First-principles calculations confirm that this phase is both thermally and dynamically stable. Moreover, the calculations on the band structure, partial density states and electron localization function suggest that the metallic behavior is attributable to the delocalized B-2p electrons, leading to second-neighbor interaction between the p z states of sp2-bonded B atoms in adjacent layers. Our findings not only enrich the BN allotrope family with 3D structures but also stimulate further experimental interest in applications of metallic BN in electronic devices.

A Computational Study on the Ground and Excited States of Nickel Silicide.

PubMed

Schoendorff, George; Morris, Alexis R; Hu, Emily D; Wilson, Angela K

2015-09-17

Nickel silicide has been studied with a range of computational methods to determine the nature of the Ni-Si bond. Additionally, the physical effects that need to be addressed within calculations to predict the equilibrium bond length and bond dissociation energy within experimental error have been determined. The ground state is predicted to be a (1)Σ(+) state with a bond order of 2.41 corresponding to a triple bond with weak π bonds. It is shown that calculation of the ground state equilibrium geometry requires a polarized basis set and treatment of dynamic correlation including up to triple excitations with CR-CCSD(T)L resulting in an equilibrium bond length of only 0.012 Å shorter than the experimental bond length. Previous calculations of the bond dissociation energy resulted in energies that were only 34.8% to 76.5% of the experimental bond dissociation energy. It is shown here that use of polarized basis sets, treatment of triple excitations, correlation of the valence and subvalence electrons, and a Λ coupled cluster approach is required to obtain a bond dissociation energy that deviates as little as 1% from experiment.

Anatase-rutile phase transformation of titanium dioxide bulk material: a DFT + U approach

NASA Astrophysics Data System (ADS)

Vu, Nam H.; Le, Hieu V.; Cao, Thi M.; Pham, Viet V.; Le, Hung M.; Nguyen-Manh, Duc

2012-10-01

The anatase-rutile phase transformation of TiO2 bulk material is investigated using a density functional theory (DFT) approach in this study. According to the calculations employing the Perdew-Burke-Ernzerhof (PBE) exchange-correlation functional with the Vanderbilt ultrasoft pseudopotential, it is suggested that the anatase phase is more energetically stable than rutile, which is in variance with the experimental observations. Consequently, the DFT + U method is employed in order to predict the correct structural stability in titania from electronic-structure-based total energy calculations. The Hubbard U term is determined by examining the band structure of rutile with various values of U from 3 to 10 eV. At U = 5 eV, a theoretical bandgap for rutile is obtained as 3.12 eV, which is in very good agreement with the reported experimental bandgap. Hence, we choose the DFT + U method (with U = 5 eV) to investigate the transformation pathway using the newly-developed solid-state nudged elastic band (ss-NEB) method, and consequently obtain an intermediate transition structure that is 9.794 eV per four-TiO2 above the anatase phase. When the Ti-O bonds in the transition state are examined using charge density analysis, seven Ti-O bonds (out of 24 bonds in the anatase unit cell) are broken, and this result is in excellent agreement with a previous experimental study (Penn and Banfield 1999 Am. Miner. 84 871-6).

AIEgens-Functionalized Inorganic-Organic Hybrid Materials: Fabrications and Applications.

PubMed

Li, Dongdong; Yu, Jihong

2016-12-01

Inorganic materials functionalized with organic fluorescent molecules combine advantages of them both, showing potential applications in biomedicine, chemosensors, light-emitting, and so on. However, when more traditional organic dyes are doped into the inorganic materials, the emission of resulting hybrid materials may be quenched, which is not conducive to the efficiency and sensitivity of detection. In contrast to the aggregation-caused quenching (ACQ) system, the aggregation-induced emission luminogens (AIEgens) with high solid quantum efficiency, offer new potential for developing highly efficient inorganic-organic hybrid luminescent materials. So far, many AIEgens have been incorporated into inorganic materials through either physical doping caused by aggregation induced emission (AIE) or chemical bonding (e.g., covalent bonding, ionic bonding, and coordination bonding) caused by bonding induced emission (BIE) strategy. The hybrid materials exhibit excellent photoactive properties due to the intramolecular motion of AIEgens is restricted by inorganic matrix. Recent advances in the fabrication of AIEgens-functionalized inorganic-organic hybrid materials and their applications in biomedicine, chemical sensing, and solid-state light emitting are presented. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanical properties of small-scale wood laminated composite poles

Treesearch

Cheng Piao; Todd F. Shupe; Chung Y. Hse

2004-01-01

Power companies in the United States consume millions of solid wood poles every year. These poles are from high-valued trees that are becoming more expensive and less available. wood laminated composite poles (LCP) are a novel alternative to solid wood poles. LCP consists of trapezoid wood strips that are bonded by a synthetic resin. The wood strips can be made from...

First principles investigations of the electronic structure and chemical bonding of U3Si2C2 - A uranium silicide-carbide with the rare [SiC] unit

NASA Astrophysics Data System (ADS)

Matar, S. F.; Pöttgen, R.

2012-10-01

The electronic structure of U3Si2C2, with the rare [SiC] unit is examined from ab initio with an assessment of the properties of chemical bonding. We show that plain GGA fails describing the experimental lattice parameters and the electronic structure. A better agreement with experiment (crystal determination and magnetic properties) is obtained with the GGA + U method and U = 4 eV. The energy-volume equation of state and the set of elastic constants are obtained showing incompressibility along the c-axis with U-C-Si alignment and a brittle material. Bonding of U1 and U2 selectively with Si and C and Si-C bonds are remarkable

Thread bonds in molecules

NASA Astrophysics Data System (ADS)

Ivlev, B.

2017-07-01

Unusual chemical bonds are proposed. Each bond is characterized by the thread of a small radius, 10-11 cm, extended between two nuclei in a molecule. An analogue of a potential well, of the depth of MeV scale, is formed within the thread. This occurs due to the local reduction of zero point electromagnetic energy. This is similar to formation of the Casimir well. The electron-photon interaction only is not sufficient for formation of thread state. The mechanism of electron mass generation is involved in the close vicinity, 10-16 cm, of the thread. Thread bonds are stable and cannot be created or destructed in chemical or optical processes.

Molecular electronics with single molecules in solid-state devices.

PubMed

Moth-Poulsen, Kasper; Bjørnholm, Thomas

2009-09-01

The ultimate aim of molecular electronics is to understand and master single-molecule devices. Based on the latest results on electron transport in single molecules in solid-state devices, we focus here on new insights into the influence of metal electrodes on the energy spectrum of the molecule, and on how the electron transport properties of the molecule depend on the strength of the electronic coupling between it and the electrodes. A variety of phenomena are observed depending on whether this coupling is weak, intermediate or strong.

Development of solid-state NMR techniques for the characterisation of pharmaceutical compounds

NASA Astrophysics Data System (ADS)

Tatton, Andrew S.

Structural characterisation in the solid state is an important step in understanding the physical and chemical properties of a material. Solid-state NMR techniques applied to solid delivery forms are presented as an alternative to more established structural characterisation methods. The effect of homonuclear decoupling upon heteronuclear couplings is investigated using a combination of experimental and density-matrix simulation results acquired from a 13C-1H spinecho pulse sequence, modulated by scalar couplings. It is found that third-order cross terms under MAS and homonuclear decoupling contribute to strong dephasing effects in the NMR signal. Density-matrix simulations allow access to parameters currently unattainable in experiment, and demonstrate that higher homonuclear decoupling rf nutation frequencies reduce the magnitude of third-order cross terms. 15N-1H spinecho experiments were applied to pharmaceutically relevant samples to differentiate between the number of directly attached protons. Using this method, proton transfer in an acid-base reaction is proven in pharmaceutical salts. The indirect detection of 14N lineshapes via protons obtained using 2D 14N-1H HMQC experiments is presented, where coherence transfer is achieved via heteronuclear through-space dipolar couplings. The importance of fast MAS frequencies is demonstrated, and it is found that increasing the recoupling duration reveals longer range NH proximities. The 2D 14N-1H HMQC method is used to demonstrate the presence of specific hydrogen bonding interactions, and thus aid in identifying molecular association in a cocrystal and an amorphous dispersion. In addition, hydrogen bonding motifs were identified by observing the changes in the 14N quadrupolar parameters between individual molecular components relative to the respective solid delivery form. First-principles calculations of NMR chemical shifts and quadrupolar parameters using the GIPAW method were combined with 14N-1H experimental results to assist with spectral assignment and the identification of the hydrogen bonding interactions.

Structure and physicochemical characterization of a naproxen–picolinamide cocrystal

PubMed Central

Kerr, Hannah E.; Softley, Lorna K.; Suresh, Kuthuru; Hodgkinson, Paul; Evans, Ivana Radosavljevic

2017-01-01

Naproxen (NPX) is a nonsteroidal anti-inflammatory drug with pain- and fever-relieving properties, currently marketed in the sodium salt form to overcome solubility problems; however, alternative solutions for improving its solubility across all pH values are desirable. NPX is suitable for cocrystal formation, with hydrogen-bonding possibilities via the COOH group. The crystal structure is presented of a 1:1 cocrystal of NPX with picolinamide as a coformer [systematic name: (S)-2-(6-meth­oxy­naphthalen-2-yl)propanoic acid–pyridine-2-carbox­amide (1/1), C14H14O3·C6H6N2O]. The pharmaceutically relevant physical properties were investigated and the intrinsic dissolution rate was found to be essentially the same as that of commercial naproxen. An NMR crystallography approach was used to investigate the H-atom positions in the two crystallographically unique COOH–CONH hydrogen-bonded dimers. 1H solid-state NMR distinguished the two carboxyl protons, despite the very similar crystallographic environments. The nature of the hydrogen bonding was confirmed by solid-state NMR and density functional theory calculations. PMID:28257010

Structure and physicochemical characterization of a naproxen-picolinamide cocrystal.

PubMed

Kerr, Hannah E; Softley, Lorna K; Suresh, Kuthuru; Hodgkinson, Paul; Evans, Ivana Radosavljevic

2017-03-01

Naproxen (NPX) is a nonsteroidal anti-inflammatory drug with pain- and fever-relieving properties, currently marketed in the sodium salt form to overcome solubility problems; however, alternative solutions for improving its solubility across all pH values are desirable. NPX is suitable for cocrystal formation, with hydrogen-bonding possibilities via the COOH group. The crystal structure is presented of a 1:1 cocrystal of NPX with picolinamide as a coformer [systematic name: (S)-2-(6-methoxynaphthalen-2-yl)propanoic acid-pyridine-2-carboxamide (1/1), C 14 H 14 O 3 ·C 6 H 6 N 2 O]. The pharmaceutically relevant physical properties were investigated and the intrinsic dissolution rate was found to be essentially the same as that of commercial naproxen. An NMR crystallography approach was used to investigate the H-atom positions in the two crystallographically unique COOH-CONH hydrogen-bonded dimers. 1 H solid-state NMR distinguished the two carboxyl protons, despite the very similar crystallographic environments. The nature of the hydrogen bonding was confirmed by solid-state NMR and density functional theory calculations.

76 FR 55256 - Definition of Solid Waste Disposal Facilities for Tax-Exempt Bond Purposes; Correction

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-07

... Definition of Solid Waste Disposal Facilities for Tax-Exempt Bond Purposes; Correction AGENCY: Internal..., 2011, on the definition of solid waste disposal facilities for purposes of the rules applicable to tax... governments that issue tax-exempt bonds to finance solid waste disposal facilities and to taxpayers that use...

76 FR 55255 - Definition of Solid Waste Disposal Facilities for Tax-Exempt Bond Purposes; Correction

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-07

... Definition of Solid Waste Disposal Facilities for Tax-Exempt Bond Purposes; Correction AGENCY: Internal..., on the definition of solid waste disposal facilities for purposes of the rules applicable to tax... governments that issue tax-exempt bonds to finance solid waste disposal facilities and to taxpayers that use...

Low energy electron induced cytosine base release in 2′-deoxycytidine-3′-monophosphate via glycosidic bond cleavage: A time-dependent wavepacket study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhaskaran, Renjith; Sarma, Manabendra, E-mail: msarma@iitg.ernet.in

2014-09-14

Low energy electron (LEE) induced cytosine base release in a selected pyrimidine nucleotide, viz., 2′-deoxycytidine-3′-monophosphate is investigated using ab initio electronic structure methods and time dependent quantum mechanical calculations. It has been noted that the cytosine base scission is comparatively difficult process than the 3′ C–O bond cleavage from the lowest π{sup *} shape resonance in energy region <1 eV. This is mainly due to the high activation energy barrier associated with the electron transfer from the π{sup *} orbital of the base to the σ{sup *} orbital of the glycosidic N–C bond. In addition, the metastable state formed aftermore » impinging LEE (0–1 eV) has very short lifetime (10 fs) which may decay in either of the two competing auto-detachment or dissociation process simultaneously. On the other hand, the selected N–C mode may cleave to form the cytosine base anion at higher energy regions (>2 eV) via tunneling of the glycosidic bond. Resonance states generated within this energy regime will exist for a duration of ∼35–55 fs. Comparison of salient features of the two dissociation events, i.e., 3′ C–O single strand break and glycosidic N–C bond cleavage in 3′-dCMPH molecule are also provided.« less

Investigation of electronic structure and chemical bonding of intermetallic Pd2HfIn: An ab-initio study

NASA Astrophysics Data System (ADS)

Bano, Amreen; Gaur, N. K.

2018-05-01

Ab-initio calculations are carried out to study the electronic and chemical bonding properties of Intermetallic full Heusler compound Pd2HfIn which crystallizes in F-43m structure. All calculations are performed by using density functional theory (DFT) based code Quantum Espresso. Generalized gradient approximations (GGA) of Perdew- Burke- Ernzerhof (PBE) have been adopted for exchange-correlation potential. Calculated electronic band structure reveals the metallic character of the compound. From partial density of states (PDoS), we found the presence of relatively high intensity electronic states of 4d-Pd atom at Fermi level. We have found a pseudo-gap just abouve the Fermi level and N(E) at Fermi level is observed to be 0.8 states/eV, these finding indicates the existence of superconducting character in Pd2HfIn.

Lie algebraic approach to valence bond theory of π-electron systems: a preliminary study of excited states

NASA Astrophysics Data System (ADS)

Paldus, J.; Li, X.

1992-10-01

Following a brief outline of various developments and exploitations of the unitary group approach (UGA), and its extension referred to as Clifford algebra UGA (CAUGA), in molecular electronic structure calculations, we present a summary of a recently introduced implementation of CAUGA for the valence bond (VB) method based on the Pariser-Parr-Pople (PPP)-type Hamiltonian. The existing applications of this PPP-VB approach have been limited to groundstates of various π-electron systems or, at any rate, to the lowest states of a given multiplicity. In this paper the method is applied to the low-lying excited states of several archetypal models, namely cyclobutadiene and benzene, representing antiaromatic and aromatic systems, hexatriene, representing linear polyenic systems and, finally, naphthalene, representing polyacenes.

Novel thixotropic gel electrolytes based on dicationic bis-imidazolium salts for quasi-solid-state dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Kim, Jun Young; Kim, Tae Ho; Kim, Dong Young; Park, Nam-Gyu; Ahn, Kwang-Duk

Novel thixotropic gel electrolytes have been successfully prepared by utilizing oligomeric poly(ethylene oxide) (PEO)-based bis-imidazolium diiodide salts and hydrophilic silica nanoparticles for application in quasi-solid-state dye-sensitized solar cells (DSSCs). The thixotropic gel-state of the ionic liquid-based composite electrolytes is confirmed by observing the typical hysteresis loop and temporary hydrogen bonding. On using the PEO-based composite electrolyte, a quasi-solid-state DSSC exhibited highly improved properties such as easy penetration of the electrolyte into the cell without leakage, long-term stability, high open-circuit voltage without the use of 4- tert-butylpyridine, and a high energy-conversion efficiency of 5.25% under AM 1.5 illumination (100 mW cm -2).

Observation of ultrafast temporal evolution of symmetry in short-pulsed laser induced transient states of matter (Conference Presentation)

NASA Astrophysics Data System (ADS)

Garnett, Joy; Krzyzanowska, Halina; Baydin, Andrey; Tolk, Norman H.

2017-02-01

In condensed matter physics, ultrafast photoexcitation has been shown to result in modification of macroscopic material properties, sometimes involving phase changes, on a subpicosecond time scale. In semiconductors, irreversible non-thermal solid-to-liquid structural transitions have been demonstrated at high laser fluences. In the pump-probe experiments reported here, we observe a striking continuously varying low-fluence pump-induced time-dependent structural symmetry modification in intrinsic gallium arsenide (GaAs) using a probe that produces femtosecond polarization-resolved second harmonic generation (f-PRSHG) data. SHG spectroscopy is particularly suited to monitor symmetry changes since its magnitude is governed by the nonlinear optical susceptibility tensor whose elements are determined by the underlying material symmetry. Conceptually, these experiments seek to provide insight into the details of the time evolution of symmetry arising from laser induced transient states of matter in GaAs. Overall, the basic explanation of these experimental observations is that as a result of the photoinduced electronic excitation, many electrons, including bond electrons are excited to higher states. This results in subpicosecond changes in the local anharmonic potential and produces a changing nonlinear polarization response thus accounting for the nonthermal time dependent symmetry changes. Clearly, our approach may be easily extended to many different crystalline materials with different levels of defects, dopants and stresses to fully characterize the time dependent behavior of laser induced transient states in material systems.

An electron-deficient small molecule accessible from sustainable synthesis and building blocks for use as a fullerene alternative in organic photovoltaics.

PubMed

McAfee, Seth M; Topple, Jessica M; Payne, Abby-Jo; Sun, Jon-Paul; Hill, Ian G; Welch, Gregory C

2015-04-27

An electron-deficient small molecule accessible from sustainable isoindigo and phthalimide building blocks was synthesized via optimized synthetic procedures that incorporate microwave-assisted synthesis and a heterogeneous catalyst for Suzuki coupling, and direct heteroarylation carbon-carbon bond forming reactions. The material was designed as a non-fullerene acceptor with the help of DFT calculations and characterized by optical, electronic, and thermal analysis. Further investigation of the material revealed a differing solid-state morphology with the use of three well-known processing conditions: thermal annealing, solvent vapor annealing and small volume fractions of 1,8-diiodooctane (DIO) additive. These unique morphologies persist in the active layer blends and have demonstrated a distinct influence on device performance. Organic photovoltaic-bulk heterojunction (OPV-BHJ) devices show an inherently high open circuit voltage (Voc ) with the best power conversion efficiency (PCE) cells reaching 1.0 V with 0.4 v/v % DIO as a processing additive. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Visualization of the ultrafast structural phase transitions in warm dense matter

NASA Astrophysics Data System (ADS)

Mo, Mianzhen

2017-10-01

It is still a great challenge to obtain real-time atomistic-scale information on the structural phase transitions that lead to warm dense matter state. Recent advances in ultrafast electron diffraction (UED) techniques have opened up exciting prospects to unravel the mechanisms of solid-liquid phase transitions under these extreme non-equilibrium conditions. Here we report on precise measurements of melt time dependency on laser excitation energy density that resolve for the first time the transition from heterogeneous to homogeneous melting. This transition appears in both polycrystalline and single-crystal gold nanofilms with distinct measurable differences. These results test predictions from molecular-dynamics simulations with different interatomic potential models. These data further deliver accurate structure factor data to large wavenumbers that allow us to constrain electron-ion equilibration constants. Our results demonstrate electron-phonon coupling strength much weaker than DFT calculations, and contrary to previous results, provide evidence for bond softening. This work is supported by DOE Office of Science, Fusion Energy Science under FWP 100182, and the DOE BES Accelerator and Detector R&D program.

