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1

The Bond Dissociation Energies of 1-Butene  

NASA Technical Reports Server (NTRS)

The bond dissociation energies of 1-butene and several calibration systems are computed using the G2(MP2) approach. The agreement between the calibration systems and experiment is very good. The computed values for 1-butene are compared with calibration systems and the agreement between the computed results for 1-butene and the "rule of thumb" values from the smaller systems is remarkably good.

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

1994-01-01

2

A comparative study of semiempirical bond dissociation energy calculations  

SciTech Connect

Anderson's modified version of the extended Hueckel molecular orbital method and the MNDO and AM1 methods of Dewar are used to study bond cleavage in molecular fragments of interest in coal liquefaction. Geometric conformations, molecular orbital coefficients for the HOMO's and LUMO's, and bond dissociation energies are computed and compared for the three methods. Qualitative agreement with experiment for bond cleavage is observed for the three methods for the neutral molecule. However the ASED-MO method appears to best describe the bond cleavage in the presence of an electron-accepting catalyst.

Ades, H.F.; Companion, A.L.; Subbaswamy, K.R. (Univ. of Kentucky, Lexington (United States))

1991-08-22

3

Characterization of CF bonds with multiple-bond character: bond lengths, stretching force constants, and bond dissociation energies.  

PubMed

Isoelectronic C=F(+) and C=O bonds contained in fluoro-substituted carbenium ions, aldehydes, and ketones are investigated with regard to their bond properties by utilizing the vibrational spectra of these molecules. It is demonstrated that bond dissociation energies (BDEs), bond lengths, vibrational stretching frequencies, and bond densities are not reliable descriptors of the bond strength. The latter is related to the intrinsic BDE, which corresponds to nonrelaxed dissociation products retaining the electronic structure and geometry they have in the molecule. It is shown that the harmonic stretching force constants k(a) of the localized internal coordinate vibrations (adiabatic vibrational modes) reflect trends in the intrinsic BDEs. The k(a) values of both CO and CF bonds are related to the bond lengths through a single exponential function. This observation is used to derive a common bond order n for 46 CO- and CF-containing molecules that reliably describes differences in bonding. CF bonds in fluorinated carbenium ions possess bond orders between 1.3 and 1.7 as a result of significant pi back-bonding from F to C, which is sensitive to electronic effects caused by substituents at the carbenium center. Therefore, the strength of the C=F(+) bond can be used as a sensor for (hyper)conjugation and other electronic effects influencing the stability of the carbenium ion. The diatomic C=F(+) ion has a true double bond due to pi donation from the F atom. The characterization of CF bonds with the help of adiabatic stretching modes is also applied to fluoronium ions (n = 0.3-0.6) and transition states involving CF cleavage and HF elimination (n = 0.7-0.8). PMID:19152353

Kraka, Elfi; Cremer, Dieter

2009-03-01

4

A C–C Bonded Phenoxyl Radical Dimer with a Zero Bond Dissociation Free Energy  

PubMed Central

The 2,6-di-tert-butyl-4-methoxy-phenoxyl radical is shown to dimerize in solution and in the solid state. The X-ray crystal structure for the dimer, the first for a para-coupled phenoxyl radical, reveals a bond length of 1.6055(23) Å for the 4-4’ C–C bond. This is significantly longer than typical C–C bonds. Solution equilibrium studies using both optical and IR spectroscopies show that the Keq for dissociation is 1.3 ± 0.2 M at 20 °C, indicating a C–C bond dissociation free energy of ?0.15 ± 0.1 kcal mol?1. Van’t Hoff analysis gives an exceptionally small bond dissociation enthalpy (BDE) of 6.1 ± 0.5 kcal mol?1. To our knowledge, this is the weakest BDE measured for a C–C bond. This very weak bond shows a large deviation from the correlation of C–C bond lengths and strengths, but the computed force constant follows Badger’s rule. PMID:23952108

Wittman, Jessica M.; Hayoun, Rebecca; Kaminsky, Werner; Coggins, Michael K.; Mayer, James M.

2014-01-01

5

Bond Dissociation Energies in Second-Row Compounds  

SciTech Connect

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Heats of formation at 0 and 298 K are predicted for PF?, PF?, PF?O, SF?, SF?, SF?, SF?O, SF?O?, and SF?O as well as a number of radicals derived from these stable compounds on the basis of coupled cluster theory [CCSD(T)] calculations extrapolated to the complete basis set limit. In order to achieve near chemical accuracy (±1 kcal/mol), additional corrections were added to the complete basis set binding energies based on frozen core coupled cluster theory energies: a correction for core-valence effects, a correction for scalar relativistic effects, a correction for first-order atomic spin-orbit effects, and vibrational zero-point energies. The calculated values substantially reduce the error limits for these species. A detailed comparison of adiabatic and diabatic bond dissociation energies (BDEs) is made and used to explain trends in the BDEs. Because the adiabatic BDEs of polyatomic molecules represent not only the energy required for breaking a specific bond but also contain any reorganization energies of the bonds in the resulting products, these BDEs can be quite different for each step in the stepwise loss of ligands in binary compounds. For example, the adiabatic BDE for the removal of one fluorine ligand from the very stable closed-shell SF? molecule to give the unstable SF? radical is 2.8 times the BDE needed for the removal of one fluorine ligand from the unstable SF? radical to give the stable closed-shell SF? molecule. Similarly, the BDE for the removal of one fluorine ligand from the stable closed-shell PF?O molecule to give the unstable PF?O radical is higher than the BDE needed to remove the oxygen atom to give the stable closed-shell PF? molecule. The same principles govern the BDEs of the phosphorus fluorides and the sulfur oxofluorides. In polyatomic molecules, care must be exercised not to equate BDEs with the bond strengths of given bonds. The measurement of the bond strength or stiffness of a given bond represented by its force constant involves only a small displacement of the atoms near equilibrium and, therefore, does not involve any reorganization energies, i.e., it may be more appropriate to correlate with the diabatic product states.

Grant, Daniel J.; Matus, Myrna H.; Switzer, Jackson R.; Dixon, David A.; Francisco, Joseph S.; Christe, Karl O.

2008-04-10

6

The dissociative bond.  

PubMed

Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other. PMID:23282044

Gordon, Nirit

2013-01-01

7

Influence of charge and coordination number on bond dissociation energies, distances, and vibrational frequencies for the phosphorus-phosphorus bond.  

PubMed

We report a comprehensive and systematic experimental and computational assessment of the P-P bond in prototypical molecules that represent a rare series of known compounds. The data presented complement the existing solid-state structural data and previous computational studies to provide a thorough thermodynamic and electronic understanding of the P-P bond. Comparison of homolytic and heterolytic bond dissociation for tricoordinate-tricoordinate, tricoordinate-tetracoordinate, and tetracoordinate-tetracoordinate P-P bonds in frameworks 1-6 provides fundamental insights into covalent bonding. For all types of P-P bond discussed, homolytic dissociation is favored over heterolytic dissociation, although the distinction is small for 2(1+) and 6(1+). The presence of a single cationic charge in a molecule substantially strengthens the P-P bond (relative to analogous neutral frameworks) such that it is comparable with the C-C bond in alkanes. Nevertheless, P-P distances are remarkably independent of molecular charge or coordination number, and trends in values of d(PC) and ?symm(PC) imply that a molecular cationic charge is distributed over the alkyl substituents. In the gas phase, the diphosphonium dication 3(2+) has similar energy to two [PMe3](+) radical cations, so that it is the lattice enthalpy of 3[OTf]2 in the solid-state that enables isolation, highlighting that values from gas-phase calculations are poor guides for synthetic planning for ionic compounds. There are no relationships or correlations between bond lengths, strengths, and vibrational frequencies. PMID:25105886

Chitnis, Saurabh S; Whalen, J Marc; Burford, Neil

2014-09-01

8

The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems  

NASA Technical Reports Server (NTRS)

The bond dissociation energies (De) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of De with respect to the one-particle basis is studied at the single-reference modified coupled-pair-functional (MCPF)level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration-interaction (MRCI) De values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size-extensive averaged-coupled-pair-functional (ACPF) method. The full-valence complete-active-space self-consistent-field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds.

Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Taylor, Peter R.

1991-01-01

9

Theoretical study of the bond dissociation energies of propyne (C3H4)  

NASA Technical Reports Server (NTRS)

The C-C and C-H bond dissociation energies (BDEs) of propyne have been computed using the modified coupled-pair functional method. Due to hyperconjugation, the C-C and methyl C-H single bonds are stronger and weaker, respectively than those in ethane. The acetylenic C-H and C triple bond C BDEs are larger and smaller, respectively, than in acetylene, also as a result of the hyperconjugation. Our best estimate of 92.5 +/- 2 kcal/mol for the methyl C-H BDE in propyne is slightly larger than the experimental value. For the acetylenic C-H BDE in propyne we predict 135.9 +/- 2 kcal/mol.

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

1992-01-01

10

Bond dissociation energies and radical stabilization energies: an assessment of contemporary theoretical procedures.  