Ultrafast forward and backward electron transfer dynamics of coumarin 337 in hydrogen-bonded anilines as studied with femtosecond UV-pump/IR-probe spectroscopy.

PubMed

Ghosh, Hirendra N; Verma, Sandeep; Nibbering, Erik T J

2011-02-10

Femtosecond infrared spectroscopy is used to study both forward and backward electron transfer (ET) dynamics between coumarin 337 (C337) and the aromatic amine solvents aniline (AN), N-methylaniline (MAN), and N,N-dimethylaniline (DMAN), where all the aniline solvents can donate an electron but only AN and MAN can form hydrogen bonds with C337. The formation of a hydrogen bond with AN and MAN is confirmed with steady state FT-IR spectroscopy, where the C═O stretching vibration is a direct marker mode for hydrogen bond formation. Transient IR absorption measurements in all solvents show an absorption band at 2166 cm(-1), which has been attributed to the C≡N stretching vibration of the C337 radical anion formed after ET. Forward electron transfer dynamics is found to be biexponential with time constants τ(ET)(1) = 500 fs, τ(ET)(2) = 7 ps in all solvents. Despite the presence of hydrogen bonds of C337 with the solvents AN and MAN, no effect has been found on the forward electron transfer step. Because of the absence of an H/D isotope effect on the forward electron transfer reaction of C337 in AN, hydrogen bonds are understood to play a minor role in mediating electron transfer. In contrast, direct π-orbital overlap between C337 and the aromatic amine solvents causes ultrafast forward electron transfer dynamics. Backward electron transfer dynamics, in contrast, is dependent on the solvent used. Standard Marcus theory explains the observed backward electron transfer rates.

Coherent π-electron dynamics of (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses: Angular momentum and ring current

NASA Astrophysics Data System (ADS)

Mineo, H.; Lin, S. H.; Fujimura, Y.

2013-02-01

The results of a theoretical investigation of coherent π-electron dynamics for nonplanar (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses are presented. Expressions for the time-dependent coherent angular momentum and ring current are derived by using the density matrix method. The time dependence of these coherences is determined by the off-diagonal density matrix element, which can be obtained by solving the coupled equations of motion of the electronic-state density matrix. Dephasing effects on coherent angular momentum and ring current are taken into account within the Markov approximation. The magnitudes of the electronic angular momentum and current are expressed as the sum of expectation values of the corresponding operators in the two phenol rings (L and R rings). Here, L (R) denotes the phenol ring in the left (right)-hand side of (P)-2,2'-biphenol. We define the bond current between the nearest neighbor carbon atoms Ci and Cj as an electric current through a half plane perpendicular to the Ci-Cj bond. The bond current can be expressed in terms of the inter-atomic bond current. The inter-atomic bond current (bond current) depends on the position of the half plane on the bond and has the maximum value at the center. The coherent ring current in each ring is defined by averaging over the bond currents. Since (P)-2,2'-biphenol is nonplanar, the resultant angular momentum is not one-dimensional. Simulations of the time-dependent coherent angular momentum and ring current of (P)-2,2'-biphenol excited by ultrashort linearly polarized UV pulses are carried out using the molecular parameters obtained by the time-dependent density functional theory (TD-DFT) method. Oscillatory behaviors in the time-dependent angular momentum (ring current), which can be called angular momentum (ring current) quantum beats, are classified by the symmetry of the coherent state, symmetric or antisymmetric. The bond current of the bridge bond linking the L and R rings is zero for the symmetric coherent state, while it is nonzero for the antisymmetric coherent state. The magnitudes of ring current and ring current-induced magnetic field are also evaluated, and their possibility as a control parameter in ultrafast switching devices is discussed. The present results give a detailed description of the theoretical treatment reported in our previous paper [H. Mineo, M. Yamaki, Y. Teranish, M. Hayashi, S. H. Lin, and Y. Fujimura, J. Am. Chem. Soc. 134, 14279 (2012), 10.1021/ja3047848].

Coherent π-electron dynamics of (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses: angular momentum and ring current.

PubMed

Mineo, H; Lin, S H; Fujimura, Y

2013-02-21

The results of a theoretical investigation of coherent π-electron dynamics for nonplanar (P)-2,2'-biphenol induced by ultrashort linearly polarized UV pulses are presented. Expressions for the time-dependent coherent angular momentum and ring current are derived by using the density matrix method. The time dependence of these coherences is determined by the off-diagonal density matrix element, which can be obtained by solving the coupled equations of motion of the electronic-state density matrix. Dephasing effects on coherent angular momentum and ring current are taken into account within the Markov approximation. The magnitudes of the electronic angular momentum and current are expressed as the sum of expectation values of the corresponding operators in the two phenol rings (L and R rings). Here, L (R) denotes the phenol ring in the left (right)-hand side of (P)-2,2'-biphenol. We define the bond current between the nearest neighbor carbon atoms Ci and Cj as an electric current through a half plane perpendicular to the Ci-Cj bond. The bond current can be expressed in terms of the inter-atomic bond current. The inter-atomic bond current (bond current) depends on the position of the half plane on the bond and has the maximum value at the center. The coherent ring current in each ring is defined by averaging over the bond currents. Since (P)-2,2'-biphenol is nonplanar, the resultant angular momentum is not one-dimensional. Simulations of the time-dependent coherent angular momentum and ring current of (P)-2,2'-biphenol excited by ultrashort linearly polarized UV pulses are carried out using the molecular parameters obtained by the time-dependent density functional theory (TD-DFT) method. Oscillatory behaviors in the time-dependent angular momentum (ring current), which can be called angular momentum (ring current) quantum beats, are classified by the symmetry of the coherent state, symmetric or antisymmetric. The bond current of the bridge bond linking the L and R rings is zero for the symmetric coherent state, while it is nonzero for the antisymmetric coherent state. The magnitudes of ring current and ring current-induced magnetic field are also evaluated, and their possibility as a control parameter in ultrafast switching devices is discussed. The present results give a detailed description of the theoretical treatment reported in our previous paper [H. Mineo, M. Yamaki, Y. Teranish, M. Hayashi, S. H. Lin, and Y. Fujimura, J. Am. Chem. Soc. 134, 14279 (2012)].

Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111).

PubMed

Fernández, Cynthia C; Pensa, Evangelina; Carro, Pilar; Salvarezza, Roberto; Williams, Federico J

2018-05-22

The electronic structure of aromatic and aliphatic thiols on Au(111) has been extensively studied in relation to possible applications in molecular electronics. In this work, the effect on the electronic structure of an additional anchor to the S-Au bond using 6-mercaptopurine as a model system has been investigated. Results from X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and density functional theory (DFT) confirm that this molecule adsorbs on Au(111) with S-Au and iminic N-Au bonds. Combined ultraviolet photoelectron spectroscopy and DFT data reveal that formation of the 6MP self-assembled monolayer generates a molecular dipole perpendicular to the surface, with negative charges residing at the metal/monolayer interface and positive charges at the monolayer/vacuum interface, which lowers the substrate work function. Scanning tunneling microscopy shows two surface molecular domains: a well-ordered rectangular lattice where molecules are tilted on average 30° with respect to the substrate and aligned 6MP islands where molecules are standing upright. Finally, we found a new electronic state located at -1.7 eV with respect to the Fermi level that corresponds to a localized π molecular state, while the state corresponding to the N-Au bond is hybridized with Au d electrons and stabilized at much lower energies (-3 eV).

DOE Office of Scientific and Technical Information (OSTI.GOV)

ALAM,TODD M.

Monte Carlo simulations of phosphate tetrahedron connectivity distributions in alkali and alkaline earth phosphate glasses are reported. By utilizing a discrete bond model, the distribution of next-nearest neighbor connectivities between phosphate polyhedron for random, alternating and clustering bonding scenarios was evaluated as a function of the relative bond energy difference. The simulated distributions are compared to experimentally observed connectivities reported for solid-state two-dimensional exchange and double-quantum NMR experiments of phosphate glasses. These Monte Carlo simulations demonstrate that the polyhedron connectivity is best described by a random distribution in lithium phosphate and calcium phosphate glasses.

Teaching Chemistry with Electron Density Models.

ERIC Educational Resources Information Center

Shusterman, Gwendolyn P.; Shusterman, Alan J.

1997-01-01

Describes a method for teaching electronic structure and its relevance to chemical phenomena that relies on computer-generated three-dimensional models of electron density distributions. Discusses the quantum mechanical background needed and presents ways of using models of electronic ground states to teach electronic structure, bonding concepts,…

Chemical bonds and vibrational properties of ordered (U, Np, Pu) mixed oxides

NASA Astrophysics Data System (ADS)

Yang, Yu; Zhang, Ping

2013-01-01

We use density functional theory +U to investigate the chemical bonding characters and vibrational properties of the ordered (U, Np, Pu) mixed oxides (MOXs), UNpO4,NpPuO4, and UPuO4. It is found that the 5f electronic states of different actinide elements keep their localized characters in all three MOXs. The occupied 5f electronic states of different actinide elements do not overlap with each other and tend to distribute over the energy band gap of the other actinide element's 5f states. As a result, the three ordered MOXs all show smaller band gaps than those of the component dioxides, with values of 0.91, 1.47, and 0.19 eV for UNpO4,NpPuO4, and UPuO4, respectively. Through careful charge density analysis, we further show that the U-O and Pu-O bonds in MOXs show more ionic character than in UO2 and PuO2, while the Np-O bonds show more covalent character than in NpO2. The change in covalencies in the chemical bonds leads to vibrational frequencies of oxygen atoms that are different in MOXs.

Macrocyclic molecular rotors with bridged steroidal frameworks.

PubMed

Czajkowska-Szczykowska, Dorota; Rodríguez-Molina, Braulio; Magaña-Vergara, Nancy E; Santillan, Rosa; Morzycki, Jacek W; Garcia-Garibay, Miguel A

2012-11-16

In this work, we describe the synthesis and solid-state dynamics of isomeric molecular rotors 7E and 7Z, consisting of two androstane steroidal frameworks linked by the D rings by triple bonds at their C17 positions to a 1,4-phenylene rotator. They are also linked by the A rings by an alkenyl diester bridge to restrict the conformational flexibility of the molecules and reduce the number of potential crystalline arrays. The analysis of the resulting molecular structures and packing motifs offered insights of the internal dynamics that were later elucidated by means of line shape analyses of the spectral features obtained through variable-temperature solid-state (13)C NMR; such analysis revealed rotations in the solid state occurring at kilohertz frequency at room temperature.

A conformationally persistent pseudo-bicyclic guanidinium for anion coordination as stabilized by dual intramolecular hydrogen bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Seipp, Charles A.; Williams, Neil J.; Bryantsev, Vyacheslav S.

2015-11-30

In this paper, the first example of a pseudo-bicyclic guanidinium ligand is reported. When bound to an anion, the N,N'-bis(2-pyridyl)guanidinium cation persistently adopts the planar α,α conformation featuring intramolecular N···H–N–H···N hydrogen bonds in the solid state, which facilitates crystallization of sulphate from aqueous mixtures of anions.

Contamination removal using various solvents and methodologies

NASA Technical Reports Server (NTRS)

Jeppsen, J. C.

1989-01-01

Critical and non-critical bonding surfaces must be kept free of contamination that may cause potential unbonds. For example, an aft-dome section of a redesigned solid rocket motor that had been contaminated with hydraulic oil did not appear to be sufficiently cleaned when inspected by the optically stimulated electron emission process (Con Scan) after it had been cleaned using a hand double wipe cleaning method. As a result, current and new cleaning methodologies as well as solvent capability in removing various contaminant materials were reviewed and testing was performed. Bonding studies were also done to verify that the cleaning methods used in removing contaminants provide an acceptable bonding surface. The removal of contaminants from a metal surface and the strength of subsequent bonds were tested using the Martin Marietta and double-wipe cleaning methods. Results are reported.

Thermodynamics, Kinetics and Structural Evolution of ε-LiVOPO 4 over Multiple Lithium Intercalation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Yuh-Chieh; Wen, Bohua; Wiaderek, Kamila M.

In this work, we demonstrate the stable cycling of more than one Li in solid-state-synthesized ε-LiVOPO4 over more than 20 cycles for the first time. Using a combination of density functional theory (DFT) calculations, X-ray pair distribution function (PDF) analysis and X-ray absorption near edge structure (XANES) measurements, we present a comprehensive analysis of the thermodynamics, kinetics, and structural evolution of ε-LixVOPO4 over the entire lithiation range. We identify two intermediate phases at x = 1.5 and 1.75 in the low-voltage regime using DFT calculations, and the computed and electrochemical voltage profiles are in excellent agreement. Operando PDF and EXAFSmore » techniques show a reversible hysteretic change in the short (<2 Å) V—O bond lengths coupled with an irreversible extension of the long V—O bond (>2.4 Å) during low-voltage cycling. Hydrogen intercalation from electrolyte decomposition is a possible explanation for the ~2.4 Å V—O bond and its irreversible extension. Finally, we show that ε-LixVOPO4 is likely a pseudo-1D ionic diffuser with low electronic conductivity using DFT calculations, which suggests that nanosizing and carbon coating is necessary to achieve good electrochemical performance in this material.« less

a Theoretical Search for AN Electronic Spectrum of the He-BeO Complex

NASA Astrophysics Data System (ADS)

Gardner, Adrian; Heaven, Michael

2014-06-01

The surprisingly high dissociation energy of the He-Be bond in the He-BeO complex was first reported 25 years ago. Following which, a number of theoretical studies have investigated similar closed shell helium containing complexes. However, despite these investigations, a complex containing a strong He-X bond has thus far eluded experimental detection. In this work, potential energy surfaces of electronically excited states of the He-BeO complex have been calculated employing high level CASSCF+MRCI+Q methodologies and utilizing extended basis sets. Several excited states show strong interactions between helium and BeO lying in Franck-Condon accessible windows of electronic transitions arising from the vibrationless electronic ground state. It is hoped that the conclusions of this study will result in the observation an electronic spectrum of this long hypothesized strongly bound complex in the near future. W. Koch, J. R. Collins and G. Frenking, Chem. Phys. Lett. 1986, 132 330-333.

Interpretation of the photoelectron spectra of FeS(2)(-) by a multiconfiguration computational approach.

PubMed

Clima, Sergiu; Hendrickx, Marc F A

2007-11-01

The ground states of FeS(2) and FeS(2)(-), and several low-lying excited electronic states of FeS(2) that are responsible for the FeS(2)(-) photoelectron spectrum, are calculated. At the B3LYP level an open, quasi-linear [SFeS](-) conformation is found as the most stable structure, which is confirmed at the ab initio CASPT2 computational level. Both the neutral and the anionic unsaturated complexes possess high-spin electronic ground states. For the first time a complete assignment of the photoelectron spectrum of FeS(2)(-) is proposed. The lowest energy band in this spectrum is ascribed to an electron detachment from the two highest-lying 3dpi antibonding orbitals (with respect to the iron-sulfur bonding) of iron. The next-lowest experimental band corresponds to an electron removal from nonbonding, nearly pure sulfur orbitals. The two highest bands in the spectra are assigned as electron detachments from pi and sigma bonding mainly sulfur orbitals.

A theory for bioinorganic chemical reactivity of oxometal complexes and analogous oxidants: the exchange and orbital-selection rules.

PubMed

Usharani, Dandamudi; Janardanan, Deepa; Li, Chunsen; Shaik, Sason

2013-02-19

Over the past decades metalloenzymes and their synthetic models have emerged as an area of increasing research interest. The metalloenzymes and their synthetic models oxidize organic molecules using oxometal complexes (OMCs), especially oxoiron(IV)-based ones. Theoretical studies have helped researchers to characterize the active species and to resolve mechanistic issues. This activity has generated massive amounts of data on the relationship between the reactivity of OMCs and the transition metal's identity, oxidation state, ligand sphere, and spin state. Theoretical studies have also produced information on transition state (TS) structures, reaction intermediates, barriers, and rate-equilibrium relationships. For example, the experimental-theoretical interplay has revealed that nonheme enzymes carry out H-abstraction from strong C-H bonds using high-spin (S = 2) oxoiron(IV) species with four unpaired electrons on the iron center. However, other reagents with higher spin states and more unpaired electrons on the metal are not as reactive. Still other reagents carry out these transformations using lower spin states with fewer unpaired electrons on the metal. The TS structures for these reactions exhibit structural selectivity depending on the reactive spin states. The barriers and thermodynamic driving forces of the reactions also depend on the spin state. H-Abstraction is preferred over the thermodynamically more favorable concerted insertion into C-H bonds. Currently, there is no unified theoretical framework that explains the totality of these fascinating trends. This Account aims to unify this rich chemistry and understand the role of unpaired electrons on chemical reactivity. We show that during an oxidative step the d-orbital block of the transition metal is enriched by one electron through proton-coupled electron transfer (PCET). That single electron elicits variable exchange interactions on the metal, which in turn depend critically on the number of unpaired electrons on the metal center. Thus, we introduce the exchange-enhanced reactivity (EER) principle, which predicts the preferred spin state during oxidation reactions, the dependence of the barrier on the number of unpaired electrons in the TS, and the dependence of the deformation energy of the reactants on the spin state. We complement EER with orbital-selection rules, which predict the structure of the preferred TS and provide a handy theory of bioinorganic oxidative reactions. These rules show how EER provides a Hund's Rule for chemical reactivity: EER controls the reactivity landscape for a great variety of transition-metal complexes and substrates. Among many reactivity patterns explained, EER rationalizes the abundance of high-spin oxoiron(IV) complexes in enzymes that carry out bond activation of the strongest bonds. The concepts used in this Account might also be applicable in other areas such as in f-block chemistry and excited-state reactivity of 4d and 5d OMCs.

Superprotonic solid acids: Structure, properties, and applications

NASA Astrophysics Data System (ADS)

Boysen, Dane Andrew

In this work, the structure and properties of superprotonic MH nXO4-type solid acids (where M = monovalent cation, X = S, Se, P, As, and n = 1, 2) have been investigated and, for the first time, applied in fuel cell devices. Several MH nXO4-type solid acids are known to undergo a "superprotonic" solid-state phase transition upon heating, in which the proton conductivity increases by several orders of magnitude and takes on values of ˜10 -2O-1cm-1. The presence of superprotonic conductivity in fully hydrogen bonded solid acids, such as CsH2PO4, has long been disputed. In these investigations, through the use of pressure, the unequivocal identification of superprotonic behavior in both RbH2PO4 and CsH2PO 4 has been demonstrated, whereas for chemically analogous compounds with smaller cations, such as KH2PO4 and NaH2PO 4, superprotonic conductivity was notably absent. Such observations have led to the adoption of radius ratio rules, in an attempt to identify a critical ion size effect on the presence of superprotonic conductivity in solid acids. It has been found that, while ionic size does play a prominent role in the presence of superprotonic behavior in solid acids, equally important are the effects of ionic and hydrogen bonding. Next, the properties of superprotonic phase transition have been investigated from a thermodynamic standpoint. With contributions from this work, a formulation has been developed that accounts for the entropy resulting from both the disordering of both hydrogen bonds and oxy-anion librations in the superprotonic phase of solid acids. This formulation, fundamentally derived from Linus Pauling's entropy rules for ice, accurately accounts for the change in entropy through a superprotonic phase transition. Lastly, the first proof-of-priniciple fuel cells based upon solid acid electrolytes have been demonstrated. Initial results based upon a sulfate electrolyte, CsHSO4, demonstrated the viability of solid acids, but poor chemical stability under the highly reducing H2 gas environment of the fuel cell anode. Later experiments employing a CsH2PO4 electrolyte proved quite successful. The results of these solid acid-based fuel cell measurements suggest solid acids could serve as an alternative to current state-of-the-art fuel cell electrolytes.

Solid state photosensitive devices which employ isolated photosynthetic complexes

DOEpatents

Peumans, Peter; Forrest, Stephen R.

2009-09-22

Solid state photosensitive devices including photovoltaic devices are provided which comprise a first electrode and a second electrode in superposed relation; and at least one isolated Light Harvesting Complex (LHC) between the electrodes. Preferred photosensitive devices comprise an electron transport layer formed of a first photoconductive organic semiconductor material, adjacent to the LHC, disposed between the first electrode and the LHC; and a hole transport layer formed of a second photoconductive organic semiconductor material, adjacent to the LHC, disposed between the second electrode and the LHC. Solid state photosensitive devices of the present invention may comprise at least one additional layer of photoconductive organic semiconductor material disposed between the first electrode and the electron transport layer; and at least one additional layer of photoconductive organic semiconductor material, disposed between the second electrode and the hole transport layer. Methods of generating photocurrent are provided which comprise exposing a photovoltaic device of the present invention to light. Electronic devices are provided which comprise a solid state photosensitive device of the present invention.

Radiation-induced defects in manganese-doped lithium tetraborate phosphor.

PubMed

Annalakshmi, O; Jose, M T; Madhusoodanan, U; Sridevi, J; Venkatraman, B; Amarendra, G; Mandal, A B

2015-01-01

Lithium tetraborate doped with manganese synthesised by solid-state sintering technique exhibits a dosimetric peak at 280°C. The high-temperature glow curve results in no fading for three months. The sensitivity of Li2B4O7:Mn is determined to be 0.9 times that of TLD-100. The infrared spectrum of this phosphor indicates the presence of bond vibrations corresponding to BO4 tetrahedral and BO3 triangles. The mechanism for thermoluminescence in this phosphor was proposed based on the thermoluminescence (TL) emission spectra, kinetic analysis of TL glow curves and electron paramagnetic resonance (EPR) measurements on non-irradiated and gamma-irradiated phosphors. It was identified that oxygen vacancies and Boron oxygen hole centre (BOHC) are the electron and hole trap centres for TL in this phosphor. When the phosphor is heated, the electrons are released from the electron trap and recombine with the trapped holes. The excitation energy during the recombination is transferred to the nearby Mn(2+) ions, which emit light at 580 nm. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

The effect of nitrogen incorporation on the bonding structure of hydrogenated carbon nitride films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camero, M.; Buijnsters, J. G.; Gomez-Aleixandre, C.

2007-03-15

This work describes the composition and bonding structure of hydrogenated carbon nitride (a-CN{sub x}:H) films synthesized by electron cyclotron resonance chemical vapor deposition using as precursor gases argon, methane, and nitrogen. The composition of the films was derived from Rutherford backscattering and elastic recoil detection analysis and the bonding structure was examined by infrared (IR) spectroscopy and x-ray absorption near edge spectroscopy (XANES). By varying the nitrogen to methane ratio in the applied gas mixture, polymeric a-CN{sub x}:H films with N/C contents varying from 0.06 to 0.49 were obtained. Remarkably, the H content of the films ({approx}40 at. %) wasmore » rather unaffected by the nitrogenation process. The different bonding states as detected in the measured XANES C(1s) and N(1s) spectra have been correlated with those of a large number of reference samples. The XANES and IR spectroscopy results indicate that N atoms are efficiently incorporated into the amorphous carbon network and can be found in different bonding environments, such as pyridinelike, graphitelike, nitrilelike, and amino groups. The nitrogenation of the films results in the formation of N-H bonding environments at the cost of C-H structures. Also, the insertion of N induces a higher fraction of double bonds in the structure at the expense of the linear polymerlike chains, hence resulting in a more cross-linked solid. The formation of double bonds takes place through complex C=N structures and not by formation of graphitic aromatic rings. Also, the mechanical and tribological properties (hardness, friction, and wear) of the films have been studied as a function of the nitrogen content. Despite the major modifications in the bonding structure with nitrogen uptake, no significant changes in these properties are observed.« less

Study of Ti 4+ substitution in ZrW 2O 8 negative thermal expansion materials

NASA Astrophysics Data System (ADS)

De Buysser, Klaartje; Van Driessche, Isabel; Putte, Bart Vande; Schaubroeck, Joseph; Hoste, Serge

2007-08-01

Powder XRD-analysis and thermo-mechanical analysis on sintered TiO 2-WO 3-ZrO 2 mixtures revealed the formation of Zr 1-xTi xW 2O 8 solid solutions. A noticeable decrease in unit cell parameter ' a' and in the order-disorder transition temperature could be seen in the case of Zr 1-xTi xW 2O 8 solid solutions. Studies performed on other ZrW 2O 8 solid solutions have attributed an increase in phase transition temperature to a decrease in free lattice volume, whereas a decrease in phase transition temperature was suggested to be due to the presence of a more disordered state. Our studies indicate that the phase transition temperature in our materials is strongly influenced by the bond dissociation energy of the substituting ion-oxygen bond. A decrease in bond strength may compensate for the effect of a decrease in lattice free volume, lowering the phase transition temperature as the degree of substitution by Ti 4+ increases. This hypothesis is proved by differential scanning calorimetry.

First-principles study of the solid solution of hydrogen in lanthanum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schoellhammer, Gunther; Herzig, Peter; Wolf, Walter

2011-09-01

Results from first-principles investigations of the energetical, structural, electronic, and vibrational properties of model structures probing the metal-rich region of the lanthanum-hydrogen system, i.e., the region of the solid solution of hydrogen in lanthanum, are presented. We have studied the site preference and the ordering tendency of hydrogen atoms interstitially bonded in close-packed lanthanum. Spatially separated hydrogen atoms have turned out to exhibit an energetical preference for the occupation of octahedral interstitial sites at low temperature. Indications for a reversal of the site preference in favor of the occupation of tetrahedral interstitial sites at elevated temperature have been found. Linearmore » arrangements consisting of pairs of octahedrally and/or tetrahedrally coordinated hydrogen atoms collinearly bonded to a central lanthanum atom have turned out to be energetically favorable structure elements. Further stabilization is achieved if such hydrogen pairs are in turn linked together so that extended chains of La-H bonds are formed. Pair formation and chain linking counteract the energetical preference for octahedral coordination observed for separated hydrogen atoms.« less

Quantum model of a solid-state spin qubit: Ni cluster on a silicon surface by the generalized spin Hamiltonian and X-ray absorption spectroscopy investigations

NASA Astrophysics Data System (ADS)

Farberovich, Oleg V.; Mazalova, Victoria L.; Soldatov, Alexander V.

2015-11-01

We present here the quantum model of a Ni solid-state electron spin qubit on a silicon surface with the use of a density-functional scheme for the calculation of the exchange integrals in the non-collinear spin configurations in the generalized spin Hamiltonian (GSH) with the anisotropic exchange coupling parameters linking the nickel ions with a silicon substrate. In this model the interaction of a spin qubit with substrate is considered in GSH at the calculation of exchange integrals Jij of the nanosystem Ni7-Si in the one-electron approach taking into account chemical bonds of all Si-atoms of a substrate (environment) with atoms of the Ni7-cluster. The energy pattern was found from the effective GSH Hamiltonian acting in the restricted spin space of the Ni ions by the application of the irreducible tensor operators (ITO) technique. In this paper we offer the model of the quantum solid-state N-spin qubit based on the studying of the spin structure and the spin-dynamics simulations of the 3d-metal Ni clusters on the silicon surface. The solution of the problem of the entanglement between spin states in the N-spin systems is becoming more interesting when considering clusters or molecules with a spectral gap in their density of states. For quantifying the distribution of the entanglement between the individual spin eigenvalues (modes) in the spin structure of the N-spin system we use the density of entanglement (DOE). In this study we have developed and used the advanced high-precision numerical techniques to accurately assess the details of the decoherence process governing the dynamics of the N-spin qubits interacting with a silicon surface. We have studied the Rabi oscillations to evaluate the N-spin qubits system as a function of the time and the magnetic field. We have observed the stabilized Rabi oscillations and have stabilized the quantum dynamical qubit state and Rabi driving after a fixed time (0.327 μs). The comparison of the energy pattern with the anisotropic exchange models conventionally used for the analysis of this system and, with the results of the experimental XANES spectra, shows that our complex investigations provide a good description of the pattern of the spin levels and the spin structures of the nanomagnetic Ni7 qubit. The results are discussed in the view of the general problem of the solid-state spin qubits and the spin structure of the Ni cluster.

When One Configuration Is Not Enough

ERIC Educational Resources Information Center

McMillin, David R.

2008-01-01

For most molecules molecular orbital theory predicts a ground-state electronic configuration that is useful for rationalizing relative bond lengths, magnetic properties, and so forth. However, when electron correlation is a dominant consideration, the ground-state configuration may provide a poor representation of the system. In such cases,…

Effect of critical molecular weight of PEO in epoxy/EPO blends as characterized by advanced DSC and solid-state NMR

NASA Astrophysics Data System (ADS)

Wang, Xiaoliang; Lu, Shoudong; Sun, Pingchuan; Xue, Gi

2013-03-01

The differential scanning calorimetry (DSC) and solid state NMR have been used to systematically study the length scale of the miscibility and local dynamics of the epoxy resin/poly(ethylene oxide) (ER/PEO) blends with different PEO molecular weight. By DSC, we found that the diffusion behavior of PEO with different Mw is an important factor in controlling these behaviors upon curing. We further employed two-dimensional 13C-{1H}PISEMA NMR experiment to elucidate the possible weak interaction and detailed local dynamics in ER/PEO blends. The CH2O group of PEO forms hydrogen bond with hydroxyl proton of cured-ER ether group, and its local dynamics frozen by such interaction. Our finding indicates that molecular weight (Mw) of PEO is a crucial factor in controlling the miscibility, chain dynamics and hydrogen bonding interaction in these blends.

Obstacles and opportunities in the commercialization of the solid state electronic fluorescent lighting ballast

NASA Astrophysics Data System (ADS)

Johnson, D. R.; Marcus, A. A.; Campbell, R. S.; Sommers, P.; Skumatz, L.; Berk, B.; Petty, P.; Eschbach, C.

1981-10-01

A solid state ballast (SSB), which improves the efficiency of fluorescent lights, is described. The first generation of solid state electronic ballasts was developed and the technology was transferred to the private sector. The opportunities for rapid dissemination of this technology into the marketplace is examined. Product characteristics and their influence on the commercialization of the SSB, a description of the technology delivery system presently used by the ballast industry, an analysis of the market for SSB, and identification of some high leverage opportunities to accelerate the commercialization process are included.

Structural properties and electrochemistry of α-LiFeO2

NASA Astrophysics Data System (ADS)

Abdel-Ghany, A. E.; Mauger, A.; Groult, H.; Zaghib, K.; Julien, C. M.

2012-01-01

In this work, we study the physico-chemistry and electrochemistry of lithium ferrite synthesized by solid-state reaction. Characterization included X-ray diffraction (XRD), scanning electronic microscopy (SEM), Raman scattering (RS), Fourier transform infrared spectroscopy (FTIR), and SQUID magnetometry. XRD peaks gradually sharpen with increasing firing temperature; all the diffraction peaks can be indexed to the cubic α-LiFeO2 phase (Fm3m space group) with the refined cell parameter a = 4.155 Å. RS and FTIR spectra show the vibrational modes due to covalent Fe-O bonds and the Li-cage mode at low-frequency. The electrochemical properties of Li/LiFeO2 are revisited along with the post-mortem analysis of the positive electrode material using XRD and Raman experiments.

3D integrated superconducting qubits

NASA Astrophysics Data System (ADS)

Rosenberg, D.; Kim, D.; Das, R.; Yost, D.; Gustavsson, S.; Hover, D.; Krantz, P.; Melville, A.; Racz, L.; Samach, G. O.; Weber, S. J.; Yan, F.; Yoder, J. L.; Kerman, A. J.; Oliver, W. D.

2017-10-01

As the field of quantum computing advances from the few-qubit stage to larger-scale processors, qubit addressability and extensibility will necessitate the use of 3D integration and packaging. While 3D integration is well-developed for commercial electronics, relatively little work has been performed to determine its compatibility with high-coherence solid-state qubits. Of particular concern, qubit coherence times can be suppressed by the requisite processing steps and close proximity of another chip. In this work, we use a flip-chip process to bond a chip with superconducting flux qubits to another chip containing structures for qubit readout and control. We demonstrate that high qubit coherence (T1, T2,echo > 20 μs) is maintained in a flip-chip geometry in the presence of galvanic, capacitive, and inductive coupling between the chips.

Dipole moment, solution, and solid state structure (-)-epicatechin, a monomer unit of procyanidin polymers

Treesearch

Frank R. Fronczek; Garret Gannuch; Wayne L. Mattice; Fred L. Tobiason; Jeff L. Broker; Richard W. Hemingway

1984-01-01

The structure of (-)-epicatechin has been determined in the crystalline state. Crystals are orthorhombic. P212121, a=670.8(1), b=1329.1 (3), c=1426.2(4) pm, Z=4. Dc=1.516 g cm-3, R=0.041 for 1624 observations. Intramolecular hydrogen bonds are absent. The...

Rotational symmetry breaking toward a string-valence bond solid phase in frustrated J1 -J2 transverse field Ising model

NASA Astrophysics Data System (ADS)

Sadrzadeh, M.; Langari, A.

2018-06-01

We study the effect of quantum fluctuations by means of a transverse magnetic field (Γ) on the highly degenerate ground state of antiferromagnetic J1 -J2 Ising model on the square lattice, at the limit J2 /J1 = 0.5 . We show that harmonic quantum fluctuations based on single spin flips can not lift such degeneracy, however an-harmonic quantum fluctuations based on multi spin cluster flip excitations lift the degeneracy toward a unique ground state with string-valence bond solid (VBS) nature. A cluster operator formalism has been implemented to incorporate an-harmonic quantum fluctuations. We show that cluster-type excitations of the model lead not only to lower the excitation energy compared with a single-spin flip but also to lift the extensive degeneracy in favor of a string-VBS state, which breaks lattice rotational symmetry with only two fold degeneracy. The tendency toward the broken symmetry state is justified by numerical exact diagonalization. Moreover, we introduce a map to find the relation between the present model on the checkerboard and square lattices.

Extreme population inversion in the fragments formed by UV photoinduced S-H bond fission in 2-thiophenethiol.

PubMed

Ingle, Rebecca A; Karsili, Tolga N V; Dennis, Gregg J; Staniforth, Michael; Stavros, Vasilios G; Ashfold, Michael N R

2016-04-28

H atom loss following near ultraviolet photoexcitation of gas phase 2-thiophenethiol molecules has been studied experimentally, by photofragment translational spectroscopy (PTS) methods, and computationally, by ab initio electronic structure calculations. The long wavelength (277.5 ≥ λ(phot) ≥ 240 nm) PTS data are consistent with S-H bond fission after population of the first (1)πσ* state. The partner thiophenethiyl (R) radicals are formed predominantly in their first excited Ã(2)A' state, but assignment of a weak signal attributable to H + R(X˜(2)A'') products allows determination of the S-H bond strength, D0 = 27,800 ± 100 cm(-1) and the Ã-X˜ state splitting in the thiophenethiyl radical (ΔE = 3580 ± 100 cm(-1)). The deduced population inversion between the à and X˜ states of the radical reflects the non-planar ground state geometry (wherein the S-H bond is directed near orthogonal to the ring plane) which, post-photoexcitation, is unable to planarise sufficiently prior to bond fission. This dictates that the dissociating molecules follow the adiabatic fragmentation pathway to electronically excited radical products. π* ← π absorption dominates at shorter excitation wavelengths. Coupling to the same (1)πσ* potential energy surface (PES) remains the dominant dissociation route, but a minor yield of H atoms attributable to a rival fragmentation pathway is identified. These products are deduced to arise via unimolecular decay following internal conversion to the ground (S0) state PES via a conical intersection accessed by intra-ring C-S bond extension. The measured translational energy disposal shows a more striking change once λ(phot) ≤ 220 nm. Once again, however, the dominant decay pathway is deduced to be S-H bond fission following coupling to the (1)πσ* PES but, in this case, many of the evolving molecules are deduced to have sufficiently near-planar geometries to allow passage through the conical intersection at extended S-H bond lengths and dissociation to ground (X˜) state radical products. The present data provide no definitive evidence that complete ring opening can compete with fast S-H bond fission following near UV photoexcitation of 2-thiophenethiol.