PubMed

Various contemporary theoretical procedures have been tested for their accuracy in predicting the bond dissociation energies (BDEs) and the radical stabilization energies (RSEs) for a test set of 22 monosubstituted methyl radicals. The procedures considered include the high-level W1, W1', CBS-QB3, ROCBS-QB3, G3(MP2)-RAD, and G3X(MP2)-RAD methods, unrestricted and restricted versions of the double-hybrid density functional theory (DFT) procedures B2-PLYP and MPW2-PLYP, and unrestricted and restricted versions of the hybrid DFT procedures BMK and MPWB1K, as well as the unrestricted DFT procedures UM05 and UM05-2X. The high-level composite procedures show very good agreement with experiment and are used to evaluate the performance of the comparatively less expensive DFT procedures. RMPWB1K and both RBMK and UBMK give very promising results for absolute BDEs, while additionally restricted and unrestricted X2-PLYP methods and UM05-2X give excellent RSE values. UM05, UB2-PLYP, UMPW2-PLYP, UM05-2X, and UMPWB1K are among the less well performing methods for BDEs, while UMPWB1K and UM05 perform less well for RSEs. The high-level theoretical results are used to recommend alternative experimental BDEs for propyne, acetaldehyde, and acetic acid. PMID:18047305

Menon, Ambili S; Wood, Geoffrey P F; Moran, Damian; Radom, Leo

2007-12-27

11

Prediction of the bond lengths, vibrational frequencies, and bond dissociation energy of octahedral seaborgium hexacarbonyl, Sg(CO){sub 6}  

SciTech Connect

The recent syntheses of several new elements (including the recent reports of elements 116 and 118), coupled with the controversy surrounding the naming of elements 104--109, have stimulated a great interest in the chemistry of the transactinide elements. This contribution addresses hypothetical hexacarbonyl complex of seaborgium (Sg, element 106), which is predicted to be a 6d-block transition element with six valence electrons, analogous to Cr, Mo, and W. The authors have previously predicted that, if it were to exist, Sg(CO){sub 6} would exhibit metal-carbonyl bonding that is very similar to that in Cr(CO){sub 6}, Mo(CO){sub 6}, and W(CO){sub 6}, and quite unlike that of the unknown valence isoelectronic actinide complex U(CO){sub 6}. This finding is in accord with the scant experimental data available for Sg. The relativistic DV-X{alpha} method used in the earlier paper facilitated the analysis of the molecular orbitals of Sg(CO){sub 6}, but did not allow for the calculation of total-energy properties, such as bond lengths and vibrational frequencies. Here the authors will use the superior methodology they have applied to other transactinide molecules to compare the bond lengths, vibrational frequencies, and CO dissociation energy of hypothetical Sg(CO){sub 6} to those of Mo(CO){sub 6} and W(CO){sub 6}.

Nash, C.S.; Bursten, B.E.

1999-11-24

12

Trends in bond dissociation energies of alcohols and aldehydes computed with multireference averaged coupled-pair functional theory.  

PubMed

As part of our ongoing investigation of the combustion chemistry of oxygenated molecules using multireference correlated wave function methods, we report bond dissociation energies (BDEs) in C1-C4 alcohols (from methanol to the four isomers of butanol) and C1-C4 aldehydes (from methanal to butanal). The BDEs are calculated with a multireference averaged coupled-pair functional-based scheme. We compare these multireference BDEs with those derived from experiment and single-reference methods. Trends in BDEs for the alcohols and aldehydes are rationalized by considering geometry relaxations of dissociated radical fragments, resonance stabilization, and hyperconjugation. Lastly, we discuss the conjectured association between bond strengths and rates of hydrogen abstraction by hydroxyl radicals. In general, abstraction reaction rates are higher at sites where the C-H bond energies are lower (and vice versa). However, comparison with available rate data shows this inverse relationship between bond strengths and abstraction rates does not hold at all temperatures. PMID:24708179

Oyeyemi, Victor B; Keith, John A; Carter, Emily A

2014-05-01

13

N-NO2 bond dissociation energies in acetonitrile: an assessment of contemporary computational methods.  

PubMed

The assessment of the N-NO2 bond dissociation energies (BDEs) was performed by various calculating methods (B3LYP, B3PW91, B3P86, B1LYP, BMK, MPWB1K, PBE0, CBS-4M and M06-2X) at 6-311+G(2d,p) basis set. Compared with the experimental BDEs, the results show that BMK and B3P86 methods reproduce the experimental values well. The mean absolute deviations from the experimental values obtained by BMK and B3P86 methods were 0.5 and 1.5 kcal/mol, respectively. B3LYP, B3PW91, B1LYP, MPWB1K and PBE0 methods underestimated the homolytic N-NO2 BDEs. B3LYP, B3PW91, B1LYP, M06-2X, CBS-4M methods failed to provide an accurate description of N-NO2 BDEs for N-Nitrosulfonamide compounds and showed larger mean absolute deviations and maximum deviations. Further, substituent effect based on BMK/6-311+G(2d,p) method was analysis. Natural bond orbital analysis shows that there exist good linear correlations between E((2)) of lpN1?BD*(O1-N2) and Hammett constants and a better correlation between the BDEs and the second order stabilization energy E((2)) of lpN1?BD*(O1-N2). PMID:23727897

Li, Xiao-Hong; Zhang, Rui-Zhou; Zhang, Xian-Zhou

2013-06-01

14

Bond dissociation energies and radical stabilization energies associated with model peptide-backbone radicals.  

PubMed

Bond dissociation energies (BDEs) and radical stabilization energies (RSEs) have been calculated for a series of models that represent a glycine-containing peptide-backbone. High-level methods that have been used include W1, CBS-QB3, U-CBS-QB3, and G3X(MP2)-RAD. Simpler methods used include MP2, B3-LYP, BMK, and MPWB1K in association with the 6-311+G(3df,2p) basis set. We find that the high-level methods produce BDEs and RSEs that are in good agreement with one another. Of the simpler methods, RBMK and RMPWB1K achieve good accuracy for BDEs and RSEs for all the species that were examined. For monosubstituted carbon-centered radicals, we find that the stabilizing effect (as measured by RSEs) of carbonyl substituents (CX=O) ranges from 24.7 to 36.9 kJ mol(-1), with the largest stabilization occurring for the CH=O group. Amino groups (NHY) also stabilize a monosubstituted alpha-carbon radical, with the calculated RSEs ranging from 44.5 to 49.5 kJ mol(-1), the largest stabilization occurring for the NH2 group. In combination, NHY and CX=O substituents on a disubstituted carbon-centered radical produce a large stabilizing effect ranging from 82.0 to 125.8 kJ mol(-1). This translates to a captodative (synergistic) stabilization of 12.8 to 39.4 kJ mol(-1). For monosubstituted nitrogen-centered radicals, we find that the stabilizing effect of methyl and related (CH2Z) substituents ranges from 25.9 to 31.7 kJ mol(-1), the largest stabilization occurring for the CH3 group. Carbonyl substituents (CX=O) destabilize a nitrogen-centered radical relative to the corresponding closed-shell molecule, with the calculated RSEs ranging from -30.8 to -22.3 kJ mol(-1), the largest destabilization occurring for the CH=O group. In combination, CH2Z and CX=O substituents at a nitrogen radical center produce a destabilizing effect ranging from -19.0 to -0.2 kJ mol(-1). This translates to an additional destabilization associated with disubstitution of -18.6 to -7.8 kJ mol(-1). PMID:16833974

Wood, Geoffrey P F; Moran, Damian; Jacob, Rebecca; Radom, Leo

2005-07-21

15

1228 J.C.S. CHEM.COMM.,1980 Stepvrise Bond Dissociation Energies for the Removal of Fluorine from  

E-print Network

the interpretation offered by Wray and Feldman. This work was supported by the U.S. Army Research Office. (Received rule permits As such, their stepwise bond dissociation energies are of more than just thermodynamic by Wray and Feldman Using Rice-Ramsperger-Kassel (RRK) theory to analyse their kinetic data, these authors

Zare, Richard N.

16

Bond Dissociation Energies of the Tungsten Fluorides and Their Singly-Charged Ions: A Density Functional Survey  

NASA Technical Reports Server (NTRS)

The dissociation of WF6 and the related singly-charged cations and anions into the lower fluorides and fluorine atoms has been investigated theoretically using density functional theory (B3LYP) and relativistic effective core potentials, with estimates of spin-orbit effects included using a simple model. The inclusion of spin-orbit is essential for a correct description of the thermochemistry. The total atomization energy of the neutral and anionic WF6 is reproduced to within 25 kcal/mol, but comparison of individual bond dissociation energies with available experimental data shows discrepancies of up to 10 kcal/mol. The results are nevertheless useful to help resolve discrepancies in experimental data and provide estimates of missing data.

Dyall, Kenneth G.; Arnold, James (Technical Monitor)

1999-01-01

17

Theoretical Bond Dissociation Energies of Halo-Heterocycles: Trends and Relationships to Regioselectivity in Palladium-Catalyzed Cross-Coupling Reactions  

PubMed Central

Selectivity of the palladium-catalyzed cross-coupling reactions of heterocycles bearing multiple identical halogens is mainly determined by the relative ease of oxidative addition. This is related to both the energy to distort the carbon halogen bond to the transition-state geometry (related to the CX bond-dissociation energy) and to the interaction between the heterocycle ?* (LUMO) and PdL2 HOMO (J. Am. Chem. Soc. 2007, 129, 12664). The computed bond dissociation energies of a larger series of halo-heterocycles have been explored with B3LYP and higher accuracy G3B3 calculations. Quantitative trends in bond dissociation energies have been identified for five- and six-membered chloro and bromo substituted heterocycles with N, O, and S heteroatoms. PMID:19368385

Garcia, Yeimy; Schoenebeck, Franziska; Legault, Claude Y.; Merlic, Craig A.; Houk, K. N.

2009-01-01

18

Thermal chemiluminescence from ?-irradiated polytetrafluoroethylene and its emission mechanism: Kinetic analysis and bond dissociation energy of fluoroperoxide group  

NASA Astrophysics Data System (ADS)

Temperature dependence of the time evolution of chemiluminescence intensity from ?-irradiated polytetrafluoroethylene was examined by heating isothermally in the range of 150 and 200 °C. Kinetic analysis was carried out to estimate the rate constants, from which the dissociation energy of the Osbnd O bond in the fluoroperoxide group was determined to be 97 ± 4 kJ mol-1, being consistent with the corresponding value for small fluorocarbon model systems obtained by quantum chemical calculations. This strongly supports the emission mechanism [sbnd CF(OOF)sbnd CF2sbnd ? sbnd COsbnd CF2sbnd + OF2 + h?] proposed in our previous paper to explain chemiluminescence from the ?-irradiated polytetrafluoroethylene.