Bond-length distributions for ions bonded to oxygen: results for the non-metals and discussion of lone-pair stereoactivity and the polymerization of PO4

PubMed Central

Gagné, Olivier Charles

2018-01-01

Bond-length distributions are examined for three configurations of the H+ ion, 16 configurations of the group 14–16 non-metal ions and seven configurations of the group 17 ions bonded to oxygen, for 223 coordination polyhedra and 452 bond distances for the H+ ion, 5957 coordination polyhedra and 22 784 bond distances for the group 14–16 non-metal ions, and 248 coordination polyhedra and 1394 bond distances for the group 17 non-metal ions. H⋯O and O—H + H⋯O distances correlate with O⋯O distance (R 2 = 0.94 and 0.96): H⋯O = 1.273 × O⋯O – 1.717 Å; O—H + H⋯O = 1.068 × O⋯O – 0.170 Å. These equations may be used to locate the hydrogen atom more accurately in a structure refined by X-ray diffraction. For non-metal elements that occur with lone-pair electrons, the most observed state between the n versus n+2 oxidation state is that of highest oxidation state for period 3 cations, and lowest oxidation state for period 4 and 5 cations when bonded to O2−. Observed O—X—O bond angles indicate that the period 3 non-metal ions P3+, S4+, Cl3+ and Cl5+ are lone-pair seteroactive when bonded to O2−, even though they do not form secondary bonds. There is no strong correlation between the degree of lone-pair stereoactivity and coordination number when including secondary bonds. There is no correlation between lone-pair stereoactivity and bond-valence sum at the central cation. In synthetic compounds, PO4 polymerizes via one or two bridging oxygen atoms, but not by three. Partitioning our PO4 dataset shows that multi-modality in the distribution of bond lengths is caused by the different bond-valence constraints that arise for Obr = 0, 1 and 2. For strongly bonded cations, i.e. oxyanions, the most probable cause of mean bond length variation is the effect of structure type, i.e. stress induced by the inability of a structure to follow its a priori bond lengths. For ions with stereoactive lone-pair electrons, the most probable cause of variation is bond-length distortion.

The influence of the local structure on proton transport in a solid oxide proton conductor La 0.8 Ba 1.2 GaO 3.9

DOE PAGES

Cheng, Yongqiang; Balachandran, Janakiraman; Bi, Zhonghe; ...

2017-07-18

The local structure around the mobile ions influences their dynamics. The knowledge about the relationship between these properties is of fundamental importance and may lead the way for development of improved solid state ionic conductors. Here, we use inelastic neutron scattering and ab initio modeling to study a representative proton conductor, La 0.8Ba 1.2GaO 3.9, where different local structures are possible for the same stoichiometry. The intrinsic correlations between the local bonding environment and the dynamical behavior of protons are presented. In particular, we identify how the local Ba/La concentration affects the proton vibrational frequencies, hydrogen bond strength, O–H rotationsmore » and in turn long-range proton mobility. Furthermore, possible mechanism for proton transport, through the inter-tetrahedral bond switching, O–H rotations and tetrahedral reorientation is anticipated.« less

Mixed-valent dicobalt and iron-cobalt complexes with high-spin configurations and short metal-metal bonds.

PubMed

Zall, Christopher M; Clouston, Laura J; Young, Victor G; Ding, Keying; Kim, Hyun Jung; Zherebetskyy, Danylo; Chen, Yu-Sheng; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C

2013-08-19

Cobalt-cobalt and iron-cobalt bonds are investigated in coordination complexes with formally mixed-valent [M2](3+) cores. The trigonal dicobalt tris(diphenylformamidinate) compound, Co2(DPhF)3, which was previously reported by Cotton, Murillo, and co-workers (Inorg. Chim. Acta 1996, 249, 9), is shown to have an energetically isolated, high-spin sextet ground-state by magnetic susceptibility and electron paramagnetic resonance (EPR) spectroscopy. A new tris(amidinato)amine ligand platform is introduced. By tethering three amidinate donors to an apical amine, this platform offers two distinct metal-binding sites. Using the phenyl-substituted variant (abbreviated as L(Ph)), the isolation of a dicobalt homobimetallic and an iron-cobalt heterobimetallic are demonstrated. The new [Co2](3+) and [FeCo](3+) cores have high-spin sextet and septet ground states, respectively. Their solid-state structures reveal short metal-metal bond distances of 2.29 Å for Co-Co and 2.18 Å for Fe-Co; the latter is the shortest distance for an iron-cobalt bond to date. To assign the positions of iron and cobalt atoms as well as to determine if Fe/Co mixing is occurring, X-ray anomalous scattering experiments were performed, spanning the Fe and Co absorption energies. These studies show only a minor amount of metal-site mixing in this complex, and that FeCoL(Ph) is more precisely described as (Fe0.94(1)Co0.06(1))(Co0.95(1)Fe0.05(1))L(Ph). The iron-cobalt heterobimetallic has been further characterized by Mössbauer spectroscopy. Its isomer shift of 0.65 mm/s and quadrupole splitting of 0.64 mm/s are comparable to the related diiron complex, Fe2(DPhF)3. On the basis of spectroscopic data and theoretical calculations, it is proposed that the formal [M2](3+) cores are fully delocalized.

Mixed-Valent Dicobalt and Iron-Cobalt Complexes with High-Spin Configurations and Short Metal-Metal Bonds

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zall, Christopher M.; Clouston, Laura J.; Young, Jr., Victor G.

2013-09-23

Cobalt–cobalt and iron–cobalt bonds are investigated in coordination complexes with formally mixed-valent [M 2] 3+ cores. The trigonal dicobalt tris(diphenylformamidinate) compound, Co 2(DPhF) 3, which was previously reported by Cotton, Murillo, and co-workers (Inorg. Chim. Acta 1996, 249, 9), is shown to have an energetically isolated, high-spin sextet ground-state by magnetic susceptibility and electron paramagnetic resonance (EPR) spectroscopy. A new tris(amidinato)amine ligand platform is introduced. By tethering three amidinate donors to an apical amine, this platform offers two distinct metal-binding sites. Using the phenyl-substituted variant (abbreviated as L Ph), the isolation of a dicobalt homobimetallic and an iron–cobalt heterobimetallic aremore » demonstrated. The new [Co 2] 3+ and [FeCo] 3+ cores have high-spin sextet and septet ground states, respectively. Their solid-state structures reveal short metal–metal bond distances of 2.29 Å for Co–Co and 2.18 Å for Fe–Co; the latter is the shortest distance for an iron–cobalt bond to date. To assign the positions of iron and cobalt atoms as well as to determine if Fe/Co mixing is occurring, X-ray anomalous scattering experiments were performed, spanning the Fe and Co absorption energies. These studies show only a minor amount of metal-site mixing in this complex, and that FeCoL Ph is more precisely described as (Fe 0.94(1)Co 0.06(1))(Co 0.95(1)Fe 0.05(1))L Ph. The iron–cobalt heterobimetallic has been further characterized by Mössbauer spectroscopy. Its isomer shift of 0.65 mm/s and quadrupole splitting of 0.64 mm/s are comparable to the related diiron complex, Fe 2(DPhF) 3. On the basis of spectroscopic data and theoretical calculations, it is proposed that the formal [M 2] 3+ cores are fully delocalized.« less

Electronic structure description of the cis-MoOS unit in models for molybdenum hydroxylases.

PubMed

Doonan, Christian J; Rubie, Nick D; Peariso, Katrina; Harris, Hugh H; Knottenbelt, Sushilla Z; George, Graham N; Young, Charles G; Kirk, Martin L

2008-01-09

The molybdenum hydroxylases catalyze the oxidation of numerous aromatic heterocycles and simple organics and, unlike other hydroxylases, utilize water as the source of oxygen incorporated into the product. The electronic structures of the cis-MoOS units in CoCp2[TpiPrMoVOS(OPh)] and TpiPrMoVIOS(OPh) (TpiPr = hydrotris(3-isopropylpyrazol-1-yl)borate), new models for molybdenum hydroxylases, have been studied in detail using S K-edge X-ray absorption spectroscopy, vibrational spectroscopy, and detailed bonding calculations. The results show a highly delocalized Mo=S pi* LUMO redox orbital that is formally Mo(dxy) with approximately 35% sulfido ligand character. Vibrational spectroscopy has been used to quantitate Mo-Ssulfido bond order changes in the cis-MoOS units as a function of redox state. Results support a redox active molecular orbital that has a profound influence on MoOS bonding through changes to the relative electro/nucleophilicity of the terminal sulfido ligand accompanying oxidation state changes. The bonding description for these model cis-MoOS systems supports enzyme mechanisms that are under orbital control and dominantly influenced by the unique electronic structure of the cis-MoOS site. The electronic structure of the oxidized enzyme site is postulated to play a role in polarizing a substrate carbon center for nucleophilic attack by metal activated water and acting as an electron sink in the two-electron oxidation of substrates.

Summary of Prior Work on Joining of Oxide Dispersion-Strengthened Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wright, Ian G; Tatlock, Gordon J; Badairy, H.

2009-08-01

There is a range of joining techniques available for use with ODS alloys, but care should be exercised in matching the technique to the final duty requirements of the joint. The goal for joining ODS alloys is a joint with no local disruption of the distribution of the oxide dispersion, and no significant change in the size and orientation of the alloy microstructure. Not surprisingly, the fusion welding processes typically employed with wrought alloys produce the least satisfactory results with ODS alloys, but some versions, such as fusion spot welding, and the laser and electron-beam welding technologies, have demonstrated potentialmore » for producing sound joints. Welds made using solid-state spot welding reportedly have exhibited parent metal properties. Thus, it is possible to employ processes that result in significant disruption of the alloy microstructure, as long as the processing parameters are adjustment to minimize the extent of or influence of the changes in the alloy microstructure. Selection among these joining approaches largely depends on the particular application and component configuration, and an understanding of the relationships among processing, alloy microstructure, and final properties is key. Recent developments have resulted in friction welding evolving to be a prime method for joining ODS sheet products, and variants of brazing/diffusion bonding have shown excellent promise for use with tubes and pipes. The techniques that come closest to the goal defined above involve solid-state diffusion bonding and, in particular, it has been found that secondary recrystallization of joints made by pulsed plasma-assisted diffusion can produce the desired, continuous, large alloy grain structure through the joint. Such joints have exhibited creep rupture failure at >82% of the load needed to fail the monolithic parent alloy at 1000 C.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ben Smida, Youssef; Marzouki, Riadh; Georges, Samuel

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, andmore » its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.« less

Spin Uncoupling in Chemisorbed OCCO and CO 2: Two High-Energy Intermediates in Catalytic CO 2 Reduction

DOE PAGES

Hedstrom, Svante; dos Santos, Egon Campos; Liu, Chang; ...

2018-05-08

Here, the production of useful compounds via the electrochemical carbon dioxide reduction reaction (CO2RR) is a matter of intense research. Although the thermodynamics and kinetic barriers of CO2RR are reported in previous computational studies, the electronic structure details are often overlooked. We study two important CO2RR intermediates: ethylenedione (OCCO) and CO 2 covalently bound to cluster and slab models of the Cu(100) surface. Both molecules exhibit a near-unity negative charge as chemisorbed, but otherwise they behave quite differently, as explained by a spin-uncoupling perspective. OCCO adopts a high-spin, quartetlike geometry, allowing two covalent bonds to the surface with an averagemore » gross interaction energy of –1.82 eV/bond. The energy cost for electronically exciting OCCO– to the quartet state is 1.5 eV which is readily repaid via the formation of its two surface bonds. CO 2, conversely, retains a low-spin, doubletlike structure upon chemisorption, and its single unpaired electron forms a single covalent surface bond of –2.07 eV. The 5.0 eV excitation energy to the CO 2 – quartet state is prohibitively costly and cannot be compensated for by an additional surface bond.« less

Role of Electronic Structure In Ion Band State Theory of Low Energy Nuclear Reactions

NASA Astrophysics Data System (ADS)

Chubb, Scott

2004-03-01

The Nuts and Bolts of our Ion Band State (IBS) theory of low energy nuclear reactions (LENR's) in palladium-deuteride (PdD) and palladium-hydride (PdH) are the electrons that hold together or tear apart the bonds (or lack of bonds) between deuterons (d's) or protons (p's) and the host material. In PdDx and PdH_x, this bonding is strongly correlated with loading: in ambient loading conditions (x< 0. 6), the bonding in hibits IBS occupation. As x arrow 1, slight increases and decreases in loading can lead to vibrations (which have conventionally been thought to occur from phonons) that can induce potential losses or increases of p/d. Naive assumptions about phonons fail to include these losses and increases. These effects can occur because neither H or D has core electrons and because in either PdD or PdH, the electrons near the Fermi Energy have negligible overlap with the nucleus of either D or H. I use these ideas to develop a formal justification, based on a generalization of conventional band theory (Scott Chubb, "Semi-Classical Conduction of Charged and Neutral Particles in Finite Lattices," 2004 March Meeting."), for the idea that occupation of IBS's can occur and that this can lead to nuclear reactions.

Exploiting the Synergy of Powder X-ray Diffraction and Solid-State NMR Spectroscopy in Structure Determination of Organic Molecular Solids

PubMed Central

2013-01-01

We report a strategy for structure determination of organic materials in which complete solid-state nuclear magnetic resonance (NMR) spectral data is utilized within the context of structure determination from powder X-ray diffraction (XRD) data. Following determination of the crystal structure from powder XRD data, first-principles density functional theory-based techniques within the GIPAW approach are exploited to calculate the solid-state NMR data for the structure, followed by careful scrutiny of the agreement with experimental solid-state NMR data. The successful application of this approach is demonstrated by structure determination of the 1:1 cocrystal of indomethacin and nicotinamide. The 1H and 13C chemical shifts calculated for the crystal structure determined from the powder XRD data are in excellent agreement with those measured experimentally, notably including the two-dimensional correlation of 1H and 13C chemical shifts for directly bonded 13C–1H moieties. The key feature of this combined approach is that the quality of the structure determined is assessed both against experimental powder XRD data and against experimental solid-state NMR data, thus providing a very robust validation of the veracity of the structure. PMID:24386493

Exploiting the Synergy of Powder X-ray Diffraction and Solid-State NMR Spectroscopy in Structure Determination of Organic Molecular Solids.

PubMed

Dudenko, Dmytro V; Williams, P Andrew; Hughes, Colan E; Antzutkin, Oleg N; Velaga, Sitaram P; Brown, Steven P; Harris, Kenneth D M

2013-06-13

We report a strategy for structure determination of organic materials in which complete solid-state nuclear magnetic resonance (NMR) spectral data is utilized within the context of structure determination from powder X-ray diffraction (XRD) data. Following determination of the crystal structure from powder XRD data, first-principles density functional theory-based techniques within the GIPAW approach are exploited to calculate the solid-state NMR data for the structure, followed by careful scrutiny of the agreement with experimental solid-state NMR data. The successful application of this approach is demonstrated by structure determination of the 1:1 cocrystal of indomethacin and nicotinamide. The 1 H and 13 C chemical shifts calculated for the crystal structure determined from the powder XRD data are in excellent agreement with those measured experimentally, notably including the two-dimensional correlation of 1 H and 13 C chemical shifts for directly bonded 13 C- 1 H moieties. The key feature of this combined approach is that the quality of the structure determined is assessed both against experimental powder XRD data and against experimental solid-state NMR data, thus providing a very robust validation of the veracity of the structure.

A Chemical Approach to Understanding Oxide Surface Structure and Reactivity

NASA Astrophysics Data System (ADS)

Enterkin, James Andrew

Transmission electron microscopy and diffraction are powerful tools for solving complex structural problems. They complement other analytical techniques, such as x-ray diffraction, elucidating problems which cannot be solved by other techniques. One area where they are of particularly great value is in the determination of surface structures. The research presented herein uses electron microscopy and diffraction as the primary experimental techniques in the development of a chemistry of surface structures. High-resolution electron microscopy revealed that the La4Cu 3MoO12 structure has turbostratic disorder and a lower symmetry space group (Pm) than was previously found. The refinement of the x-ray data was significantly improved by using a disordered model and the Pm space group. A bond valence analysis confirmed that the disordered structure is the superior model. Strontium titanate, SrTiO3, single crystal surfaces were examined principally via transmission electron diffraction. A homologous series with intergrowths was discovered on the (110) surface of strontium titanate, marking the first time that these important concepts of solid state chemistry have been found at the surface. Atmospheric adsorbates, such as H2O and CO2, were found to help to stabilize undercoordinated surface structures on the (100) surface. It was shown that chemical bonding, bond valence, atomic coordination, and stoichiometry greatly influence the development of surface structures. Additionally, such chemistry based analysis was demonstrated to be able to predict surface structure stability and reactivity. Application of a modified Wulff construction to the observed shape of strontium titanate nanocuboids revealed that the surface structure and particle stoichiometry are interlinked, with control over one allowing equally precise control over the other. Platinum nanoparticles on the strontium titanate nanocuboids were shown via high resolution electron microscopy to have cube-on-cube epitaxy, with the shape of the platinum nanoparticles governed by the Winterbottom construction. Precise modification of the support surface will therefore allow engineering of supported metal particles with precise control over which facets are exposed. These results suggest that control over the support surface chemistry can be used to engineer thermodynamically stable, face selective catalysts.

Homoleptic Ce(III) and Ce(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bogart, Justin A.; Lewis, Andrew J.; Medling, Scott A.

2014-06-25

Electrochemical experiments performed on the complex Ce-IV[2-((BuNO)-Bu-t)py](4), where [2-((BuNO)-Bu-t)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(Bu4N)-Bu-n](2)[Ce(NO3)(6)] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with delta symmetry. The results speak to the behavior of CeO2 and related solid solutions inmore » oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.« less

Theoretical investigation of the reactivity in the C-F bond activation of CH 3F by Lu + in the gas phase

NASA Astrophysics Data System (ADS)

Liu, Ze-Yu; Wang, Yong-Cheng; Geng, Zhi-Yuan; Yang, Xiao-Yan; Wang, Han-Qing

2006-11-01

The reaction of Lu + with CH 3F, which was selected as a representative system of the activation of C-F bond in fluorohydrocarbons by late lanthanide cations, has been examined using density functional theory (DFT). The potential energy surfaces (PESs) of [Lu, C, H 3, F] + were explored in detail in both singlet and triplet electronic states. The electron-transfer reactivity of the reaction was analyzed using the two-state model, and a strongly avoided crossing behaviour on the transition state (TS) area was shown. The theoretical results can act as a guide to further theoretical and experimental researches.

Millimeter Thin and Rubber-Like Solid-State Lighting Modules Fabricated Using Roll-to-Roll Fluidic Self-Assembly and Lamination.