Yamada, Emi; Noguchi, Tsuyoshi; Akai, Nobuyuki; Ishii, Hiroshi; Satoh, Chikahiro; Hironiwa, Takayuki; Millington, Keith R.; Nakata, Munetaka

2014-11-01

19

Electron transfer associated to bond breaking: Passage from sequential mechanism to dissociative electron transfer as a function of molecular structure, environment and energy of the incoming electron  

SciTech Connect

A simple and approximate model for dissociative electron transfer, based on a Morse curve description, is presented. The quantitative rate data presently available are correctly reproduced by the model. Application of the theory allows the estimation of bond dissociation energies in starting compounds and of the standard potential and intrinsic barrier of the reaction. The model also leads to rationalize the concerted or stepwise character of the electron transfer-bond breaking process as a function of molecular structure and energy of the incoming electron.

Andrieux, C. P.; Robert, M.; Saveant, J-M. [Laboratoire d'Electrochimie Moleculaire, Universite Denis Diderot (Paris 7), URA CNRS 438, 2 Place Jussiaeu, 75251 Paris Cedex 05 (France)

1996-04-01

20

S-OO bond dissociation energies and enthalpies of formation of the thiomethyl peroxyl radicals CH3S(O)nOO (n=0,1,2)  

NASA Astrophysics Data System (ADS)

Optimized geometries, S-OO bond dissociation energies and enthalpies of formation for a series of thiomethyl peroxyl radicals are investigated using high level ab initio and density functional theory methods. The results show that the S-OO bond dissociation energy is largest in the methylsulfonyl peroxyl radical, CH3S(O)2OO, which contains two sulfonic type oxygen atoms followed by the methylthiyl peroxyl radical, CH3SOO. The methylsulfinyl peroxyl radical, CH3S(O)OO, which contains only one sulfonic type oxygen shows the least stability with regard to dissociation to CH3S(O)+O2. This stabilization trend is nicely reflected in the variations of the S-OO bond distance which is found to be shortest in CH3S(O)2OO and longest in CH3S(O)OO.

Salta, Zoi; Kosmas, Agnie Mylona; Lesar, Antonija

2014-10-01

21

Theoretical study of bond distances and dissociation energies of actinide oxides AnO and AnO2.  

PubMed

In the present study we evaluated trends in the bond distances and dissociation enthalpies of actinide oxides AnO and AnO(2) (An = Th-Lr) on the basis of consistent computed data obtained by using density functional theory in conjunction with relativistic small-core pseudopotentials. Computations were carried out on AnO (An = Th-Lr) and AnO(2) (An = Np, Pu, Bk-Lr) species, while for the remaining AnO(2) species recent literature data (Theor. Chem. Acc. 2011, 129, 657) were utilized. The most important computed properties include the geometries, vibrational frequencies, dissociation enthalpies, and several excited electronic states. These molecular properties of the late actinide oxides (An = Bk-No) are reported here for the first time. We present detailed analyses of the bond distances, covalent bonding properties, and dissociation enthalpies. PMID:22471700

Kovács, Attila; Pogány, Peter; Konings, Rudy J M

2012-04-16

22

Effect of an external electric field on the dissociation energy and the electron density properties: The case of the hydrogen bonded dimer HF...HF.  

PubMed

The effect of a homogeneous external electric field parallel to the hydrogen bond in the FH...FH dimer has been studied by theoretical methods. The quantum theory of atoms in molecules methodology has been used for analyzing the electron distribution of the dimer, calculated with different hydrogen bond distances and external field magnitudes. It is shown that an electric field in the opposite direction to the dipole moment of the system strengthens the interaction due to a larger mutual polarization between both molecules and increases the covalent character of the hydrogen bond, while an external field in the opposite direction has the inverse effect. The properties of the complex at its equilibrium geometry with applied field have been calculated, showing that dependencies between hydrogen bond distance, dissociation energy, and properties derived from the topological analysis of the electron distribution are analogous to those observed in families of XDH...AY complexes. The application of an external field appears as a useful tool for studying the effect of the atomic environment on the hydrogen bond interaction. In the case of FH...FH, both the kinetic energy density and the curvature of the electron density along the hydrogen bond at the bond critical point present a surprisingly good linear dependence on the dissociation energy. The interaction energy can be modeled by the sum of two exponential terms that depend on both the hydrogen bond distance and the applied electric field. Moreover, as indicated by the resulting interaction energy observed upon application of different external fields, the equilibrium distance varies linearly with the external field, and the dependence of the dissociation energy on either the hydrogen bond distance or the external electric field is demonstrated to be exponential. PMID:19191374

Mata, Ignasi; Molins, Elies; Alkorta, Ibon; Espinosa, Enrique

2009-01-28

23

Size-extensivity-corrected multireference configuration interaction schemes to accurately predict bond dissociation energies of oxygenated hydrocarbons  

SciTech Connect

Oxygenated hydrocarbons play important roles in combustion science as renewable fuels and additives, but many details about their combustion chemistry remain poorly understood. Although many methods exist for computing accurate electronic energies of molecules at equilibrium geometries, a consistent description of entire combustion reaction potential energy surfaces (PESs) requires multireference correlated wavefunction theories. Here we use bond dissociation energies (BDEs) as a foundational metric to benchmark methods based on multireference configuration interaction (MRCI) for several classes of oxygenated compounds (alcohols, aldehydes, carboxylic acids, and methyl esters). We compare results from multireference singles and doubles configuration interaction to those utilizing a posteriori and a priori size-extensivity corrections, benchmarked against experiment and coupled cluster theory. We demonstrate that size-extensivity corrections are necessary for chemically accurate BDE predictions even in relatively small molecules and furnish examples of unphysical BDE predictions resulting from using too-small orbital active spaces. We also outline the specific challenges in using MRCI methods for carbonyl-containing compounds. The resulting complete basis set extrapolated, size-extensivity-corrected MRCI scheme produces BDEs generally accurate to within 1 kcal/mol, laying the foundation for this scheme's use on larger molecules and for more complex regions of combustion PESs.

Oyeyemi, Victor B. [Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544 (United States)] [Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Krisiloff, David B. [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States)] [Department of Chemistry, Princeton University, Princeton, New Jersey 08544 (United States); Keith, John A.; Libisch, Florian [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States)] [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Pavone, Michele [Department of Chemical Sciences, University of Napoli Federico II, Napoli 80120 (Italy)] [Department of Chemical Sciences, University of Napoli Federico II, Napoli 80120 (Italy); Carter, Emily A., E-mail: eac@princeton.edu [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Program in Applied and Computational Mathematics, Princeton University, Princeton, New Jersey 08544 (United States); Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey 08544 (United States)

2014-01-28

24

On the dissociation energies and bonding in NiCO(+) and TiCO(+)  

NASA Technical Reports Server (NTRS)

Ab initio calculations on the NiCO(+) and TiCO(+) molecules are carried out using large Gaussian basis sets and extensive treatment of electron correlation. The NiCO(+) molecule is found to have a 2Sigma(+) ground state with a 2Delta state only 2.1 kcal/mole higher in energy. The Ni(+)-CO structure is about 11 and 28 kcal/mole more stable than the Ni(+)-OC and the T-shaped structures, respectively.

Bauschlicher, Charles W., Jr.; Barnes, Leslie A.

1988-01-01

25

Diffusion Monte Carlo Study of Bond Dissociation Energies for BH2, B(OH)2, BCl2, and BCl  

NASA Astrophysics Data System (ADS)

On basis of bond dissociation energies (BDEs) for BH2, B(OH)2, BCl2, and BCl, the diffusion Monte Carlo (DMC) method is applied to explore the BDEs of HB-H, HOB-OH, ClB-Cl, and B-Cl. The effect of the choice of orbitals, as well as the backflow transformation, is studied. The Slater-Jastrow DMC algorithm gives BDEs of 359.1±0.12 kJ/mol for HB-H, 410.5±0.50 kJ/mol for HOB-OH, 357.8±1.46 kJ/mol for ClB-Cl, and 504.5±0.96 kJ/mol for B-Cl using B3PW91 orbitals and similar BDEs when B3LYP orbitals are used. DMC with backflow corrections (BF-DMC) gives a HB-H BDE of 369.9±0.12 kJ/mol which is close to one of the available experimental value (375.8 kJ/mol). In the case of HOB-OH BDE, the BF-DMC calculation is 446.0±1.84 kJ/mol that is closer to the experimental BDE. The BF-DMC BDE for ClB-Cl is 343.2±2.34 kJ/mol and the BF-DMC B-Cl BDE is 523.3±0.33 kJ/mol, which are close to the experimental BDEs, 341.9 and 530.0 kJ/mol, respectively.

Li, Hui-ran; Cheng, Xin-lu; Zhang, Hong

2012-02-01

26

The antimony-group 11 chemical bond: Dissociation energies of the diatomic molecules CuSb, AgSb, and AuSb  

SciTech Connect

The intermetallic molecules CuSb, AgSb, and AuSb were identified in the effusive molecular beam produced at high temperature under equilibrium conditions in a double-cell-like Knudsen source. Several gaseous equilibria involving these species were studied by mass spectrometry as a function of temperature in the overall range 1349–1822 K, and the strength of the chemical bond formed between antimony and the group 11 metals was for the first time measured deriving the following thermochemical dissociation energies (D{sub 0}{sup ?}, kJ/mol): 186.7 ± 5.1 (CuSb), 156.3 ± 4.9 (AgSb), 241.3 ± 5.8 (AuSb). The three species were also investigated computationally at the coupled cluster level with single, double, and noniterative quasiperturbative triple excitations (CCSD(T)). The spectroscopic parameters were calculated from the potential energy curves and the dissociation energies were evaluated at the Complete Basis Set limit, resulting in an overall good agreement with experimental values. An approximate evaluation of the spin-orbit effect was also performed. CCSD(T) calculations were further extended to the corresponding group 11 arsenide species which are here studied for the first time and the following dissociation energies (D{sub 0}{sup ?}, kJ/mol): 190 ± 10 (CuAs), 151 ± 10 (AgAs), 240 ± 15 (AuAs) are proposed. Taking advantage of the new experimental and computational information here presented, the bond energy trends along group 11 and 4th and 5th periods of the periodic table were analyzed and the bond energies of the diatomic species CuBi and AuBi, yet experimentally unobserved, were predicted on an empirical basis.

Carta, V.; Ciccioli, A., E-mail: guido.gigli@uniroma1.it, E-mail: andrea.ciccioli@uniroma1.it; Gigli, G., E-mail: guido.gigli@uniroma1.it, E-mail: andrea.ciccioli@uniroma1.it [Dipartimento di Chimica, Sapienza Università di Roma, p.le A. Moro 5, 00185 Roma (Italy)

2014-02-14

27

The antimony-group 11 chemical bond: dissociation energies of the diatomic molecules CuSb, AgSb, and AuSb.  

PubMed

The intermetallic molecules CuSb, AgSb, and AuSb were identified in the effusive molecular beam produced at high temperature under equilibrium conditions in a double-cell-like Knudsen source. Several gaseous equilibria involving these species were studied by mass spectrometry as a function of temperature in the overall range 1349-1822 K, and the strength of the chemical bond formed between antimony and the group 11 metals was for the first time measured deriving the following thermochemical dissociation energies (D°(0), kJ/mol): 186.7 ± 5.1 (CuSb), 156.3 ± 4.9 (AgSb), 241.3 ± 5.8 (AuSb). The three species were also investigated computationally at the coupled cluster level with single, double, and noniterative quasiperturbative triple excitations (CCSD(T)). The spectroscopic parameters were calculated from the potential energy curves and the dissociation energies were evaluated at the Complete Basis Set limit, resulting in an overall good agreement with experimental values. An approximate evaluation of the spin-orbit effect was also performed. CCSD(T) calculations were further extended to the corresponding group 11 arsenide species which are here studied for the first time and the following dissociation energies (D°(0), kJ/mol): 190 ± 10 (CuAs), 151 ± 10 (AgAs), 240 ± 15 (AuAs) are proposed. Taking advantage of the new experimental and computational information here presented, the bond energy trends along group 11 and 4th and 5th periods of the periodic table were analyzed and the bond energies of the diatomic species CuBi and AuBi, yet experimentally unobserved, were predicted on an empirical basis. PMID:24527913

Carta, V; Ciccioli, A; Gigli, G

2014-02-14

28

Mechanistic investigation of phosphate ester bond cleavages of glycylphosphoserinyltryptophan radical cations under low-energy collision-induced dissociation.  

PubMed

Under the conditions of low-energy collision-induced dissociation (CID), the canonical glycylphosphoserinyltryptophan radical cation having its radical located on the side chain of the tryptophan residue ([G(p)SW](•+)) fragments differently from its tautomer with the radical initially generated on the ?-carbon atom of the glycine residue ([G(•)(p)SW](+)). The dissociation of [G(•)(p)SW](+) is dominated by the neutral loss of H3PO4 (98 Da), with backbone cleavage forming the [b2 - H](•+)/y1(+) pair as the minor products. In contrast, for [G(p)SW](•+), competitive cleavages along the peptide backbone, such as the formation of [G(p)SW - CO2](•+) and the [c2 + 2H](+)/[z(1) - H](•+) pair, significantly suppress the loss of neutral H3PO4. In this study, we used density functional theory (DFT) to examine the mechanisms for the tautomerizations of [G(•)(p)SW](+) and [G(p)SW](•+) and their dissociation pathways. Our results suggest that the dissociation reactions of these two peptide radical cations are more efficient than their tautomerizations, as supported by Rice-Ramsperger-Kassel-Marcus (RRKM) modeling. We also propose that the loss of H3PO4 from both of these two radical cationic tautomers is preferentially charge-driven, similar to the analogous dissociations of even-electron protonated peptides. The distonic radical cationic character of [G(•)(p)SW](+) results in its charge being more mobile, thereby favoring charge-driven loss of H3PO4; in contrast, radical-driven pathways are more competitive during the CID of [G(p)SW](•+). PMID:23516067

Quan, Quan; Hao, Qiang; Song, Tao; Siu, Chi-Kit; Chu, Ivan K

2013-04-01

29

Mechanistic Investigation of Phosphate Ester Bond Cleavages of Glycylphosphoserinyltryptophan Radical Cations under Low-Energy Collision-Induced Dissociation  

NASA Astrophysics Data System (ADS)

Under the conditions of low-energy collision-induced dissociation (CID), the canonical glycylphosphoserinyltryptophan radical cation having its radical located on the side chain of the tryptophan residue ([G p SW]•+) fragments differently from its tautomer with the radical initially generated on the ?-carbon atom of the glycine residue ([G• p SW]+). The dissociation of [G• p SW]+ is dominated by the neutral loss of H3PO4 (98 Da), with backbone cleavage forming the [b2 - H]•+/y1 + pair as the minor products. In contrast, for [G p SW]•+, competitive cleavages along the peptide backbone, such as the formation of [G p SW - CO2]•+ and the [c2 + 2H]+/[z1 - H]•+ pair, significantly suppress the loss of neutral H3PO4. In this study, we used density functional theory (DFT) to examine the mechanisms for the tautomerizations of [G• p SW]+ and [G p SW]•+ and their dissociation pathways. Our results suggest that the dissociation reactions of these two peptide radical cations are more efficient than their tautomerizations, as supported by Rice-Ramsperger-Kassel-Marcus (RRKM) modeling. We also propose that the loss of H3PO4 from both of these two radical cationic tautomers is preferentially charge-driven, similar to the analogous dissociations of even-electron protonated peptides. The distonic radical cationic character of [G• p SW]+ results in its charge being more mobile, thereby favoring charge-driven loss of H3PO4; in contrast, radical-driven pathways are more competitive during the CID of [G p SW]•+.

Quan, Quan; Hao, Qiang; Song, Tao; Siu, Chi-Kit; Chu, Ivan K.

2013-04-01

30

Dispersion-correcting potentials can significantly improve the bond dissociation enthalpies and noncovalent binding energies predicted by density-functional theory  

SciTech Connect

Dispersion-correcting potentials (DCPs) are atom-centered Gaussian functions that are applied in a manner that is similar to effective core potentials. Previous work on DCPs has focussed on their use as a simple means of improving the ability of conventional density-functional theory methods to predict the binding energies of noncovalently bonded molecular dimers. We show in this work that DCPs developed for use with the LC-?PBE functional along with 6-31+G(2d,2p) basis sets are capable of simultaneously improving predicted noncovalent binding energies of van der Waals dimer complexes and covalent bond dissociation enthalpies in molecules. Specifically, the DCPs developed herein for the C, H, N, and O atoms provide binding energies for a set of 66 noncovalently bonded molecular dimers (the “S66” set) with a mean absolute error (MAE) of 0.21 kcal/mol, which represents an improvement of more than a factor of 10 over unadorned LC-?PBE/6-31+G(2d,2p) and almost a factor of two improvement over LC-?PBE/6-31+G(2d,2p) used in conjunction with the “D3” pairwise dispersion energy corrections. In addition, the DCPs reduce the MAE of calculated X-H and X-Y (X,Y = C, H, N, O) bond dissociation enthalpies for a set of 40 species from 3.2 kcal/mol obtained with unadorned LC-?PBE/6-31+G(2d,2p) to 1.6 kcal/mol. Our findings demonstrate that broad improvements to the performance of DFT methods may be achievable through the use of DCPs.

DiLabio, Gino A., E-mail: Gino.DiLabio@nrc.ca [National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9 (Canada); Department of Chemistry, University of British Columbia, Okanagan, 3333 University Way, Kelowna, British Columbia V1V 1V7 (Canada); Koleini, Mohammad [National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9 (Canada) [National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta T6G 2M9 (Canada); Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4 (Canada)

2014-05-14

31

Dispersion-correcting potentials can significantly improve the bond dissociation enthalpies and noncovalent binding energies predicted by density-functional theory  

NASA Astrophysics Data System (ADS)

Dispersion-correcting potentials (DCPs) are atom-centered Gaussian functions that are applied in a manner that is similar to effective core potentials. Previous work on DCPs has focussed on their use as a simple means of improving the ability of conventional density-functional theory methods to predict the binding energies of noncovalently bonded molecular dimers. We show in this work that DCPs developed for use with the LC-?PBE functional along with 6-31+G(2d,2p) basis sets are capable of simultaneously improving predicted noncovalent binding energies of van der Waals dimer complexes and covalent bond dissociation enthalpies in molecules. Specifically, the DCPs developed herein for the C, H, N, and O atoms provide binding energies for a set of 66 noncovalently bonded molecular dimers (the "S66" set) with a mean absolute error (MAE) of 0.21 kcal/mol, which represents an improvement of more than a factor of 10 over unadorned LC-?PBE/6-31+G(2d,2p) and almost a factor of two improvement over LC-?PBE/6-31+G(2d,2p) used in conjunction with the "D3" pairwise dispersion energy corrections. In addition, the DCPs reduce the MAE of calculated X-H and X-Y (X,Y = C, H, N, O) bond dissociation enthalpies for a set of 40 species from 3.2 kcal/mol obtained with unadorned LC-?PBE/6-31+G(2d,2p) to 1.6 kcal/mol. Our findings demonstrate that broad improvements to the performance of DFT methods may be achievable through the use of DCPs.

DiLabio, Gino A.; Koleini, Mohammad

2014-05-01

32

Mechanical switching and coupling between two dissociation pathways in a P-selectin adhesion bond  

E-print Network

Mechanical switching and coupling between two dissociation pathways in a P-selectin adhesion bond energy barrier. Using a sensitive force probe to test the leukocyte adhesion bond P-selectin glycoprotein bonds exhibit a mechanical strength that increases in proportion to the logarithm of the rate of force

Peterson, Ellengene

33

Photodissociation of CS2 in the vacuum ultraviolet - Determination of bond dissociation energy from the lowest vibrational level of the ground state CS2.  