PubMed

Park, Se-Chul; Biswas, Shantonu; Fang, Jun; Mozafari, Mahsa; Stauden, Thomas; Jacobs, Heiko O

2015-06-24

A millimeter thin rubber-like solid-state lighting module is reported. The fabrication of the lighting module incorporates assembly and electrical connection of light-emitting diodes (LEDs). The assembly is achieved using a roll-to-roll fluidic self-assembly. The LEDs are sandwiched in-between a stretchable top and bottom electrode to relieve the mechanical stress. The top contact is realized using a lamination technique that eliminates wire-bonding. © 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sun Oven Grown Cuprates Superconductivity and Periodic Lattice Distortions PLD

NASA Astrophysics Data System (ADS)

Acrivos, Juana V.; Chidvinadze, J. G.; Gulanova, D. D.; Loy, D.

2011-03-01

Bi 1.7 Pb 0.3 Sr 2 Ca n-1 Cu n O4 + 2 n + δ identified by the layer heavy element composition with substitution, s (2 s :2:n-1:n > 2) cuprates grown by green chemistry, transition temperatures to superconductivity Tc = 87 to 150K are related to their structure. Enhanced XRD at energies near but below the Cu K, and Pb and Bi L3-edges for pure n=2, 3 phases show Darwin shaped preferred [HKL] reflections that identify the magnitude of the allowed transition moment from the core state to extended unoccupied states determined by the electron density symmetry in that plane, confirmed by XAS of 3 μ m thick films. Weak PLD are still detected, but the stability gained by substitution of Bi by Pb is the formation of nearly symmetric Pb8 cubes in (2s : 2 : 1 : 2)13 and (2s < formula > < ? TeX super-lattices. The preferred 2D [HKL] reflection planes play the same role in the chemical activity of 3D solids as the linear bonds do in molecular reactions, governed by scattering dependent on the electron density symmetry in their highest and lowest unoccupied states. Supported by US NSF, Dreyfus, DOE Laboratories SSRL-SLAC, STUC-Ukraine and Georgia NSF.

BOOK REVIEW: Solid State Physics: An Introduction

NASA Astrophysics Data System (ADS)

Jakoby, Bernhard

2009-07-01

There's a wealth of excellent textbooks on solid state physics. The author of the present book is well aware of this fact and does not attempt to write just another one. Rather, he has provided a very compact introduction to solid state physics for third-year students. As we are faced with the continuous appearance interdisciplinary fields and associated study curricula in natural and engineering sciences (biophysics, mechatronics, etc), a compact text in solid state physics would be appreciated by students of these disciplines as well. The book features 11 chapters where each is provided with supplementary discussion questions and problems. The first chapters deal with a review of chemical bonding mechanisms, crystal structures and mechanical properties of solids, which are brief but by no means superficial. The following, somewhat more detailed chapter on thermal properties of lattices includes a nice introduction to phonons. The foundations of solid state electronics are treated in the next three chapters. Here the author first discusses the classical treatment of electronic behaviour in metals (Drude model) and continues with a quantum-theoretical approach starting with the free-electron model and leading to the band structures in conductive solids. The next chapter is devoted to semiconductors and ends with a brief but, with respect to the topical scope, adequate discussion of semiconductor devices. The classical topics of magnetic and dielectric behaviour are treated in the sequel. The book closes with a chapter on superconductivity and a brief chapter covering the modern topics of quantum confinement and aspects of nanoscale physics. In my opinion, the author has succeeded in creating a very concise yet not superficial textbook. The account presented often probes subjects deep enough to lay the basis for a thorough understanding, preparing the reader for more specialized textbooks. For instance, I think that this book may serve as an excellent first introduction to semiconductor physics. Of course, the detailed treatment of some topics had to be spared and it is certainly a matter of taste which subjects should be treated in detail in a solid state textbook and which can be covered by references to other textbooks or further literature. A typical example for the latter is the decision to omit the detailed treatment of the local field concept leading to the Clausius-Mosotti relation. What could be improved in further editions (which will hopefully be coming) are more specific cross-references within the book and to other textbooks. In the current edition, missing internal cross-references can be compensated for by consulting the subject index, but it would be nicer to have these in the text. As mentioned above, I expect that this book will also be useful to engineering students. For these, it would be beneficial to provide more details on underlying terms and concepts that they, according to common engineering curricula, may not be that familiar with. Examples for such topics are quantum theory beyond the very first principles (e.g., multi-particle treatment, operators and observables) and thermodynamics (e.g., the relevance of electrochemical potential and Fermi levels). These topics could be treated in a concise manner in additional appendices. The current appendix is very short and rudimentary at times, e.g., for the microscopic form of Maxwell's equations, electric and magnetic fluxes are introduced but not outlined further (in that respect, it could also be useful to have a list of used symbols). In summary, this textbook definitely has an interesting scope within an established field and it has been written with appealing didactic skills. This first edition truly deserves to be discovered by students of various disciplines, who want to obtain a quick introduction to solid state physics.

Hypo-electronic triple-decker sandwich complexes: synthesis and structural characterization of [(Cp*Mo)2{μ-η(6):η(6)-B4H4E-Ru(CO)3}] (E = S, Se, Te or Ru(CO)3 and Cp* = η(5)-C5Me5).

PubMed

Mondal, Bijan; Bhattacharyya, Moulika; Varghese, Babu; Ghosh, Sundargopal

2016-07-05

The syntheses and structural characterization of hypo-electronic di-molybdenum triple-decker sandwich clusters are reported. Thermolysis of [Ru3(CO)12] with an in situ generated intermediate obtained from the reaction of [Cp*MoCl4] with [LiBH4·THF] yielded an electron deficient triple-decker sandwich complex, [(Cp*Mo)2{μ-η(6):η(6)-B4H4Ru2(CO)6}], . In an effort to generate analogous triple-deckers containing group-16 elements, we isolated [(Cp*Mo)2{μ-η(6):η(6)-B4H4ERu(CO)3}] (: E = Te; : E = S; : E = Se). These clusters show a high metal coordination number and cross cluster Mo-Mo bond. The formal cluster electron count of these compounds is four or three skeletal electron pairs less than required for a canonical closo-structure of the same nuclearity. Therefore, these compounds represent a novel class of triple-decker sandwich complex with 22 or 24 valence-electrons (VE), wherein the "chair" like hexagonal middle ring is composed of B, Ru and chalcogen. One of the key differences among the synthesized triple-decker molecules is the puckering nature of the middle ring [B4RuE], which increases in the order S < Se < Ru(CO)3 < Te. In addition, Fenske-Hall and quantum-chemical calculations with DFT methods at the BP86 level of theory have been used to analyze the bonding of these novel complexes. The studies not only explain the electron unsaturation of the molecules, but also reveal the reason for the significant puckering of the middle deck. All the compounds have been characterized by IR, (1)H, (11)B, and (13)C NMR spectroscopy in solution and the solid state structures were established by crystallographic analysis.

Description of ground and excited electronic states by ensemble density functional method with extended active space

DOE PAGES

Filatov, Michael; Martínez, Todd J.; Kim, Kwang S.

2017-08-14

An extended variant of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, the REKS(4,4) method, designed to describe the ground electronic states of strongly multireference systems is modified to enable calculation of excited states within the time-independent variational formalism. The new method, the state-interaction state-averaged REKS(4,4), i.e., SI-SA-REKS(4,4), is capable of describing several excited states of a molecule involving double bond cleavage, polyradical character, or multiple chromophoric units.We demonstrate that the newmethod correctly describes the ground and the lowest singlet excited states of a molecule (ethylene) undergoing double bond cleavage. The applicability of the new method for excitonic states is illustrated withmore » π stacked ethylene and tetracene dimers. We conclude that the new method can describe a wide range of multireference phenomena.« less

Description of ground and excited electronic states by ensemble density functional method with extended active space

DOE Office of Scientific and Technical Information (OSTI.GOV)

Filatov, Michael; Martínez, Todd J.; Kim, Kwang S.

An extended variant of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, the REKS(4,4) method, designed to describe the ground electronic states of strongly multireference systems is modified to enable calculation of excited states within the time-independent variational formalism. The new method, the state-interaction state-averaged REKS(4,4), i.e., SI-SA-REKS(4,4), is capable of describing several excited states of a molecule involving double bond cleavage, polyradical character, or multiple chromophoric units.We demonstrate that the newmethod correctly describes the ground and the lowest singlet excited states of a molecule (ethylene) undergoing double bond cleavage. The applicability of the new method for excitonic states is illustrated withmore » π stacked ethylene and tetracene dimers. We conclude that the new method can describe a wide range of multireference phenomena.« less

Electrodeposition of Polypyrrole and Reduced Graphene Oxide onto Carbon Bundle Fibre as Electrode for Supercapacitor.

PubMed

Abdul Bashid, Hamra Assyaima; Lim, Hong Ngee; Kamaruzaman, Sazlinda; Abdul Rashid, Suraya; Yunus, Robiah; Huang, Nay Ming; Yin, Chun Yang; Rahman, Mohammad Mahbubur; Altarawneh, Mohammednoor; Jiang, Zhong Tao; Alagarsamy, Pandikumar

2017-12-01

A nanocomposite comprising of polypyrrole and reduced graphene oxide was electrodeposited onto a carbon bundle fibre (CBF) through a two-step approach (CBF/PPy-rGO-2). The CBF/PPy-rGO-2 had a highly porous structure compared to a nanocomposite of polypyrrole and reduced graphene oxide that was electrodeposited onto a CBF in a one-step approach (CBF/PPy-rGO), as observed through a field emission scanning electron microscope. An X-ray photoelectron spectroscopic analysis revealed the presence of hydrogen bond between the oxide functional groups of rGO and the amine groups of PPy in PPy-rGO-2 nanocomposite. The fabricated CBF/PPy-rGO-2 nanocomposite material was used as an electrode material in a symmetrical solid-state supercapacitor, and the device yielded a specific capacitance, energy density and power density of 96.16 F g - 1 , 13.35 Wh kg - 1 and of 322.85 W kg - 1 , respectively. Moreover, the CBF/PPy-rGO-2 showed the capacitance retention of 71% after 500 consecutive charge/discharge cycles at a current density of 1 A g - 1 . The existence of a high degree of porosity in CBF/PPy-rGO-2 significantly improved the conductivity and facilitated the ionic penetration. The CBF/PPy-rGO-2-based symmetrical solid-state supercapacitor device demonstrated outstanding pliability because the cyclic voltammetric curves remained the same upon bending at various angles. Carbon bundle fibre modified with porous polypyrrole/reduced graphene oxide nanocomposite for flexible miniature solid-state supercapacitor.

Bond angle variations in XH3 [X = N, P, As, Sb, Bi]: the critical role of Rydberg orbitals exposed using a diabatic state model.

PubMed

Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

2015-10-14

Ammonia adopts sp(3) hybridization (HNH bond angle 108°) whereas the other members of the XH3 series PH3, AsH3, SbH3, and BiH3 instead prefer octahedral bond angles of 90-93°. We use a recently developed general diabatic description for closed-shell chemical reactions, expanded to include Rydberg states, to understand the geometry, spectroscopy and inversion reaction profile of these molecules, fitting its parameters to results from Equation of Motion Coupled-Cluster Singles and Doubles (EOM-CCSD) calculations using large basis sets. Bands observed in the one-photon absorption spectrum of NH3 at 18.3 eV, 30 eV, and 33 eV are reassigned from Rydberg (formally forbidden) double excitations to valence single-excitation resonances. Critical to the analysis is the inclusion of all three electronic states in which two electrons are placed in the lone-pair orbital n and/or the symmetric valence σ* antibonding orbital. An illustrative effective two-state diabatic model is also developed containing just three parameters: the resonance energy driving the high-symmetry planar structure, the reorganization energy opposing it, and HXH bond angle in the absence of resonance. The diabatic orbitals are identified as sp hybrids on X; for the radical cations XH3(+) for which only 2 electronic states and one conical intersection are involved, the principle of orbital following dictates that the bond angle in the absence of resonance is acos(-1/5) = 101.5°. The multiple states and associated multiple conical intersection seams controlling the ground-state structure of XH3 renormalize this to acos[3 sin(2)(2(1/2)atan(1/2))/2 - 1/2] = 86.7°. Depending on the ratio of the resonance energy to the reorganization energy, equilibrium angles can vary from these limiting values up to 120°, and the anomalously large bond angle in NH3 arises because the resonance energy is unexpectedly large. This occurs as the ordering of the lowest Rydberg orbital and the σ* orbital swap, allowing Rydbergization to compresses σ* to significantly increase the resonance energy. Failure of both the traditional and revised versions of the valence-shell electron-pair repulsion (VSEPR) theory to explain the ground-state structures in simple terms is attributed to exclusion of this key physical interaction.

Charge disproportionation in tetragonal La2MoO5, a small band gap semiconductor influenced by direct Mo-Mo bonding.

PubMed

Colabello, Diane M; Camino, Fernando E; Huq, Ashfia; Hybertsen, Mark; Khalifah, Peter G

2015-01-28

The structure of the novel compound La2MoO5 has been solved from powder X-ray and neutron diffraction data and belongs to the tetragonal space group P4/m (no. 83) with a = 12.6847(3) Å and c = 6.0568(2) Å and with Z = 8. It consists of equal proportions of bioctahedral (Mo2O10) and square prismatic (Mo2O8) dimers, both of which contain direct Mo-Mo bonds and are arranged in 1D chains. The Mo-Mo bond length in the Mo2O10 dimers is 2.684(8) Å, while there are two types of Mo2O8 dimers with Mo-Mo bonds lengths of 2.22(2) and 2.28(2) Å. Although the average Mo oxidation state in La2MoO5 is 4+, the very different Mo-Mo distances reflect the fact that the Mo2O10 dimers contain only Mo(5+) (d(1)), while the prismatic Mo2O8 dimers only contain Mo(3+) (d(3)), a result directly confirmed by density function theory calculations. This is due to the complete disproportionation of Mo(4+), a phenomenon which has not previously been observed in solid-state compounds. La2MoO5 is diamagnetic, behavior which is not expected for a nonmetallic transition-metal oxide whose cation sites have an odd number of d-electrons. The resistivity displays the Arrhenius-type activated behavior expected for a semiconductor with a band gap of 0.5 eV, exhibiting an unusually small transport gap relative to other diamagnetic oxides. Diffuse reflectance studies indicate that La2MoO5 is a rare example of a stable oxide semiconductor with strong infrared absorbance. It is shown that the d-orbital splitting associated with the Mo2O8 and Mo2O10 dimeric units can be rationalized using simple molecular orbital bonding concepts.

Definition and effect of chemical properties of surfaces in friction, wear, and lubrication

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1978-01-01

Chemical properties relative to their role in adhesion, friction, wear and lubrication discussed in this paper will include: (1) adsorption, both physical and chemical; (2) orientation of the solid as well as the lubricant; (3) surface energy; (4) surface segregation; (5) surface versus bulk metallurgical effects; (6) electronic nature of the surface; and (7) bonding mechanisms.

X-ray diffraction, crystal structure, and spectral features of the optical susceptibilities of single crystals of the ternary borate oxide lead bismuth tetraoxide, PbBiBO4.

PubMed

Reshak, Ali Hussain; Kityk, I V; Auluck, S; Chen, Xuean

2009-05-14

The all-electron full-potential linearized augmented plane-wave method has been used for an ab initio theoretical study of the band structure, the spectral features of the optical susceptibilities, the density of states, and the electron charge density for PbBiBO4. Our calculations show that the valence-band maximum (VBM) and conduction-band minimum (CBM) are located at the center of the Brillouin zone, resulting in a direct energy gap of about 3.2 eV. We have synthesized the PbBiBO4 crystal by employing a conventional solid-state reaction method. The theoretical calculations in this work are based on the structure built from our measured atomic parameters. We should emphasize that the observed experimental X-ray diffraction (XRD) pattern is in good agreement with the theoretical one, confirming that our structural model is valid. Our calculated bond lengths show excellent agreement with the experimental data. This agreement is attributed to our use of full-potential calculations. The spectral features of the optical susceptibilities show a small positive uniaxial anisotropy.

The potentials and challenges of electron microscopy in the study of atomic chains

NASA Astrophysics Data System (ADS)

Banhart, Florian; Torre, Alessandro La; Romdhane, Ferdaous Ben; Cretu, Ovidiu

2017-04-01

The article is a brief review on the potential of transmission electron microscopy (TEM) in the investigation of atom chains which are the paradigm of a strictly one-dimensional material. After the progress of TEM in the study of new two-dimensional materials, microscopy of free-standing one-dimensional structures is a new challenge with its inherent potentials and difficulties. In-situ experiments in the TEM allowed, for the first time, to generate isolated atomic chains consisting of metals, carbon or boron nitride. Besides having delivered a solid proof for the existence of atomic chains, in-situ TEM studies also enabled us to measure the electrical properties of these fundamental linear structures. While ballistic quantum conductivity is observed in chains of metal atoms, electrical transport in chains of sp1-hybridized carbon is limited by resonant states and reflections at the contacts. Although substantial progress has been made in recent TEM studies of atom chains, fundamental questions have to be answered, concerning the structural stability of the chains, bonding states at the contacts, and the suitability for applications in nanotechnology. Contribution to the topical issue "The 16th European Microscopy Congress (EMC 2016)", edited by Richard Brydson and Pascale Bayle-Guillemaud

First principle investigation of electronic structure, chemical bonding and optical properties of tetrabarium gallium trinitride oxide single crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khan, Saleem Ayaz, E-mail: sayaz_usb@yahoo.com; Azam, Sikander

The electronic band structure, valence electron charge density and optical susceptibilities of tetrabarium gallium trinitride (TGT) were calculated via first principle study. The electronic band structure calculation describes TGT as semiconductor having direct band gap of 1.38 eV. The valence electronic charge density contour verified the non-polar covalent nature of the bond. The absorption edge and first peak of dielectric tensor components showed electrons transition from N-p state to Ba-d state. The calculated uniaxial anisotropy (0.4842) and birefringence (−0.0061) of present paper is prearranged as follow the spectral components of the dielectric tensor. The first peak in energy loss functionmore » (ELOS) shows the energy loss of fast traveling electrons in the material. The first sharp peak produced in ELOS around 10.5 eV show plasmon loss having plasma frequencies 0.1536, 0.004 and 0.066 of dielectric tensor components. This plasmon loss also cause decrease in reflectivity spectra.« less

Chemical bond and superconductivity. Technical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Messmer, R.P.