NASA Technical Reports Server (NTRS)

Photolysis in the vacuum ultraviolet results almost exclusively in the production of S(super-3)P atoms, which is in apparent violation of spin conservation. The threshold energy of incident photons required to produce fluorescence was used to calculate the bond dissociation energy (from the lowest vibrational level of the ground state), and the result agrees with the value previously derived from the photoionization of CS2. The fluorescence excitation spectrum shows peaks corresponding to Rydberg series I and II, indicating that the observed photodissociation of CS2 in the vacuum ultraviolet is mainly the result of predissociation from Rydberg states. The absorption coefficient of CS2 was measured in the region of 1200 to 1400 A.

Okabe, H.

1972-01-01

34

Thermochemistry of C7H16 to C10H22 alkane isomers: primary, secondary, and tertiary C-H bond dissociation energies and effects of branching.  

PubMed

Standard enthalpies of formation (?H°f 298) of methyl, ethyl, primary and secondary propyl, and n-butyl radicals are evaluated and used in work reactions to determine internal consistency. They are then used to calculate the enthalpy of formation for the tert-butyl radical. Other thermochemical properties including standard entropies (S°(T)), heat capacities (Cp(T)), and carbon-hydrogen bond dissociation energies (C-H BDEs) are reported for n-pentane, n-heptane, 2-methylhexane, 2,3-dimethylpentane, and several branched higher carbon number alkanes and their radicals. ?H°f 298 and C-H BDEs are calculated using isodesmic work reactions at the B3LYP (6-31G(d,p) and 6-311G(2d,2p) basis sets), CBS-QB3, CBS-APNO, and G3MP2B3 levels of theory. Structures, moments of inertia, vibrational frequencies, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level for contributions to entropy and heat capacities. Enthalpy calculations for these hydrocarbon radical species are shown to have consistency with the CBS-QB3 and CBS-APNO methods using all work reactions. Our recommended ideal gas phase ?H°f 298 values are from the average of all CBS-QB3, CBS-APNO, and for G3MP2B3, only where the reference and target radical are identical types, and are compared with literature values. Calculated values show agreement between the composite calculation methods and the different work reactions. Secondary and tertiary C-H bonds in the more highly branched alkanes are shown to have bond energies that are several kcal mol(-1) lower than the BDEs in corresponding smaller molecules often used as reference species. Entropies and heat capacities are calculated and compared to literature values (when available) when all internal rotors are considered. PMID:25180943

Hudzik, Jason M; Bozzelli, Joseph W; Simmie, John M

2014-10-01

35

C-C and C-Heteroatom Bond Dissociation Energies in CH3R?C(OH)2: Energetics for Photocatalytic Processes of Organic Diolates on TiO2 Surfaces  

SciTech Connect

The bond energies of a range of gem-diols, CH3R?C(OH)2 (R? = H, F, Cl, Br, CN, NO2, CF3, CH3CH2, CH3CH2CH2, CH3CH2CH2CH2, ((CH3)2)CH, (CH3)3C, ((CH3)2CH)CH2, (CH3CH2)(CH3)CH, C6H5 (CH3CH2)(CH3)CH) which serve as models for binding to a surface have been studied with density functional theory (DFT) and the molecular orbital G3(MP2) methods to provide thermodynamic data for the analysis of the photochemistry of ketones on TiO2. The ultraviolet (UV) photon-induced photodecomposition of adsorbed acetone and 3,3-dimethylbutanone on the rutile TiO2 (110) surface have been investigated with photon stimulated desorption (PSD) and temperature programmed desorption (TPD). The C-CH3 and C-C(R?) bond dissociation energies in CH3R?C(OH)2 were predicted, and our calculated bond dissociation energies are in excellent agreement with the available experimental values. We used a series of isodemic reactions to provide small corrections to the various bond dissociation energies. The calculated bond dissociation energies are in agreement with the observed photodissociation processes except for R? = CF3, suggesting that these processes are under thermodynamic control. For R? = CF3, reaction dynamics also play a role in determining the photodissociation mechanism. The gas phase Brönsted acidities of the gem-diols were calculated. For three molecules, R? = Cl, Br, and NO2, loss of a proton leads to the formation of a complex of acetic acid with the anion Cl-, Br-, and NO2-. The acidities of these three species are very high with the former two having acidities comparable to CF3SO3H. The ketones (R?RC(=O)) are weak Lewis acids except where addition of OH- leads to the dissociation of the complex to form an anion bonded to acetic acid, R' = NO2, Cl, and Br. The X-C bond dissociation energies for a number of X-CO2- species were calculated and these should be useful in correlating with photochemical reactivity studies.

Wang, Tsang-Hsiu; Dixon, David A.; Henderson, Michael A.

2010-08-26

36

Three methods to measure RH bond energies  

SciTech Connect

In this paper the authors compare and contrast three powerful methods for experimentally measuring bond energies in polyatomic molecules. The methods are: radical kinetics; gas phase acidity cycles; and photoionization mass spectroscopy. The knowledge of the values of bond energies are a basic piece of information to a chemist. Chemical reactions involve the making and breaking of chemical bonds. It has been shown that comparable bonds in polyatomic molecules, compared to the same bonds in radicals, can be significantly different. These bond energies can be measured in terms of bond dissociation energies.

Berkowitz, J. [Argonne National Lab., IL (United States); Ellison, G.B. [Univ. of Colorado, Boulder, CO (United States). Dept. of Chemistry and Biochemistry; Gutman, D. [Catholic Univ. of America, Washington, DC (United States). Dept. of Chemistry

1993-03-21

37

Exploring the energy disposal immediately after bond-breaking in solution: the wavelength-dependent excited state dissociation pathways of para-methylthiophenol.  

PubMed

A wavelength-resolved (?pump = 295, 285, 270, and 267 nm) photodissociation study of para-methylthiophenol (p-MePhSH) in ethanol solution has been performed using femtosecond transient absorption (TA) spectroscopy, and the results compared with those from studies of the corresponding photodissociation in cyclohexane solution at 270 nm. Anisotropy spectra are used to identify the electronic character of the initially populated excited state(s). S-H bond fission is found to occur via the dissociative S2(1(1)??*) state, which can be populated directly, or by ultrafast nonradiative transitions from the S3(2(1)??*) state, or by very efficient tunneling from the S1(1(1)??*) state, depending on the excitation wavelength, in line with conclusions from previous gas-phase studies of this same molecular photodissociation (Oliver, T. A. A.; King, G. A.; Tew, D. P.; Dixon R. N.; Ashfold, M. N. R. J. Phys. Chem. A 2012, 116, 12444). p-MePhS radicals are observed on a time scale faster than the instrument response at all wavelengths, but the available time resolution affords a rare opportunity to explore the branching between different electronic states of a product (the à and X? states of the p-MePhS radical in this case). The present study provides estimates of this branching in the products formed immediately after the first pass through the conical intersection (CI) between the S2 and S0 states. At 270 nm, for example, we identify a marked population inversion in the radical products, in contrast to the reported gas phase behavior. The finding that the contrast in branching ratio is largest between cyclohexane solution and the gas phase, with ethanol being intermediate, can be rationalized by recognizing the differing distributions of the S-H torsion angle (relative to the ring plane) in a room temperature solution compared with those in a jet-cooled molecular beam. The available time resolution also allows exploration of the electronic quenching of nascent à state radicals as solvent motion encourages recrossing of the S2/S0 CI. The average separation distance, , between the H + p-MePhS products arising in successful dissociation events is seen to increase with decreasing photolysis wavelength. This finding accords with the previous gas phase results, which determined that most of the excess energy following population of the dissociative S2 state (directly, or by ultrafast coupling from the S3 state) is released as product translation, and the expectation that should scale with the total kinetic energy release. The present work also confirms that geminate recombination of the H + p-MePhS products leads not just to reformation of parent p-MePhSH molecules but also to alternative adducts wherein the H atom bonds to the benzene ring. Analysis of the present data and results of high level ab initio calculations together with recent UV-IR pump-probe measurements (Murdock, D.; Harris, S. J.; Karsili, T. N. V.; Greetham, G. M.; Clark, I. P.; Towrie, M.; Orr-Ewing, A. J.; Ashfold, M. N. R. J. Phys. Chem. Lett. 2012, 3, 3715) allows identification of the likely adduct structures. PMID:24047130

Zhang, Yuyuan; Oliver, Thomas A A; Das, Saptaparna; Roy, Anirban; Ashfold, Michael N R; Bradforth, Stephen E

2013-11-21

38

Evidence for a lower enthalpy of formation of hydroxyl radical and a lower gas-phase bond dissociation energy of water  

Microsoft Academic Search

There are two experimental approaches to determining ÎH{sub f0}{sup o}(OH), which produce values of this key thermodynamic quantity that differ by >0.5 kcal\\/mol. The apparent uncertainty of the positive ion cycle approach resides in the measurement of the appearance energy of OH{sup +} from HâO, while the uncertainty of the spectroscopic approach resides in the determination of the dissociation energy

Branko Ruscic; David Feller; David A. Dixon; Kirk A. Peterson; Lawrence B. Harding; Robert L. Asher; Albert F. Wagner

2001-01-01

39

Dissociation energy and dynamics of water clusters  

NASA Astrophysics Data System (ADS)

The state-to-state vibrational predissociation (VP) dynamics of water clusters were studied following excitation of a vibrational mode of each cluster. Velocity-map imaging (VMI) and resonance-enhanced multiphoton ionization (REMPI) were used to determine pair-correlated center-of-mass translational energy distributions. Product energy distributions and dissociation energies were determined. Following vibrational excitation of the HCl stretch fundamental of the HCl-H2O dimer, HCl fragments were detected by 2 + 1 REMPI via the f 3?2(nu' = 0) ? X 1Sigma+(nu'' = 0) and V1Sigma + (nu' = 11 and 12) ? X1Sigma+ (nu'' = 0) transitions. REMPI spectra clearly show HCl from dissociation produced in the ground vibrational state with J'' up to 11. The fragments' center-of-mass translational energy distributions were determined from images of selected rotational states of HCl and were converted to rotational state distributions of the water cofragment. All the distributions could be fit well when using a dimer dissociation energy of bond dissociation energy D0 = 1334 +/- 10 cm--1. The rotational distributions in the water cofragment pair-correlated with specific rotational states of HCl appear nonstatistical when compared to predictions of the statistical phase space theory. A detailed analysis of pair-correlated state distributions was complicated by the large number of water rotational states available, but the data show that the water rotational populations increase with decreasing translational energy. H2O fragments of this dimer were detected by 2 + 1 REMPI via the C˜1B1(000) ? X˜1A1(000) transition. REMPI clearly shows that H2O from dissociation is produced in the ground vibrational state. The fragment's center-of-mass translational energy distributions were determined from images of selected rotational states of H2O and were converted to rotational state distributions of the HCl cofragment. The distributions gave D0 = 1334 +/- 10 cm --1 and show a clear preference for rotational levels in the HCl fragment that minimize translational energy release. The usefulness of 2 + 1 REMPI detection of water fragment is discussed. The hydrogen bonding in water is dominated by pair-wise dimer interactions, and the predissociation of the water dimer following vibrational excitation is reported. The measured D0 values of (H 2O)2 and (D2O)2, 1105 and 1244 +/- 10 cm--1, respectively, are in excellent agreement with the calculated values of 1103 and 1244 +/- 5 cm--1. Pair-correlated water fragment rovibrational state distributions following vibrational predissociation of (H2O)2 and (D2O) 2 were obtained upon excitation of the hydrogen bonded OH and OD stretch fundamentals, respectively. Quasiclassical trajectory calculations, using an accurate full-dimensional potential energy surface, are in accord with and help to elucidate experiment. Experiment and theory find predominant excitation of the fragment bending mode upon hydrogen bond breaking. A minor channel is also observed in which both fragments are in the ground vibrational state and are highly rotationally excited. The theoretical calculations reveal equal probability of bending excitation in the donor and acceptor subunits, which is a result of interchange of donor and acceptor roles. The rotational distributions associated with the major channel, in which one water fragment has one quantum of bend, and the minor channel with both water fragments in the ground vibrational state are calculated, and are in agreement with experiment. (Abstract shortened by UMI.)

Ch'ng, Lee Chiat

40

Energy pulse bonding  

NASA Technical Reports Server (NTRS)

To eliminate many of the present termination problems a technique called energy pulse bonding (EPB) was developed. The process demonstrated the capability of: (1) joining conductors without prior removal of insulations, (2) joining conductors without danger of brittle intermetallics, (3) increased joint temperature capability, (4) simultaneous formation of several bonds, (5) capability of higher joint density, and (6) a production oriented process. The following metals were successfully bonded in the solid state: copper, beryllium copper, phosphor bronze, aluminum, brass, and Kovar.

Smith, G. C.

1972-01-01

41

Study of the kinetics of the gas-phase, iodine catalyzed elimination of HBr from isobutylbromide: the tertiary C-H bond dissociation energy in isobutylbromide.  

E-print Network

pressure and T K. Thus i f A-B represents a molecule with a bond between A and B fragments, then DH'(A-B)=AH'(1. 1, T) for the process: 7 r A-B(g) ? A(g)+B(g) (I 1) Since most bond breaking reactions are endothermic processes, DH will generally...

Jirustithipong, Pongsiri

2012-06-07

42

Heteronuclear rare-gas dimer bonding: Understanding the nature of the Rydberg states that dissociate to the highest energy level of the Xe*(5d) manifold  

NASA Astrophysics Data System (ADS)

(1+1') resonance enhanced multiphoton ionization (REMPI) spectra of jet-cooled KrXe and ArXe in the vicinity of the high energy Xe*5d[3/2]10?Xe(1S0) atomic line at 83889.99 cm-1 were obtained by exciting the neutral dimers with tunable coherent vacuum ultraviolet (VUV) radiation generated by four-wave sum mixing in mercury vapor, and then detecting the resultant ions in a time-of-flight (TOF) mass spectrometer. Precise excited state constants were derived from analyses of the resultant vibrational fine structure, while equilibrium bond lengths were estimated from Franck-Condon factor intensity simulations. Excited state symmetries were deduced from separate ultraviolet (UV) (2+1) REMPI spectra recorded with linearly and circularly polarized light. The results of this work confirm a recent model proposed by Lipson and Field, where the RgXe*(5d) states are predicted to be strongly destabilized relative to RgXe*(6p) due to strong 5d-6p Xe* l-mixing induced by the ground state Rg atom partner making up the dimer. Orbital mixing is also responsible for the observation of appreciably strong RgXe*(5d) spectra in both one- and two-photon excitation.

Mao, D. M.; Hu, X. K.; Shi, Y. J.; Lipson, R. H.

1999-08-01

43

Nature of one-dimensional short hydrogen bonding: bond distances, bond energies, and solvent effects.  

PubMed

On the basis of recently synthesized calix[4]hydroquinone (CHQ) nanotubes which were self-assembled with infinitely long one-dimensional (1-D) short hydrogen bonds (SHB), we have investigated the nature of 1-D SHB using first-principles calculations for all the systems including the solvent water. The H-bonds relay (i.e., contiguous H-bonds) effect in CHQs shortens the H...O bond distances significantly (by more than 0.2 A) and increases the bond dissociation energy to a large extent (by more than approximately 4 kcal/mol) due to the highly enhanced polarization effect along the H-bond relay chain. The H-bonds relay effect shows a large increase in the chemical shift associated with the SHB. The average binding energies for the infinite 1-D H-bond arrays of dioles and dions increase by approximately 4 and approximately 9 kcal/mol per H-bond, respectively. The solvent effect (due to nonbridging water molecules) has been studied by explicitly adding water molecules in the CHQ tube crystals. This effect is found to be small with slight weakening of the SHB strength; the H...O bond distance increases only by 0.02 A, and the average binding energy decreases by approximately 1 kcal/mol per H-bond. All these results based on the first-principles calculations are the first detailed analysis of energy gain by SHB and energy loss by solvent effect, based on a partitioning scheme of the interaction energy components. These reliable results elucidate not only the self-assembly phenomena based on the H-bond relay but also the solvent effect on the SHB strength. PMID:14971954

Suh, Seung Bum; Kim, Jong Chan; Choi, Young Cheol; Yun, Sunggoo; Kim, Kwang S

2004-02-25

44

Reconfiguration and dissociation of bonded hydrogen in silicon by energetic ions  

SciTech Connect

We report in situ infrared measurements of ion-induced reconfiguration and dissociation of bonded hydrogen associated with various defects in silicon at low temperatures. Defect-associated Si-H complexes were prepared by low-temperature proton implantation in silicon followed by room-temperature annealing. As a result of subsequent low-temperature {sup 3}He ion irradiation, we observed (1) ion-induced dissociation of Si-H complexes, (2) a notable difference in the dissociation rate of interstitial- and vacancy-type defects, and, unexpectedly, (3) the growth of bond-centered hydrogen, which is generally observed in association with low-temperature proton implantation. These findings provide insight into the mechanisms responsible for the dissociation of hydrogen bonds in silicon and thus have important implications for bond-selective nanoscale engineering and the long-term reliability of state-of-the-art silicon semiconductor and photovoltaic devices.

Nageswara Rao, S. V. S. [Department of Physics, Pondicherry University, Puducherry 605014 (India); Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37235 (United States); Dixit, S. K. [Interdisciplinary Materials Science Program, Vanderbilt University, Nashville, Tennessee 37235 (United States); Vanderbilt Institute of Nanoscale Science and Engineering, Vanderbilt University, Tennessee TN 37235 (United States); Luepke, G. [Department of Applied Science, College of William and Mary, Williamsburg, Virginia 23187 (United States); Tolk, N. H. [Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37235 (United States); Vanderbilt Institute of Nanoscale Science and Engineering, Vanderbilt University, Tennessee TN 37235 (United States); Feldman, L. C. [Department of Physics and Astronomy, Vanderbilt University, Nashville, Tennessee 37235 (United States); Interdisciplinary Materials Science Program, Vanderbilt University, Nashville, Tennessee 37235 (United States); Vanderbilt Institute of Nanoscale Science and Engineering, Vanderbilt University, Tennessee TN 37235 (United States); Institute for Advanced Materials Devices and Nanotechnology, Rutgers University, Piscataway, NJ 08901 (United States)

2011-01-15

45

Understanding Trends in C-H, N-H, and O-H Bond Dissociation Enthalpies  

NASA Astrophysics Data System (ADS)

Theory and experiment are now in good agreement for bond dissociation enthalpies (BDE's) and can be used as checks on each other to identify anomalous data. Both theory and experiment agree that XO-H, XNH-H, and XCH2-H BDE's decrease monotonically by ca. 60 kJ/mol along the series for X = H, but by only ca. 13 kJ/mol for X = CH3. More surprising is the fact that for X = C6H5 the O-H bond is the weakest and the N-H bond is the strongest (by 10-15 kJ/mol). By contrast, BDE's are essentially identical for X = CF3 and X = H. These interesting trends are discussed in terms of a number of concepts useful in advanced organic chemistry courses, including electronegativity, bond length, orbital overlap, unpaired electron delocalization by conjugation and hyperconjugation, and radical stabilization energy. The discussion is supported by EPR data for unpaired electron spin densities and the most recent thermochemical data for BDE's.

Ingold, K. U.; Wright, J. S.

2000-08-01

46

Birge-Sponer Estimation of the C-H Bond Dissociation Energy in Chloroform Using Infrared, Near-Infrared, and Visible Absorption Spectroscopy: An Experiment in Physical Chemistry  

ERIC Educational Resources Information Center

The fundamental and overtone vibrational absorption spectroscopy of the C-H unit in CHCl[subscript 3] is measured for transitions from the v = 0 energy level to v = 1 through v = 5 energy levels. The energies of the transitions exhibit a linearly-decreasing spacing between adjacent vibrational levels as the vibrational quantum number increases.…

Myrick, M. L.; Greer, A. E.; Nieuwland, A. A.; Priore, R. J.; Scaffidi, J.; Andreatta, Danielle; Colavita, Paula

2008-01-01

47

High-level ab initio predictions for the ionization energy, bond dissociation energies, and heats of formation of nickel carbide (NiC) and its cation (NiC+).  