1987-07-01

The search for understanding of the physical mechanisms operating in the recently discovered high-T/sub c/ superconductors forces a re-examination of the basic concepts and physical assumptions of current theoretical approaches. The attractive interaction of a more-general theory may be rather more complicated than the electron-phonon interaction usually assumed. In fact, it probably contains the critical chemical parameters of the material. This is the motivation for the present work in which the focus is two-fold: first, to call attention to some recent developments in our understanding of the chemical bond, and second, to prepose that this new understanding is not onlymore » germane to the electronic structure of solids but also provides a new perspective on the relationship between the chemical bond and superconductivity. Studying the connection between chemical bonding and superconductivity would seem to be rather an academic exercise if it were not for the high-temperature superconductors. These materials have brought attention in a dramatic fashion to the ignorance that exists in relating chemistry to the important physical parameters of a superconductor. Although this point was raised in numerous contributions by Matthias, its full import was never so apparent when the superconductors were traditional metals and alloys.« less

Atomic-scale investigation of nuclear quantum effects of surface water: Experiments and theory

NASA Astrophysics Data System (ADS)

Guo, Jing; Li, Xin-Zheng; Peng, Jinbo; Wang, En-Ge; Jiang, Ying

2017-12-01

Quantum behaviors of protons in terms of tunneling and zero-point motion have significant effects on the macroscopic properties, structure, and dynamics of water even at room temperature or higher. In spite of tremendous theoretical and experimental efforts, accurate and quantitative description of the nuclear quantum effects (NQEs) is still challenging. The main difficulty lies in that the NQEs are extremely susceptible to the structural inhomogeneity and local environments, especially when interfacial systems are concerned. In this review article, we will highlight the recent advances of scanning tunneling microscopy and spectroscopy (STM/S), which allows the access to the quantum degree of freedom of protons both in real and energy space. In addition, we will also introduce recent development of ab initio path-integral molecular dynamics (PIMD) simulations at surfaces/interfaces, in which both the electrons and nuclei are treated as quantum particles in contrast to traditional ab initio molecular dynamics (MD). Then we will discuss how the combination of STM/S and PIMD are used to directly visualize the concerted quantum tunneling of protons within the water clusters and quantify the impact of zero-point motion on the strength of a single hydrogen bond (H bond) at a water/solid interface. Those results may open up the new possibility of exploring the exotic quantum states of light nuclei at surfaces, as well as the quantum coupling between the electrons and nuclei.

Glycerol-bonded 3C-SiC nanocrystal solid films exhibiting broad and stable violet to blue-green emission.

PubMed

Wang, J; Xiong, S J; Wu, X L; Li, T H; Chu, Paul K

2010-04-14

We have produced glycerol-bonded 3C-SiC nanocrystal (NC) films, which when excited by photons of different wavelengths, produce strong and tunable violet to blue-green (360-540 nm) emission as a result of the quantum confinement effects rendered by the 3C-SiC NCs. The emission is so intense that the emission spots are visible to the naked eyes. The light emission is very stable and even after storing in air for more than six months, no intensity degradation can be observed. X-ray photoelectron spectroscopy and absorption fine structure measurements indicate that the Si-terminated NC surfaces are completely bonded to glycerol molecules. Calculations of geometry optimization and electron structures based on the density functional theory for 3C-SiC NCs with attached glycerol molecules show that these molecules are bonded on the NCs causing strong surface structural change, while the isolated levels in the conduction band of the bare 3C-SiC NCs are replaced with quasi-continuous bands that provide continuous tunability of the emitted light by changing the frequencies of exciting laser. As an application, we demonstrate the potential of using 3C-SiC NCs to fabricate full-color emitting solid films by incorporating porous silicon.

Nonadiabatic one-electron transfer mechanism for the O-O bond formation in the oxygen-evolving complex of photosystem II

NASA Astrophysics Data System (ADS)

Shoji, Mitsuo; Isobe, Hiroshi; Shigeta, Yasuteru; Nakajima, Takahito; Yamaguchi, Kizashi

2018-04-01

The reaction mechanism of the O2 formation in the S4 state of the oxygen-evolving complex of photosystem II was clarified at the quantum mechanics/molecular mechanics (QM/MM) level. After the Yz (Y161) oxidation and the following proton transfer in the S3 state, five reaction steps are required to produce the molecular dioxygen. The highest barrier step is the first proton transfer reaction (0 → 1). The following reactions involving electron transfers were precisely analyzed in terms of their energies, structures and spin densities. We found that the one-electron transfer from the Mn4Ca cluster to Y161 triggers the O-O sigma bond formation.

Infrared vibrational nanocrystallography and nanoimaging

PubMed Central

Muller, Eric A.; Pollard, Benjamin; Bechtel, Hans A.; van Blerkom, Peter; Raschke, Markus B.

2016-01-01

Molecular solids and polymers can form low-symmetry crystal structures that exhibit anisotropic electron and ion mobility in engineered devices or biological systems. The distribution of molecular orientation and disorder then controls the macroscopic material response, yet it is difficult to image with conventional techniques on the nanoscale. We demonstrated a new form of optical nanocrystallography that combines scattering-type scanning near-field optical microscopy with both optical antenna and tip-selective infrared vibrational spectroscopy. From the symmetry-selective probing of molecular bond orientation with nanometer spatial resolution, we determined crystalline phases and orientation in aggregates and films of the organic electronic material perylenetetracarboxylic dianhydride. Mapping disorder within and between individual nanoscale domains, the correlative hybrid imaging of nanoscale heterogeneity provides insight into defect formation and propagation during growth in functional molecular solids. PMID:27730212

Ferromagnetic bond of Li{sub 10} cluster: An alternative approach in terms of effective ferromagnetic sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Donoso, Roberto; Fuentealba, Patricio, E-mail: pfuentea@hotmail.es, E-mail: cardena@macul.ciencias.uchile.cl; Cárdenas, Carlos, E-mail: pfuentea@hotmail.es, E-mail: cardena@macul.ciencias.uchile.cl

In this work, a model to explain the unusual stability of atomic lithium clusters in their highest spin multiplicity is presented and used to describe the ferromagnetic bonding of high-spin Li{sub 10} and Li{sub 8} clusters. The model associates the (lack of-)fitness of Heisenberg Hamiltonian with the degree of (de-)localization of the valence electrons in the cluster. It is shown that a regular Heisenberg Hamiltonian with four coupling constants cannot fully explain the energy of the different spin states. However, a more simple model in which electrons are located not at the position of the nuclei but at the positionmore » of the attractors of the electron localization function succeeds in explaining the energy spectrum and, at the same time, explains the ferromagnetic bond found by Shaik using arguments of valence bond theory. In this way, two different points of view, one more often used in physics, the Heisenberg model, and the other in chemistry, valence bond, come to the same answer to explain those atypical bonds.« less

Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

PubMed

Zhang, Rongchun; Ramamoorthy, Ayyalusamy

2015-07-21

Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

Solid-phase materials for chelating metal ions and methods of making and using same

DOEpatents

Harrup, Mason K.; Wey, John E.; Peterson, Eric S.

2003-06-10

A solid material for recovering metal ions from aqueous streams, and methods of making and using the solid material, are disclosed. The solid material is made by covalently bonding a chelating agent to a silica-based solid, or in-situ condensing ceramic precursors along with the chelating agent to accomplish the covalent bonding. The chelating agent preferably comprises a oxime type chelating head, preferably a salicylaldoxime-type molecule, with an organic tail covalently bonded to the head. The hydrocarbon tail includes a carbon-carbon double bond, which is instrumental in the step of covalently bonding the tail to the silica-based solid or the in-situ condensation. The invented solid material may be contacted directly with aqueous streams containing metal ions, and is selective to ions such as copper (II) even in the presence of such ions as iron (III) and other materials that are present in earthen materials. The solid material with high selectivity to copper may be used to recover copper from mining and plating industry streams, to replace the costly and toxic solvent extraction steps of conventional copper processing.

Imaging quasiperiodic electronic states in a synthetic Penrose tiling

NASA Astrophysics Data System (ADS)

Collins, Laura C.; Witte, Thomas G.; Silverman, Rochelle; Green, David B.; Gomes, Kenjiro K.

2017-06-01

Quasicrystals possess long-range order but lack the translational symmetry of crystalline solids. In solid state physics, periodicity is one of the fundamental properties that prescribes the electronic band structure in crystals. In the absence of periodicity and the presence of quasicrystalline order, the ways that electronic states change remain a mystery. Scanning tunnelling microscopy and atomic manipulation can be used to assemble a two-dimensional quasicrystalline structure mapped upon the Penrose tiling. Here, carbon monoxide molecules are arranged on the surface of Cu(111) one at a time to form the potential landscape that mimics the ionic potential of atoms in natural materials by constraining the electrons in the two-dimensional surface state of Cu(111). The real-space images reveal the presence of the quasiperiodic order in the electronic wave functions and the Fourier analysis of our results links the energy of the resonant states to the local vertex structure of the quasicrystal.

Imaging quasiperiodic electronic states in a synthetic Penrose tiling.

PubMed

Collins, Laura C; Witte, Thomas G; Silverman, Rochelle; Green, David B; Gomes, Kenjiro K

2017-06-22

Quasicrystals possess long-range order but lack the translational symmetry of crystalline solids. In solid state physics, periodicity is one of the fundamental properties that prescribes the electronic band structure in crystals. In the absence of periodicity and the presence of quasicrystalline order, the ways that electronic states change remain a mystery. Scanning tunnelling microscopy and atomic manipulation can be used to assemble a two-dimensional quasicrystalline structure mapped upon the Penrose tiling. Here, carbon monoxide molecules are arranged on the surface of Cu(111) one at a time to form the potential landscape that mimics the ionic potential of atoms in natural materials by constraining the electrons in the two-dimensional surface state of Cu(111). The real-space images reveal the presence of the quasiperiodic order in the electronic wave functions and the Fourier analysis of our results links the energy of the resonant states to the local vertex structure of the quasicrystal.

An Electron Density Source-Function Study of DNA Base Pairs in Their Neutral and Ionized Ground States†.

PubMed

Gatti, Carlo; Macetti, Giovanni; Boyd, Russell J; Matta, Chérif F

2018-07-05

The source function (SF) decomposes the electron density at any point into contributions from all other points in the molecule, complex, or crystal. The SF "illuminates" those regions in a molecule that most contribute to the electron density at a point of reference. When this point of reference is the bond critical point (BCP), a commonly used surrogate of chemical bonding, then the SF analysis at an atomic resolution within the framework of Bader's Quantum Theory of Atoms in Molecules returns the contribution of each atom in the system to the electron density at that BCP. The SF is used to locate the important regions that control the hydrogen bonds in both Watson-Crick (WC) DNA dimers (adenine:thymine (AT) and guanine:cytosine (GC)) which are studied in their neutral and their singly ionized (radical cationic and anionic) ground states. The atomic contributions to the electron density at the BCPs of the hydrogen bonds in the two dimers are found to be delocalized to various extents. Surprisingly, gaining or loosing an electron has similar net effects on some hydrogen bonds concealing subtle compensations traced to atomic sources contributions. Coarser levels of resolutions (groups, rings, and/or monomers-in-dimers) reveal that distant groups and rings often have non-negligible effects especially on the weaker hydrogen bonds such as the third weak CH⋅⋅⋅O hydrogen bond in AT. Interestingly, neither the purine nor the pyrimidine in the neutral or ionized forms dominate any given hydrogen bond despite that the former has more atoms that can act as source or sink for the density at its BCP. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Computational simulation of the effects of oxygen on the electronic states of hydrogenated 3C-porous SiC

PubMed Central

2012-01-01

A computational study of the dependence of the electronic band structure and density of states on the chemical surface passivation of cubic porous silicon carbide (pSiC) was performed using ab initio density functional theory and the supercell method. The effects of the porosity and the surface chemistry composition on the energetic stability of pSiC were also investigated. The porous structures were modeled by removing atoms in the [001] direction to produce two different surface chemistries: one fully composed of silicon atoms and one composed of only carbon atoms. The changes in the electronic states of the porous structures as a function of the oxygen (O) content at the surface were studied. Specifically, the oxygen content was increased by replacing pairs of hydrogen (H) atoms on the pore surface with O atoms attached to the surface via either a double bond (X = O) or a bridge bond (X-O-X, X = Si or C). The calculations show that for the fully H-passivated surfaces, the forbidden energy band is larger for the C-rich phase than for the Si-rich phase. For the partially oxygenated Si-rich surfaces, the band gap behavior depends on the O bond type. The energy gap increases as the number of O atoms increases in the supercell if the O atoms are bridge-bonded, whereas the band gap energy does not exhibit a clear trend if O is double-bonded to the surface. In all cases, the gradual oxygenation decreases the band gap of the C-rich surface due to the presence of trap-like states. PMID:22913486

Chirality-selected phase behaviour in ionic polypeptide complexes

DOE PAGES

Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; ...

2015-01-14

In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with amore » β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.« less

Reduction of electron accumulation at InN(0001) surfaces via saturation of surface states by potassium and oxygen as donor- or acceptor-type adsorbates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eisenhardt, A.; Reiß, S.; Krischok, S., E-mail: stefan.krischok@tu-ilmenau.de

2014-01-28

The influence of selected donor- and acceptor-type adsorbates on the electronic properties of InN(0001) surfaces is investigated implementing in-situ photoelectron spectroscopy. The changes in work function, surface band alignment, and chemical bond configurations are characterized during deposition of potassium and exposure to oxygen. Although an expected opponent charge transfer characteristic is observed with potassium donating its free electron to InN, while dissociated oxygen species extract partial charge from the substrate, a reduction of the surface electron accumulation occurs in both cases. This observation can be explained by adsorbate-induced saturation of free dangling bonds at the InN resulting in the disappearancemore » of surface states, which initially pin the Fermi level and induce downward band bending.« less

Hydrogen-bond Specific Materials Modification in Group IV Semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tolk, Norman H.; Feldman, L. C.; Luepke, G.

Executive summary Semiconductor dielectric crystals consist of two fundamental components: lattice atoms and electrons. The former component provides a crystalline structure that can be disrupted by various defects or the presence of an interface, or by transient oscillations known as phonons. The latter component produces an energetic structure that is responsible for the optical and electronic properties of the material, and can be perturbed by lattice defects or by photo-excitation. Over the period of this project, August 15, 1999 to March 31, 2015, a persistent theme has been the elucidation of the fundamental role of defects arising from the presencemore » of radiation damage, impurities (in particular, hydrogen), localized strain or some combination of all three. As our research effort developed and evolved, we have experienced a few title changes, which reflected this evolution. Throughout the project, ultrafast lasers usually in a pump-probe configuration provided the ideal means to perturb and study semiconductor crystals by both forms of excitation, vibrational (phonon) and electronic (photon). Moreover, we have found in the course of this research that there are many interesting and relevant scientific questions that may be explored when phonon and photon excitations are controlled separately. Our early goals were to explore the dynamics of bond-selective vibrational excitation of hydrogen from point defects and impurities in crystalline and amorphous solids, initiating an investigation into the behavior of hydrogen isotopes utilizing a variety of ultrafast characterization techniques, principally transient bleaching spectroscopy to experimentally obtain vibrational lifetimes. The initiative could be divided into three related areas: (a) investigation of the change in electronic structure of solids due to the presence of hydrogen defect centers, (b) dynamical studies of hydrogen in materials and (c) characterization and stability of metastable hydrogen impurity states under transient compression. This research focused on the characterization of photon and ion stimulated hydrogen related defect and impurity reactions and migration in solid state matter, which requires a detailed understanding of the rates and pathways of vibrational energy flow, of the transfer channels and of the coupling mechanisms between local vibrational modes (LVMs) and phonon bath as well as the electronic system of the host material. It should be stressed that researchers at Vanderbilt and William and Mary represented a unique group with a research focus and capabilities for low temperature creation and investigation of such material systems. Later in the program, we carried out a vigorous research effort addressing the roles of defects, interfaces, and dopants on the optical and electronic characteristics of semiconductor crystals, using phonon generation by means of ultrafast coherent acoustic phonon (CAP) spectroscopy, nonlinear characterization using second harmonic generation (SHG), and ultrafast pump-and-probe reflectivity and absorption measurements. This program featured research efforts from hydrogen defects in silicon alone to other forms of defects such as interfaces and dopant layers, as well as other important semiconducting systems. Even so, the emphasis remains on phenomena and processes far from equilibrium, such as hot electron effects and travelling localized phonon waves. This program relates directly to the mission of the Department of Energy. Knowledge of the rates and pathways of vibrational energy flow in condensed matter is critical for understanding dynamical processes in solids including electronically, optically and thermally stimulated defect and impurity reactions and migration. The ability to directly probe these pathways and rates allows tests of theory and scaling laws at new levels of precision. Hydrogen embedded in model crystalline semiconductors and metal oxides is of particular interest, since the associated local mode can be excited cleanly, and is usually well-separated in energy from the phonon bath. These basic dynamical studies have provided new insights for example into the fundamental mechanisms that control proton diffusion in these oxides. This area of materials science has largely fulfilled its promise to identify degradation mechanisms in electronic and optoelectronic devices, and to advance solid oxide proton conductors for fuel cells, gas sensors and proton-exchange membrane applications. It also provides the basis for innovations in materials synthesis involving atomic-selective diffusion and desorption.« less

Solid state transport-based thermoelectric converter

DOEpatents

Hu, Zhiyu

2010-04-13

A solid state thermoelectric converter includes a thermally insulating separator layer, a semiconducting collector and an electron emitter. The electron emitter comprises a metal nanoparticle layer or plurality of metal nanocatalyst particles disposed on one side of said separator layer. A first electrically conductive lead is electrically coupled to the electron emitter. The collector layer is disposed on the other side of the separator layer, wherein the thickness of the separator layer is less than 1 .mu.m. A second conductive lead is electrically coupled to the collector layer.