PubMed

The ionization energy (IE) of NiC and the 0 K bond dissociation energies (D(0)) and heats of formation at 0 K (?H(o)(f0)) and 298 K (?H(o)(f298)) for NiC and NiC(+) are predicted by the wavefunction based CCSDTQ(Full)/CBS approach and the multireference configuration interaction (MRCI) method with Davidson correction (MRCI+Q). The CCSDTQ(Full)/CBS calculations presented here involve the approximation to the complete basis set (CBS) limit at the coupled cluster level up to full quadruple excitations along with the zero-point vibrational energy (ZPVE), high-order correlation, core-valence electronic (CV), spin-orbit coupling (SO), and scalar relativistic effect (SR) corrections. The present calculations provide the correct symmetry predictions for the ground states of NiC and NiC(+) to be (1)?(+) and (2)?(+), respectively. The CCSDTQ(Full)/CBS IE(NiC)=8.356 eV is found to compare favorably with the experimental IE value of 8.372 05±0.000 06 eV. The predicted IE(NiC) value at the MRCI+Q/cc-pwCV5Z level, including the ZPVE, SO, and SR effects is 8.00 eV, which is 0.37 eV lower than the experimental value. This work together with the previous experimental and theoretical investigations supports the conclusion that the CCSDTQ(Full)/CBS method is capable of providing reliable IE predictions for 3d-transition metal carbides, such as FeC and NiC. Furthermore, the CCSDTQ(Full)/CBS calculations give the prediction of D(0)(Ni-C)-D(0)(Ni(+)-C)=0.688 eV, which is also consistent with the experimental determination of 0.732 21±0.000 06 eV, whereas the MRCI+Q calculations (with relativistic and CV effects) predict a significantly lower value of 0.39 eV for D(0)(Ni-C)-D(0)(Ni(+)-C). The analysis of the correction terms shows that the CV and valence-valence electronic correlations beyond CCSD(T) wavefunction and the relativistic effect make significant contributions to the calculated thermochemical properties of NiC/NiC(+). For the experimental D(0) and ?H(o)(f0) values of NiC/NiC(+), which are not known experimentally, we recommend the CCSDTQ(Full)/CBS predictions [D(0)(Ni-C)=4.048 eV, D(0)(Ni(+)-C)=3.360 eV, ?H(o)(f0)(NiC)=749.0 kJ/mol, and ?H(o)(f0)(NiC(+))=1555.1 kJ/mol]. PMID:20866136

Lau, Kai-Chung; Chang, Yih Chung; Shi, Xiaoyu; Ng, C Y

2010-09-21

48

Effect of loading conditions on the dissociation behaviour of catch bond clusters  

PubMed Central

Under increasing tensile load, the lifetime of a single catch bond counterintuitively increases up to a maximum and then decreases exponentially like a slip bond. So far, the characteristics of single catch bond dissociation have been extensively studied. However, it remains unclear how a cluster of catch bonds behaves under tensile load. We perform computational analysis on the following models to examine the characteristics of clustered catch bonds: (i) clusters of catch bonds with equal load sharing, (ii) clusters of catch bonds with linear load sharing, and (iii) clusters of catch bonds in micropipette-manipulated cell detachment. We focus on the differences between the slip and catch bond clusters, identifying the critical factors for exhibiting the characteristics of catch bond mechanism for the multiple-bond system. Our computation reveals that for a multiple-bond cluster, the catch bond behaviour could only manifest itself under relatively uniform loading conditions and at certain stages of decohesion, explaining the difficulties in observing the catch bond mechanism under real biological conditions. PMID:21937488

Sun, L.; Cheng, Q. H.; Gao, H. J.; Zhang, Y. W.

2012-01-01

49

A density functional theory for symmetric radical cations from bonding to dissociation.  

PubMed

It has been known for quite some time that approximate density functional (ADF) theories fail disastrously when describing the dissociative symmetric radical cations R(2)(+). By considering this dissociation limit, previous work has shown that Hartree-Fock (HF) theory favors the R(+1)-R(0) charge distribution, whereas DF approximations favor the R(+0.5)-R(+0.5). Yet, general quantum mechanical principles indicate that both these (as well as all intermediate) average charge distributions are asymptotically energy degenerate. Thus, HF and ADF theories mistakenly break the symmetry but in a contradicting way. In this letter, we show how to construct system-dependent long-range corrected (LC) density functionals that can successfully treat this class of molecules, avoiding the spurious symmetry breaking. Examples and comparisons to experimental data is given for R = H, He, and Ne, and it is shown that the new LC theory improves considerably the theoretical description of the R(2)(+) bond properties, the long-range form of the asymptotic potential curve, and the atomic polarizability. The broader impact of this finding is discussed as well, and it is argued that the widespread semiempirical approach which advocates treating the LC parameter as a system-independent parameter is in fact inappropriate under general circumstances. PMID:18834098

Livshits, Ester; Baer, Roi

2008-12-18

50

Theoretical dissociation energies for ionic molecules  

NASA Technical Reports Server (NTRS)

Ab initio calculations at the self-consistent-field and singles plus doubles configuration-interaction level are used to determine accurate spectroscopic parameters for most of the alkali and alkaline-earth fluorides, chlorides, oxides, sulfides, hydroxides, and isocyanides. Numerical Hartree-Fock (NHF) calculations are performed on selected systems to ensure that the extended Slater basis sets employed for the diatomic systems are near the Hartree-Fock limit. Extended Gaussian basis sets of at least triple-zeta plus double polarization equality are employed for the triatomic system. With this model, correlation effects are relatively small, but invariably increase the theoretical dissociation energies. The importance of correlating the electrons on both the anion and the metal is discussed. The theoretical dissociation energies are critically compared with the literature to rule out disparate experimental values. Theoretical (sup 2)Pi - (sup 2)Sigma (sup +) energy separations are presented for the alkali oxides and sulfides.

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

51

The beryllium pentamer: trailing an uneven sequence of dissociation energies.  

PubMed

Recent high-resolution spectroscopic studies by Merritt, Bondybey, and Heaven (Science 2009, 324, 1548) have heightened the anticipation that small beryllium clusters will soon be observed in the laboratory. Beryllium clusters are important discrete models for the theoretical study of metals. The trigonal bipyramidal Be(5) molecule is studied using high-level coupled cluster methods. We obtain the optimized geometry, atomization and dissociation energies, and vibrational frequencies. The c~CCSDT(Q) method is employed to compute the atomization and dissociation energies. In this approach, complete basis set (CBS) extrapolations at the CCSD(T) level of theory are combined with an additive correction for the effect of iterative triple and perturbative quadruple excitations. Harmonic vibrational frequencies are obtained using analytic gradients computed at the CCSD(T) level of theory. We report an atomization energy of 129.6 kcal mol(-1) at the trigonal bipyramid global minimum geometry. The Be(5)?Be(4)+Be dissociation energy is predicted to be 39.5 kcal mol(-1). The analogous dissociation energies for the smaller beryllium clusters are 64.0 kcal mol(-1) (Be(4)?Be(3)+Be), 24.2 kcal mol(-1) (Be(3)?Be(2)+Be), and 2.7 kcal mol(-1) (Be(2)?Be+Be). The trigonal bipyramidal Be(5) structure has an equatorial-equatorial bond length of 2.000 Å and an axial-equatorial distance of 2.060 Å. Harmonic frequencies of 730, 611, 456, 583, 488, and 338 cm(-1) are obtained at the CCSD(T)/cc-pCVQZ level of theory. Quadruple excitations are found to make noticeable contributions to the energetics of the pentamer, which exhibits a significant level of static correlation. PMID:22392888

Ascik, Peter N; Rugango, René; Simmonett, Andrew C; Compaan, Katherine R; Schaefer, Henry F

2012-04-10

52

Coupling of disulfide bond and distal histidine dissociation in human ferrous cytoglobin regulates ligand binding.  

PubMed

Earlier kinetics studies on cytoglobin did not assign functional properties to specific structural forms. Here, we used defined monomeric and dimeric forms and cysteine mutants to show that an intramolecular disulfide bond (C38-C83) alters the dissociation rate constant of the intrinsic histidine (H81) (?1000fold), thus controlling binding of extrinsic ligands. Through time-resolved spectra we have unequivocally assigned CO binding to hexa- and penta-coordinate forms and have made direct measurement of histidine rebinding following photolysis. We present a model that describes how the cysteine redox state of the monomer controls histidine dissociation rate constants and hence extrinsic ligand binding. PMID:25601563

Beckerson, Penny; Reeder, Brandon J; Wilson, Michael T

2015-02-13

53

Dissociation energies of some high temperature molecules containing aluminum  

NASA Technical Reports Server (NTRS)

The Knudsen cell mass spectrometric method has been used to investigate the gaseous molecules Al2, AlSi,AlSiO, AlC2, Al2C2, and AlAuC2. Special attention was given to the experimental considerations and techniques needed to identify and to measure ion intensities for very low abundance molecular species. Second- and third-law procedures were used to obtain reaction enthalpies for pressure calibration independent and isomolecular exchange reactions. Dissociation energies for the molecules were derived from the measured ion intensities, free-energy functions obtained from estimated molecular constants, and auxiliary thermodynamic data. The bonding and stability of these aluminum containing molecules are compared with other similar species.

Stearns, C. A.; Kohl, F. J.

1972-01-01

54

Accurate predictions of C-SO2R bond dissociation enthalpies using density functional theory methods.  