Synthesis of [{AgO2CCH2OMe(PPh3)}n] and theoretical study of its use in focused electron beam induced deposition

PubMed Central

Noll, Julian; Frenzel, Peter; Rüffer, Tobias; Jakob, Alexander; Walfort, Bernhard

2017-01-01

The synthesis, chemical and physical properties of [{AgO2CCH2OMe}n] (1) and [{AgO2CCH2OMe(PPh3)}n] (2) are reported. Consecutive reaction of AgNO3 with HO2CCH2OMe gave 1, which upon treatment with PPh3 produced 2. Coordination compound 2 forms a 1D coordination polymer in the solid state as evidenced by single crystal X-ray structure analysis. The coordination geometry at Ag+ is of the [3 + 1] type, whereby the carboxylate anions act as bridging ligands. The formation of PPh3–Ag(I) coordinative bonds results in distorted T-shaped AgPO2 units, which are stabilized further by an additional O–Ag dative bond. TG and TG–MS measurements show that 1 and 2 decompose at 190–250 °C (1) and 260–300 °C (2) via decarboxylation, involving Ag–P (2), C–C and C–O bond cleavages to give elemental silver as confirmed by PXRD studies. In order to verify if polymeric 2 is suitable as a FEBID precursor for silver deposition, its vapor pressure was determined (p 170 °C = 5.318 mbar, ∆H vap = 126.1 kJ mol−1), evincing little volatility. Also EI and ESI mass spectrometric studies were carried out. The dissociation of the silver(I) compound 2 under typical electron-driven FEBID conditions was studied by DFT (B3LYP) calculations on monomeric [AgO2CCH2OMe(PPh3)]. At an energy of the secondary electrons up to 0.8 eV elimination of PPh3 occurs, giving Ag+ and O2CCH2OMe−. Likewise, by release of PPh3 from [AgO2CCH2OMe(PPh3)] the fragment [AgO2CCH2OMe]− is formed from which Ag+ and O2CCH2OMe− is generated, further following the first fragmentation route. However, at 1.3 eV the initial step is decarboxylation giving [AgCH2OMe(PPh3)], followed by Ag–P and Ag–C bond cleavages. PMID:29259876

Synthesis of [{AgO2CCH2OMe(PPh3)} n ] and theoretical study of its use in focused electron beam induced deposition.

PubMed

Tamuliene, Jelena; Noll, Julian; Frenzel, Peter; Rüffer, Tobias; Jakob, Alexander; Walfort, Bernhard; Lang, Heinrich

2017-01-01

The synthesis, chemical and physical properties of [{AgO 2 CCH 2 OMe} n ] ( 1 ) and [{AgO 2 CCH 2 OMe(PPh 3 )} n ] ( 2 ) are reported. Consecutive reaction of AgNO 3 with HO 2 CCH 2 OMe gave 1 , which upon treatment with PPh 3 produced 2 . Coordination compound 2 forms a 1D coordination polymer in the solid state as evidenced by single crystal X-ray structure analysis. The coordination geometry at Ag + is of the [3 + 1] type, whereby the carboxylate anions act as bridging ligands. The formation of PPh 3 -Ag(I) coordinative bonds results in distorted T-shaped AgPO 2 units, which are stabilized further by an additional O-Ag dative bond. TG and TG-MS measurements show that 1 and 2 decompose at 190-250 °C ( 1 ) and 260-300 °C ( 2 ) via decarboxylation, involving Ag-P ( 2 ), C-C and C-O bond cleavages to give elemental silver as confirmed by PXRD studies. In order to verify if polymeric 2 is suitable as a FEBID precursor for silver deposition, its vapor pressure was determined ( p 170 °C = 5.318 mbar, ∆H vap = 126.1 kJ mol -1 ), evincing little volatility. Also EI and ESI mass spectrometric studies were carried out. The dissociation of the silver(I) compound 2 under typical electron-driven FEBID conditions was studied by DFT (B3LYP) calculations on monomeric [AgO 2 CCH 2 OMe(PPh 3 )]. At an energy of the secondary electrons up to 0.8 eV elimination of PPh 3 occurs, giving Ag + and O 2 CCH 2 OMe - . Likewise, by release of PPh 3 from [AgO 2 CCH 2 OMe(PPh 3 )] the fragment [AgO 2 CCH 2 OMe] - is formed from which Ag + and O 2 CCH 2 OMe - is generated, further following the first fragmentation route. However, at 1.3 eV the initial step is decarboxylation giving [AgCH 2 OMe(PPh 3 )], followed by Ag-P and Ag-C bond cleavages.

A combined solid-state NMR and X-ray crystallography study of the bromide ion environments in triphenylphosphonium bromides.

PubMed

Burgess, Kevin M N; Korobkov, Ilia; Bryce, David L

2012-04-27

Multinuclear ((31)P and (79/81)Br), multifield (9.4, 11.75, and 21.1 T) solid-state nuclear magnetic resonance experiments are performed for seven phosphonium bromides bearing the triphenylphosphonium cation, a molecular scaffold found in many applications in chemistry. This is undertaken to fully characterise their bromine electric field gradient (EFG) tensors, as well as the chemical shift (CS) tensors of both the halogen and the phosphorus nuclei, providing a rare and novel insight into the local electronic environments surrounding them. New crystal structures, obtained from single-crystal X-ray diffraction, are reported for six compounds to aid in the interpretation of the NMR data. Among them is a new structure of BrPPh(4), because the previously reported one was inconsistent with our magnetic resonance data, thereby demonstrating how NMR data of non-standard nuclei can correct or improve X-ray diffraction data. Our results indicate that, despite sizable quadrupolar interactions, (79/81)Br magnetic resonance spectroscopy is a powerful characterisation tool that allows for the differentiation between chemically similar bromine sites, as shown through the range in the characteristic NMR parameters. (35/37)Cl solid-state NMR data, obtained for an analogous phosphonium chloride sample, provide insight into the relationship between unit cell volume, nuclear quadrupolar coupling constants, and Sternheimer antishielding factors. The experimental findings are complemented by gauge-including projector-augmented wave (GIPAW) DFT calculations, which substantiate our experimentally determined strong dependence of the largest component of the bromine CS tensor, δ(11), on the shortest Br-P distance in the crystal structure, a finding that has possible application in the field of NMR crystallography. This trend is explained in terms of Ramsey's theory on paramagnetic shielding. Overall, this work demonstrates how careful NMR studies of underexploited exotic nuclides, such as (79/81)Br, can afford insights into structure and bonding environments in the solid state. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Metalloprotein entatic control of ligand-metal bonds quantified by ultrafast x-ray spectroscopy

DOE PAGES

Mara, Michael W.; Hadt, Ryan G.; Reinhard, Marco Eli; ...

2017-06-23

The multifunctional protein cytochrome c (cyt c) plays key roles in electron transport and apoptosis, switching function by modulating bonding between a heme iron and the sulfur in a methionine residue. This Fe–S(Met) bond is too weak to persist in the absence of protein constraints. We ruptured the bond in ferrous cyt c using an optical laser pulse and monitored the bond reformation within the protein active site using ultrafast x-ray pulses from an x-ray free-electron laser, determining that the Fe–S(Met) bond enthalpy is ~4 kcal/mol stronger than in the absence of protein constraints. As a result, the 4 kcal/molmore » is comparable with calculations of stabilization effects in other systems, demonstrating how biological systems use an entatic state for modest yet accessible energetics to modulate chemical function.« less

Metalloprotein entatic control of ligand-metal bonds quantified by ultrafast x-ray spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mara, Michael W.; Hadt, Ryan G.; Reinhard, Marco Eli

The multifunctional protein cytochrome c (cyt c) plays key roles in electron transport and apoptosis, switching function by modulating bonding between a heme iron and the sulfur in a methionine residue. This Fe–S(Met) bond is too weak to persist in the absence of protein constraints. We ruptured the bond in ferrous cyt c using an optical laser pulse and monitored the bond reformation within the protein active site using ultrafast x-ray pulses from an x-ray free-electron laser, determining that the Fe–S(Met) bond enthalpy is ~4 kcal/mol stronger than in the absence of protein constraints. As a result, the 4 kcal/molmore » is comparable with calculations of stabilization effects in other systems, demonstrating how biological systems use an entatic state for modest yet accessible energetics to modulate chemical function.« less

A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state

PubMed Central

Krakowiak, Joanna; Lundberg, Daniel

2012-01-01

The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen donor solvents water, dimethylsulfoxide (dmso) and N,N′-dimethylpropyleneurea (dmpu) has been studied in solution by EXAFS and large angle X-ray scattering (LAXS) and in solid state by single crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and dimethylsulfoxide solvated oxovanadium(IV) ions vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O=V-Operp bond angle is ca. 98°. In the dmpu solvated oxovanadium(IV) ion, the space demanding properties of the dmpu molecule leaving no solvent molecule in the trans position to the oxo group which reduces the coordination number to 5. The O=V-O bond angle is consequently much larger, 106°, and the mean V=O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and dimethylsulfoxide solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in cis position with mean V=O bond distances of 1.6 Å and a O=V=O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen donor ligands. PMID:22950803

Fabrication of Solid-State Multilayer Glass Capacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilke, Rudeger H. T.; Brown-Shaklee, Harlan James; Casias, Adrian L.

Alkali-free glasses show immense promise for the development of high-energy density capacitors. The high breakdown strengths on single-layer sheets of glass suggest the potential for improved energy densities over existing state-of-the art polymer capacitors. In this paper, we demonstrate the ability to package thin glass to make solid-state capacitors. Individual layers are bonded using epoxy, leading to capacitors that exhibit stable operation over the temperature range -55 °C to +65 °C. Here, this fabrication approach is scalable and allows for proof testing individual layers prior to incorporation of the stack, providing a blueprint for the fabrication of high-energy density capacitors.

Fabrication of Solid-State Multilayer Glass Capacitors

DOE PAGES

Wilke, Rudeger H. T.; Brown-Shaklee, Harlan James; Casias, Adrian L.; ...

2017-07-31

Alkali-free glasses show immense promise for the development of high-energy density capacitors. The high breakdown strengths on single-layer sheets of glass suggest the potential for improved energy densities over existing state-of-the art polymer capacitors. In this paper, we demonstrate the ability to package thin glass to make solid-state capacitors. Individual layers are bonded using epoxy, leading to capacitors that exhibit stable operation over the temperature range -55 °C to +65 °C. Here, this fabrication approach is scalable and allows for proof testing individual layers prior to incorporation of the stack, providing a blueprint for the fabrication of high-energy density capacitors.

Four new polymorphic forms of suplatast tosilate.

PubMed

Nagai, Keiko; Ushio, Takanori; Miura, Hidenori; Nakamura, Takashi; Moribe, Kunikazu; Yamamoto, Keiji

2014-01-02

We found four new polymorphic forms (γ-, ε-, ζ-, and η-forms) of suplatast tosilate (ST) by recrystallization and seeding with ST-analogous compounds; three polymorphic forms (α-, β-, and δ-forms) of ST have been previously reported. The physicochemical properties of these new forms were investigated using infrared (IR) spectroscopy, solid-state nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and powder X-ray diffractometry. The presence of hydrogen bonds in the new forms was assessed from the IR and solid-state NMR spectra. The crystal structures of the ε- and η-forms were determined from their powder X-ray diffraction data using the direct space approach and the Monte Carlo method, followed by Rietveld refinement. The structures determined for the ε- and η-forms supported the presence of hydrogen bonds between the ST molecules, as the IR and solid-state NMR spectra indicated. The thermodynamic characteristics of the seven polymorphic forms were evaluated by determining the solubility of each form. The α-form was the most insoluble in 2-propanol at 35°C, and was thus concluded to be the most stable form. The ε-form was the most soluble, and a polymorphic transition from the ε- to the α-form was observed during solubility testing. Copyright © 2013 Elsevier B.V. All rights reserved.

Review of Graphene as a Solid State Diffusion Barrier.

PubMed

Morrow, Wayne K; Pearton, Stephen J; Ren, Fan

2016-01-06

Conventional thin-film diffusion barriers consist of 3D bulk films with high chemical and thermal stability. The purpose of the barrier material is to prevent intermixing or penetration from the two materials that encase it. Adhesion to both top and bottom materials is critical to the success of the barrier. Here, the effectiveness of a single atomic layer of graphene as a solid-state diffusion barrier for common metal schemes used in microelectronics is reviewed, and specific examples are discussed. Initial studies of electrical contacts to graphene show a distinct separation in behavior between metallic groups that strongly or weakly bond to it. The two basic classes of metal reactions with graphene are either physisorbed metals, which bond weakly with graphene, or chemisorbed metals, which bond strongly to graphene. For graphene diffusion barrier testing on Si substrates, an effective barrier can be achieved through the formation of a carbide layer with metals that are chemisorbed. For physisorbed metals, the barrier failure mechanism is loss of adhesion at the metal–graphene interface. A graphene layer encased between two metal layers, in certain cases, can increase the binding energy of both films with graphene, however, certain combinations of metal films are detrimental to the bonding with graphene. While the prospects for graphene's future as a solid-state diffusion barrier are positive, there are open questions, and areas for future research are discussed. A better understanding of the mechanisms which influence graphene's ability to be an effective diffusion barrier in microelectronic applications is required, and additional experiments are needed on a broader range of metals, as well as common metal stack contact structures used in microelectronic applications. The role of defects in the graphene is also a key area, since they will probably influence the barrier properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic, structural and chemical effects of charge-transfer at organic/inorganic interfaces

NASA Astrophysics Data System (ADS)

Otero, R.; Vázquez de Parga, A. L.; Gallego, J. M.

2017-07-01

During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical reactivity of the adsorbates. The aim of this review is to start drawing general conclusions and developing new concepts which will help the scientific community to proceed more efficiently towards the understanding of organic/inorganic interfaces in the strong interaction limit, where charge-transfer effects must be taken into consideration.

Solid state protein monolayers: Morphological, conformational, and functional properties

NASA Astrophysics Data System (ADS)

Pompa, P. P.; Biasco, A.; Frascerra, V.; Calabi, F.; Cingolani, R.; Rinaldi, R.; Verbeet, M. Ph.; de Waal, E.; Canters, G. W.

2004-12-01

We have studied the morphological, conformational, and electron-transfer (ET) function of the metalloprotein azurin in the solid state, by a combination of physical investigation methods, namely atomic force microscopy, intrinsic fluorescence spectroscopy, and scanning tunneling microscopy. We demonstrate that a "solid state protein film" maintains its nativelike conformation and ET function, even after removal of the aqueous solvent.

Spectroscopic investigations of ThF and ThF+.

PubMed

Barker, Beau J; Antonov, Ivan O; Heaven, Michael C; Peterson, Kirk A

2012-03-14

The electronic spectra of ThF and ThF(+) have been examined using laser induced fluorescence and resonant two-photon ionization techniques. The results from high-level ab initio calculations have been used to guide the assignment of these data. Spectra for ThF show that the molecule has an X (2)Δ(3/2) ground state. The upper spin-orbit component, X (2)Δ(5/2) was found at an energy of 2575(15) cm(-1). The low-lying states of ThF(+) were probed using dispersed fluorescence and pulsed field ionization-zero kinetic energy (PFI-ZEKE) photoelectron spectroscopy. Vibronic progressions belonging to four electronic states were identified. The lowest energy states were clearly (1)Σ(+) and (3)Δ(1). Although the energy ordering could not be rigorously determined, the evidence favors assignment of (1)Σ(+) as the ground state. The (3)Δ(1) state, of interest for investigation of the electron electric dipole moment, is just 315.0(5) cm(-1) above the ground state. The PFI-ZEKE measurements for ThF yielded an ionization energy of 51 581(3) cm(-1). Molecular constants show that the vibrational constant increases and the bond length shortens on ionization. This is consistent with removal of a non-bonding Th-centered 6d or 7s electron. Laser excitation of ThF(+) was used to probe electronically excited states in the range of 19,000-21,500 cm(-1).

Racemic crystals of trolox derivatives compared to their chiral counterparts: Structural studies using solid-state NMR, DFT calculations and X-ray diffraction

NASA Astrophysics Data System (ADS)

Wałejko, P.; Paradowska, K.; Szeleszczuk, Ł.; Wojtulewski, S.; Baj, A.

2018-03-01

Trolox C (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid) is a water-soluble vitamin E analogue that is available in enantiomeric forms R or S. Enantiomerically pure Trolox 1, its derivatives 2, 3 (R and S enantiomers) and racemic forms 1-3 were studied using solid-state 13C cross-polarisation (CP) magic angle spinning (MAS) NMR (13C CPMAS NMR). Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of the shielding constants supported the assignment of 13C resonances in the solid-state NMR spectra. For the 13C CPMAS NMR spectra of 1, resonances of pure enantiomers were significantly broader than those of the racemic R/S form. In order to explain these effects, five of the available crystal structures were analysed (1R/S, 3R/S, 2S and the newly measured 2R/S and 3S). Cyclic dimers with one R and one S enantiomer linked by two OHsbnd Odbnd C2b hydrogen bonds were formed in 1R/S. Similar hydrogen-bonded dimers were present in 3S but not in 3R/S, in which interactions are water-mediated. A comparison of X-ray diffraction, CPMAS NMR data and the DFT GIPAW calculations of racemic forms and pure enantiomers was conducted for the first time. Our results, particularly the solid-state NMR data, were discussed in relation to Wallach's rule, that the racemic crystal appears as more ordered than its chiral counterpart.

Bonding quandary in the [Cu3S2]3+ core: insights from the analysis of domain averaged fermi holes and the local spin.

PubMed

Ponec, Robert; Ramos-Cordoba, Eloy; Salvador, Pedro

2013-03-07

The electronic structure of the trinuclear symmetric complex [(tmedaCu)3S2 ](3+), whose Cu3S2 core represents a model of the active site of metalloenzymes involved in biological processes, has been in recent years the subject of vigorous debate. The complex exists as an open-shell triplet, and discussions concerned the question whether there is a direct S-S bond in the [Cu3S2](3+) core, whose answer is closely related to the problem of the formal oxidation state of Cu atoms. In order to contribute to the elucidation of the serious differences in the conclusions of earlier studies, we report in this study the detailed comprehensive analysis of the electronic structure of the [Cu3S2](3+) core using the methodologies that are specifically designed to address three particular aspects of the bonding in the core of the above complex, namely, the presence and/or absence of direct S-S bond, the existence and the nature of spin-spin interactions among the atoms in the core, and the formal oxidation state of Cu atoms in the core. Using such a combined approach, it was possible to conclude that the picture of bonding consistently indicates the existence of a weak direct two-center-three-electron (2c-3e) S-S bond, but at the same time, the observed lack of any significant local spin in the core of the complex is at odds with the suggested existence of antiferromagnetic coupling among the Cu and S atoms, so that the peculiarities of the bonding in the complex seem to be due to extensive delocalization of the unpaired spin in the [Cu3S2](3+) core. Finally, a scrutiny of the effective atomic hybrids and their occupations points to a predominant formal Cu(II) oxidation state, with a weak contribution of partial Cu(I) character induced mainly by the partial flow of electrons from S to Cu atoms and high delocalization of the unpaired spin in the [Cu3S2](3+) core.

Electron Transfer Dissociation: Effects of Cation Charge State on Product Partitioning in Ion/Ion Electron Transfer to Multiply Protonated Polypeptides

PubMed Central

Liu, Jian; McLuckey, Scott A.

2012-01-01

The effect of cation charge state on product partitioning in the gas-phase ion/ion electron transfer reactions of multiply protonated tryptic peptides, model peptides, and relatively large peptides with singly charged radical anions has been examined. In particular, partitioning into various competing channels, such as proton transfer (PT) versus electron transfer (ET), electron transfer with subsequent dissociation (ETD) versus electron transfer with no dissociation (ET,noD), and fragmentation of backbone bonds versus fragmentation of side chains, was measured quantitatively as a function of peptide charge state to allow insights to be drawn about the fundamental aspects of ion/ion reactions that lead to ETD. The ET channel increases relative to the PT channel, ETD increases relative to ET,noD, and fragmentation at backbone bonds increases relative to side-chain cleavages as cation charge state increases. The increase in ET versus PT with charge state is consistent with a Landau-Zener based curve-crossing model. An optimum charge state for ET is predicted by the model for the ground state-to-ground state reaction. However, when the population of excited product ion states is considered, it is possible that a decrease in ET efficiency as charge state increases will not be observed due to the possibility of the population of excited electronic states of the products. Several factors can contribute to the increase in ETD versus ET,noD and backbone cleavage versus side-chain losses. These factors include an increase in reaction exothermicity and charge state dependent differences in precursor and product ion structures, stabilities, and sites of protonation. PMID:23264749

An Alternative to the Ionic Model

ERIC Educational Resources Information Center

Sanderson, R. T.

1975-01-01

Describes the "coordinated polymeric model," which yields more accurate energy calculations than the "ionic model" for compounds which exhibit considerable covalency. The dichotomy between ionic and covalent bonding is thus largely broken down for solids which are nonmolecular in the crystalline state. (MLH)

Structural studies of TiC{sub 1−x}O{sub x} solid solution by Rietveld refinement and first-principles calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Bo, E-mail: youqin5912@yahoo.com.cn; Hou, Na; Huang, Shanyan

2013-08-15

The lattice parameters, structural stability and electronic structure of titanium oxycarbides (TiC{sub 1−x}O{sub x}, 0≤x≤1) solid solution were investigated by Rietveld refinement and first-principles calculations. Series of TiC{sub 1−x}O{sub x} were precisely synthesized by sintering process under the vacuum. Rietveld refinement results of XRD patterns show the properties of continuous solid solution in TiC{sub 1−x}O{sub x} over the whole composition range. The lattice parameters vary from 0.4324 nm to 0.4194 nm decreasing with increasing oxygen concentration. Results of first-principles calculations reveal that the disorder C/O structure is stable than the order C/O structure. Further investigations of the vacancy in Ti{submore » 1−Va}(C{sub 1−x}O{sub x}){sub 1−Va} solid solution present that the structure of vacancy segregated in TiO-part is more stable than the disorder C/O structure, which can be ascribed to the Ti–Ti bond across O-vacancy and the charge redistributed around Ti-vacancy via the analysis of the electron density difference plots and PDOS. - Graphical abstract: XRD of series of titanium oxycarbides (TiC{sub 1−x}O{sub x}, 0≤x≤1) solid solution prepared by adjusting the proportion of TiO in the starting material. Highlights: • Titanium oxycarbides were obtained by sintering TiO and TiC under carefully controlled conditions. • Rietveld refinement results show continuous solid solution with FCC structure in TiC{sub 1−x}O{sub x}. • The disorder C/O structure is stable than the order C/O structure. • Introduction of vacancy segregated in TiO-part is more stable than disorder C/O structure. • Ti–Ti bond across O-vacancy and the charge redistributed around Ti-vacancy enhance structural stability.« less

A kinetico-mechanistic study on the C-H bond activation of primary benzylamines; cooperative and solid-state cyclopalladation on dimeric complexes.

PubMed

Font, Helena; Font-Bardia, Mercè; Gómez, Kerman; González, Gabriel; Granell, Jaume; Macho, Israel; Martínez, Manuel

2014-09-28

The cyclometallation reactions of dinuclear μ-acetato complexes of the type [Pd(AcO)(μ-AcO)L]2 (L = 4-RC6H4CH2NH2, R = H, Cl, F, CF3), a process found to occur readily even in the solid state, have been studied from a kinetico-mechanistic perspective. Data indicate that the dinuclear acetato bridged derivatives are excellent starting materials to activate carbon-hydrogen bonds in a facile way. In all cases the established concerted ambiphilic proton abstraction by a coordinated acetato ligand has been proved. The metallation has also been found to occur in a cooperative manner, with the metallation of the first palladium unit of the dimeric complex being rate determining; no intermediate mono-metallated compounds are observed in any of the processes. The kinetically favoured bis-cyclopalladated compound obtained after complete C-H bond activation does not correspond to the final isolated XRD-characterized complexes. This species, bearing the classical open-book dimeric form, has a much more complex structure than the final isolated compound, with different types of acetato ligands.

Superstrong encapsulated monolayer graphene by the modified anodic bonding.

PubMed

Jung, Wonsuk; Yoon, Taeshik; Choi, Jongho; Kim, Soohyun; Kim, Yong Hyup; Kim, Taek-Soo; Han, Chang-Soo

2014-01-07

We report a superstrong adhesive of monolayer graphene by modified anodic bonding. In this bonding, graphene plays the role of a superstrong and ultra-thin adhesive between SiO2 and glass substrates. As a result, monolayer graphene presented a strong adhesion energy of 1.4 J m(-2) about 310% that of van der Waals bonding (0.45 J m(-2)) to SiO2 and glass substrates. This flexible solid state graphene adhesive can tremendously decrease the adhesive thickness from about several tens of μm to 0.34 nm for epoxy or glue at the desired bonding area. As plausible causes of this superstrong adhesion, we suggest conformal contact with the rough surface of substrates and generation of C-O chemical bonding between graphene and the substrate due to the bonding process, and characterized these properties using optical microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy.

Controlling the hydrogenolysis of silica-supported tungsten pentamethyl leads to a class of highly electron deficient partially alkylated metal hydrides

DOE PAGES

Maity, Niladri; Barman, Samir; Callens, Emmanuel; ...

2015-11-30

The well-defined single-site silica-supported tungsten complex [(Si–O–)W(Me) 5], 1, is an excellent precatalyst for alkane metathesis. The unique structure of 1 allows the synthesis of unprecedented tungsten hydrido methyl surface complexes via a controlled hydrogenolysis. Specifically, in the presence of molecular hydrogen, 1 is quickly transformed at -78 °C into a partially alkylated tungsten hydride, 4, as characterized by 1H solid-state NMR and IR spectroscopies. Species 4, upon warming to 150 °C, displays the highest catalytic activity for propane metathesis yet reported. DFT calculations using model systems support the formation of [(Si–O–)WH 3(Me) 2], as the predominant species at -78more » °C following several elementary steps of hydrogen addition (by σ-bond metathesis or α-hydrogen transfer). Rearrangement of 4 occuring between -78 °C and room temperature leads to the formation of an unique methylidene tungsten hydride [(Si–O–)WH 3(CH 2)], as determined by solid-state 1H and 13C NMR spectroscopies and supported by DFT. Thus for the first time, a coordination sphere that incorporates both carbene and hydride functionalities has been observed.« less

Single layers and multilayers of GaN and AlN in square-octagon structure: Stability, electronic properties, and functionalization

NASA Astrophysics Data System (ADS)

Gürbüz, E.; Cahangirov, S.; Durgun, E.; Ciraci, S.

2017-11-01

Further to planar single-layer hexagonal structures, GaN and AlN can also form free-standing, single-layer structures constructed from squares and octagons. We performed an extensive analysis of dynamical and thermal stability of these structures in terms of ab initio finite-temperature molecular dynamics and phonon calculations together with the analysis of Raman and infrared active modes. These single-layer square-octagon structures of GaN and AlN display directional mechanical properties and have wide, indirect fundamental band gaps, which are smaller than their hexagonal counterparts. These density functional theory band gaps, however, increase and become wider upon correction. Under uniaxial and biaxial tensile strain, the fundamental band gaps decrease and can be closed. The electronic and magnetic properties of these single-layer structures can be modified by adsorption of various adatoms, or by creating neutral cation-anion vacancies. The single-layer structures attain magnetic moment by selected adatoms and neutral vacancies. In particular, localized gap states are strongly dependent on the type of vacancy. The energetics, binding, and resulting electronic structure of bilayer, trilayer, and three-dimensional (3D) layered structures constructed by stacking the single layers are affected by vertical chemical bonds between adjacent layers. In addition to van der Waals interaction, these weak vertical bonds induce buckling in planar geometry and enhance their binding, leading to the formation of stable 3D layered structures. In this respect, these multilayers are intermediate between van der Waals solids and wurtzite crystals, offering a wide range of tunability.

Structural and spectroscopic features of proton hydrates in the crystalline state. Solid-state DFT study on HCl and triflic acid hydrates

NASA Astrophysics Data System (ADS)

Vener, M. V.; Chernyshov, I. Yu.; Rykounov, A. A.; Filarowski, A.

2018-01-01

Crystalline HCl and CF3SO3H hydrates serve as excellent model systems for protonated water and perfluorosulphonic acid membranes, respectively. They contain characteristic H3O+, H5О+2, H7О+3 and H3O+(H2O)3 (the Eigen cation) structures. The properties of these cations in the crystalline hydrates of strong monobasic acids are studied by solid-state density function theory (DFT). Simultaneous consideration of the HCl and CF3SO3H hydrates reveals the impact of the size of a counter ion and the crystalline environment on the structure and infrared active bands of the simplest proton hydrates. The H7O+3 structure is very sensitive to the size of the counter ion and symmetry of the local environment. This makes it virtually impossible to identify the specific features of H7O+3 in molecular crystals. The H3O+ ion can be treated as the Eigen-like cation in the crystalline state. Structural, infrared and electron-density features of H5О+2 and the Eigen cation are virtually insensitive to the size of the counter ion and the symmetry of the local crystalline environment. These cations can be considered as the simplest stable proton hydrates in the condensed phase. Finally, the influence of the Grimme correction on the structure and harmonic frequencies of the molecular crystals with short (strong) intermolecular O-H···O bonds is discussed.

Chemical Bonding in Sulfide Minerals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vaughan, David J.; Rosso, Kevin M.

An understanding of chemical bonding and electronic structure in sulfide minerals is central to any attempt at understanding their crystal structures, stabilities and physical properties. It is also an essential precursor to understanding reactivity through modeling surface structure at the molecular scale. In recent decades, there have been remarkable advances in first principles (ab initio) methods for the quantitative calculation of electronic structure. These advances have been made possible by the very rapid development of high performance computers. Several review volumes that chart the applications of these developments in mineralogy and geochemistry are available (Tossell and Vaughan, 1992; Cygan andmore » Kubicki, 2001). An important feature of the sulfide minerals is the diversity of their electronic structures, as evidenced by their electrical and magnetic properties (see Pearce et al. 2006, this volume). Thus, sulfide minerals range from insulators through semiconductors to metals, and exhibit every type of magnetic behavior. This has presented problems for those attempting to develop bonding models for sulfides, and also led to certain misconceptions regarding the kinds of models that may be appropriate. In this chapter, chemical bonding and electronic structure models for sulfides are reviewed with emphasis on more recent developments. Although the fully ab initio quantitative methods are now capable of a remarkable degree of sophistication in terms of agreement with experiment and potential to interpret and predict behavior with varying conditions, both qualitative and more simplistic quantitative approaches will also be briefly discussed. This is because we believe that the insights which they provide are still helpful to those studying sulfide minerals. In addition to the application of electronic structure models and calculations to solid sulfides, work on sulfide mineral surfaces (Rosso and Vaughan 2006a,b) and solution complexes and clusters (Rickard and Luther, 2006) are discussed in detail later in this volume.« less

rac-4-(2-Meth­oxy­phen­yl)-2,6-dimethyl­cyclo­hex-3-ene­carb­oxy­lic acid

PubMed Central

Xie, Songwen; Fowler, Brian P.; Deyo, Sara M.; Pink, Maren

2010-01-01

The title compound, C16H20O3, was synthesized to study the hydrogen-bonding inter­actions of the two enanti­omers in the solid state. Inter­molecular O—H⋯O hydrogen bonds produce centrosymmetric R 2 2(8) rings which dimerize the two chiral enanti­omers together through their carboxyl groups. PMID:21579575

Number series of atoms, interatomic bonds and interface bonds defining zinc-blende nanocrystals as function of size, shape and surface orientation: Analytic tools to interpret solid state spectroscopy data

DOE Office of Scientific and Technical Information (OSTI.GOV)

König, Dirk, E-mail: dirk.koenig@unsw.edu.au

2016-08-15

Semiconductor nanocrystals (NCs) experience stress and charge transfer by embedding materials or ligands and impurity atoms. In return, the environment of NCs experiences a NC stress response which may lead to matrix deformation and propagated strain. Up to now, there is no universal gauge to evaluate the stress impact on NCs and their response as a function of NC size d{sub NC}. I deduce geometrical number series as analytical tools to obtain the number of NC atoms N{sub NC}(d{sub NC}[i]), bonds between NC atoms N{sub bnd}(d{sub NC}[i]) and interface bonds N{sub IF}(d{sub NC}[i]) for seven high symmetry zinc-blende (zb) NCsmore » with low-index faceting: {001} cubes, {111} octahedra, {110} dodecahedra, {001}-{111} pyramids, {111} tetrahedra, {111}-{001} quatrodecahedra and {001}-{111} quadrodecahedra. The fundamental insights into NC structures revealed here allow for major advancements in data interpretation and understanding of zb- and diamond-lattice based nanomaterials. The analytical number series can serve as a standard procedure for stress evaluation in solid state spectroscopy due to their deterministic nature, easy use and general applicability over a wide range of spectroscopy methods as well as NC sizes, forms and materials.« less

Spectroscopic studies of the intramolecular hydrogen bonding in o-hydroxy Schiff bases, derived from diaminomaleonitrile, and their deprotonation reaction products

NASA Astrophysics Data System (ADS)

Szady-Chełmieniecka, Anna; Kołodziej, Beata; Morawiak, Maja; Kamieński, Bohdan; Schilf, Wojciech

2018-01-01

The structural study of five Schiff bases derived from diaminomaleonitrile (DAMN) and 2-hydroxy carbonyl compounds was performed using 1H, 13C and 15N NMR methods in solution and in the solid state as well. ATR-FTIR and X-Ray spectroscopies were used for confirmation of the results obtained by NMR method. The imine obtained from DAMN and benzaldehyde was synthesized as a model compound which lacks intramolecular hydrogen bond. Deprotonation of all synthesized compounds was done by treating with tetramethylguanidine (TMG). NMR data revealed that salicylidene Schiff bases in DMSO solution exist as OH forms without intramolecular hydrogen bonds and independent on the substituents in aromatic ring. In the case of 2-hydroxy naphthyl derivative, the OH proton is engaged into weak intramolecular hydrogen bond. Two of imines (salDAMN and 5-BrsalDAMN) exist in DMSO solution as equilibrium mixtures of two isomers (A and B). The structures of equilibrium mixture in the solid state have been studied by NMR, ATR-FTIR and X-Ray methods. The deprotonation of three studied compounds (salDAMN, 5-BrsalDAMN, and 5-CH3salDAMN) proceeded in two different ways: deprotonation of oxygen atom (X form) or of nitrogen atom of free primary amine group of DAMN moiety (Y form). For 5-NO2salDAMN and naphDAMN only one form (X) was observed.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, D.; Ladipo, F.T.; Braddock-Wilking, J.

Low temperature crystal structures of (DABCO)H{sup +}Co(CO){sub 4}{sup -} (1) and (DABCO)H{sup +}Co(CO){sub 3}PPh{sub 3}{sup -} (2) (DABCO = 1,4-diazabicyclooctane) indicate that both salts exhibit N-H...Co hydrogen bonding. IR and NMR data indicate that these hydrogen bonded species persist in nonpolar solvents such as toluene, but exist as solvent separated ions in more polar solvents. Replacement of the axial CO ligand by PPh{sub 3} leads to a shortening of the N...Co separation in the solid state from 3.437(3) to 3.294(6) A. This change is accompanied by an increase in the angle between the equatorial carbonyl ligands. Thus, the crystallographic resultsmore » suggest a strengthening of the N-H...Co hydrogen bond upon increasing the basicity of the metal center, the first observation of this type in the solid state. This assertion is supported by variable-temperature {sup 1}H and {sup 13}C NMR data in toluene-d{sub 8} solution which, discussed in the light of ab initio calculations, indicate that the barrier to a fluxional process involving cleavage of the N-H...Co hydrogen bond is greater in 2 than in 1. The crystal structures of 1 and 2 have been determined by X-ray diffraction at 135(5) and 123(5) K, respectively. 19 refs., 2 figs., 5 tabs.« less

Electronic structure of Ag7GeS5I superionic compound

NASA Astrophysics Data System (ADS)

Bletskan, Dmytro; Studenyak, Ihor; Bletskan, Mykhailo; Vakulchak, Vasyl

2018-05-01

This paper presents the originally results of ab initio calculations of electronic structure, total and partial densities of electronic states as well as electronic charge density distribution of Ag7GeS5I crystal performed within the density functional theory (DFT) in the local density approximation (LDA) for exchange-correlation potential. According to performed calculations, Ag7GeS5I is the direct-gap semiconductor with the valence band top and the conductivity band bottom in the Γ point of Brillouin zone. The band gap width calculated in the LDA-approximation is Egd = 0.73 eV. The analysis of total and partial densities of electronic states allow us to identify the atomic orbital contributions into the crystal orbitals as well as the formation data of chemical bond in the studied crystal. In the top part of Ag7GeS5I valence band it was revealed the considerable mixing (hybridization) of the occupied d-states of Ag noble metal and the delocalized p-states of sulfur and iodine, which is undoubtedly associated with the covalent character of chemical bond between S, I atoms and noble metal atom.

Photodissociation spectroscopy of the dysprosium monochloride molecular ion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dunning, Alexander, E-mail: alexander.dunning@gmail.com; Schowalter, Steven J.; Puri, Prateek

2015-09-28

We have performed a combined experimental and theoretical study of the photodissociation cross section of the molecular ion DyCl{sup +}. The photodissociation cross section for the photon energy range 35 500 cm{sup −1} to 47 500 cm{sup −1} is measured using an integrated ion trap and time-of-flight mass spectrometer; we observe a broad, asymmetric profile that is peaked near 43 000 cm{sup −1}. The theoretical cross section is determined from electronic potentials and transition dipole moments calculated using the relativistic configuration-interaction valence-bond and coupled-cluster methods. The electronic structure of DyCl{sup +} is extremely complex due to the presence of multiple open electronic shells,more » including the 4f{sup 10} configuration. The molecule has nine attractive potentials with ionically bonded electrons and 99 repulsive potentials dissociating to a ground state Dy{sup +} ion and Cl atom. We explain the lack of symmetry in the cross section as due to multiple contributions from one-electron-dominated transitions between the vibrational ground state and several resolved repulsive excited states.« less