PubMed

The dissociation of the C-SO2R bond is frequently involved in organic and bio-organic reactions, and the C-SO2R bond dissociation enthalpies (BDEs) are potentially important for understanding the related mechanisms. The primary goal of the present study is to provide a reliable calculation method to predict the different C-SO2R bond dissociation enthalpies (BDEs). Comparing the accuracies of 13 different density functional theory (DFT) methods (such as B3LYP, TPSS, and M05 etc.), and different basis sets (such as 6-31G(d) and 6-311++G(2df,2p)), we found that M06-2X/6-31G(d) gives the best performance in reproducing the various C-S BDEs (and especially the C-SO2R BDEs). As an example for understanding the mechanisms with the aid of C-SO2R BDEs, some primary mechanistic studies were carried out on the chemoselective coupling (in the presence of a Cu-catalyst) or desulfinative coupling reactions (in the presence of a Pd-catalyst) between sulfinic acid salts and boryl/sulfinic acid salts. PMID:25170742

Yu, Hai-Zhu; Fu, Fang; Zhang, Liang; Fu, Yao; Dang, Zhi-Min; Shi, Jing

2014-10-14

55

H-atom high-n Rydberg time-of-flight spectroscopy of C-H bond fission in acrolein dissociated at 193 nm  

NASA Astrophysics Data System (ADS)

The experiments presented in this work use H-atom high-n Rydberg time-of-flight spectroscopy to measure the H-atom velocity distribution from one- and multiple-photon dissociation processes in acrolein following excitation at 193 nm. The one-photon H-atom signal is dominated by primary C-H bond fission in acrolein. We compare some of the qualitative features of the recoil translational energy distribution for the observed H atoms with what would be expected based on theoretical results for aldehydic C-H bond fission on the ground and lowest singlet and triplet excited states and conclude that the dissociation cannot proceed through either of these paths. A possible dissociation mechanism is proposed to account for the observed P(ET) that is consistent with the observation of an isotropic dissociation. Finally, we report results on methyl vinyl ketone photodissociation which provide evidence that the primary C-H bond fission process in acrolein is fission of the aldehydic bond.

Parsons, B. F.; Szpunar, D. E.; Butler, L. J.

2002-11-01

56

C?-C? and C?-N bond cleavage in the dissociation of protonated N-benzyllactams: dissociative proton transfer and intramolecular proton-transport catalysis.  

PubMed

In mass spectrometry of protonated N-benzylbutyrolactams, the added proton is initially localized on the carbonyl oxygen, which is the thermodynamically preferred protonation site. Upon collisional activation, dissociative proton transfer takes place leading to the occurrence of fragmentation reactions. The major fragmentations observed are the cleavages of C(?)-C(?) and C(?)-N bonds on the two sides of the methylene linker, which is different to the cleavage of the amide bond itself seen in most amide cases. Theoretical calculations and isotopic labeling experiments demonstrate that the phenyl ring regulates the proton transfer reactions. The proton directly migrates to the C(?) position via a 1,5-H shift leading to the efficient loss of benzene, while it stepwise migrates to the amide nitrogen resulting in the formation of a benzyl cation. The stepwise proton transfer is achieved via intramolecular proton-transport catalysis. The C(?) position accepts the proton from the carbonyl oxygen via a 1,6-H shift, and then donates it to the amide nitrogen via a 1,4-H shift. The general 1,3-H shift from the carbonyl oxygen to the amide nitrogen can be excluded in this case due to its significant energy barrier. The substituent effects are also applied to explore the reaction mechanism, and it proves that both C(?) and C(?) are involved in the dissociative proton transfer processes. For monosubstituted N-benzylbutyrolactams, the abundance ratios of the two competing product ions are well correlated with the nature of the substituents. PMID:22120184

Chai, Yunfeng; Guo, Cheng; Jiang, Kezhi; Pan, Yuanjiang; Sun, Cuirong

2012-01-28

57

Qualifying Energy Conservation Bonds  

E-print Network

will not come after you or your project. 10 20% Savings Clarified ESL-KT-13-12-39 CATEE 2013: Clean Air Through Energy Efficiency Conference, San Antonio, Texas Dec. 16-18 11 Joshua Briggs Vice President Green Campus Partners, LLC 732.917.2322 | Office 720...

Briggs, J.

2013-01-01

58

Theoretical dissociation energies for the alkali and alkaline-earth monofluorides and monochlorides  

NASA Technical Reports Server (NTRS)

Spectroscopic parameters are accurately determined for the alkali and alkaline-earth monofluorides and monochlorides by means of ab initio self-consistent field and correlated wave function calculations. Numerical Hartree-Fock calculations are performed on selected systems to ensure that the extended Slater basis sets employed are near the Hartree-Fock limit. Since the bonding is predominantly electrostatic in origin, a strong correlation exists between the dissociation energy (to ions) and the spectroscopic parameter r(e). By dissociating to the ionic limits, most of the differential correlation effects can be embedded in the accurate experimental electron affinities and ionization potentials.

Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.

1986-01-01

59

H-atom high-n Rydberg time-of-flight spectroscopy of C–H bond fission in acrolein dissociated at 193 nm  

Microsoft Academic Search

The experiments presented in this work use H-atom high-n Rydberg time-of-flight spectroscopy to measure the H-atom velocity distribution from one- and multiple-photon dissociation processes in acrolein following excitation at 193 nm. The one-photon H-atom signal is dominated by primary C–H bond fission in acrolein. We compare some of the qualitative features of the recoil translational energy distribution for the observed

B. F. Parsons; D. E. Szpunar; L. J. Butler

2002-01-01

60

H-atom high-n Rydberg time-of-flight spectroscopy of CH bond fission in acrolein dissociated at 193 nm  

Microsoft Academic Search

The experiments presented in this work use H-atom high-n Rydberg time-of-flight spectroscopy to measure the H-atom velocity distribution from one- and multiple-photon dissociation processes in acrolein following excitation at 193 nm. The one-photon H-atom signal is dominated by primary C-H bond fission in acrolein. We compare some of the qualitative features of the recoil translational energy distribution for the observed

B. F. Parsons; D. E. Szpunar; L. J. Butler

2002-01-01

61

Inhomogeneous electron gas theory of molecular dissociation energies  

Microsoft Academic Search

By separating the total energy of atoms and diatomic molecules into the sum of Thomas-Fermi, density gradient and exchange energies, the dissociation energy D, divided by the square of the total number of electrons in the molecule, is related by a simple analytic formula to the inhomogeneity kinetic energy of electron gas theory, for the equilibrium molecule. The shape of

N. H. March

1991-01-01

62

Cleavage of Multiple Disulfide Bonds in Insulin via Gold Cationization and Collision-induced Dissociation  

PubMed Central

Intact bovine insulin, with its two chains linked via two disulfide linkages, has been used as a model system to study the incorporation of one or more gold cations as means for facilitating the cleavage of multiple disulfide bonds in a tandem mass spectrometry experiment. Gas-phase ion/ion reactions involving Au(I)Cl2? or Au(III)Cl4? were used to incorporate either one or two gold cations into multiply-protonated insulin cations, followed by ion trap collision-induced dissociation (CID) of the products. The incorporation of a single gold cation followed by CID showed little evidence for disulfide bond cleavage. Rather, the CID spectra were similar to those acquired for the same charge state with only excess protons present. However, the incorporation of two gold cations, regardless of oxidation state, resulted in efficient cleavage of the disulfide bonds connecting the two chains of insulin. Furthermore, ion trap CID of the insulin complexes containing two gold cations showed more sequence information compared to the complexes containing only one gold cation or no gold cations. The partitioning of the gold cations between the two chains upon CID proved to be largely asymmetric, as both gold cations tended to stay together. There appeared to be a slight preference for both gold cations to partition into the B-chain. However, the relatively low contribution from single chain ions with only one gold ion suggests a degree of cooperativity in the overall mechanism for separation of the two chains. PMID:22125416

Mentinova, Marija; McLuckey, Scott A.

2011-01-01

63

Effects of Carbonyl Bond and Metal Cluster Dissociation and Evaporation Rates on Predictions of Nanotube Production in HiPco  

NASA Technical Reports Server (NTRS)

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNT) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the co-formation of CO2. It is shown that the production of CO2 is significantly greater for FeCO due to its lower bond energy as compared with that ofNiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

Scott, Carl D.; Smalley, Richard E.

2002-01-01

64

C-H bond dissociation enthalpies in norbornane. An experimental and computational study.  

PubMed

Gas-phase C-H bond dissociation enthalpies (BDEs) in norbornane were determined by quantum chemistry calculations and the C2-H BDE was experimentally obtained for the first time by time-resolved photoacoustic calorimetry. CBS-Q and CBS-QB3 methods were used to derive the values DH degrees (C1-H) = 449 kJ mol-1, DH degrees (C7-H) = 439 kJ mol-1, and DH degrees (C2-H) = 413 kJ mol-1. The experimental result DH degrees (C2-H) = 414.6 +/- 5.4 kJ mol-1 is in excellent agreement with the theoretical value. The trend DH degrees (C1-H) > DH degrees (C7-H) > DH degrees (C2-H) is discussed. PMID:18348570

Nunes, Paulo M; Estacio, Sílvia G; Lopes, Gustavo T; Costa Cabral, Benedito J; Borges dos Santos, Rui M; Martinho Simões, José A

2008-04-17

65

Defining the Disulfide Bonds of Insulin-like Growth Factor-binding Protein-5 by Tandem Mass Spectrometry with Electron Transfer Dissociation and Collision-induced Dissociation*  

PubMed Central

The six high-affinity insulin-like growth factor-binding proteins (IGFBPs) comprise a conserved family of secreted molecules that modulate IGF actions by regulating their half-life and access to signaling receptors, and also exert biological effects that are independent of IGF binding. IGFBPs are composed of cysteine-rich amino- (N-) and carboxyl- (C-) terminal domains, along with a cysteine-poor central linker segment. IGFBP-5 is the most conserved IGFBP, and contains 18 cysteines, but only 2 of 9 putative disulfide bonds have been mapped to date. Using a mass spectrometry (MS)-based strategy combining sequential electron transfer dissociation (ETD) and collision-induced dissociation (CID) steps, in which ETD fragmentation preferentially induces cleavage of disulfide bonds, and CID provides exact disulfide linkage assignments between liberated peptides, we now have definitively mapped 5 disulfide bonds in IGFBP-5. In addition, in conjunction with ab initio molecular modeling we are able to assign the other 4 disulfide linkages to within a GCGCCXXC motif that is conserved in five IGFBPs. Because of the nature of ETD fragmentation MS experiments were performed without chemical reduction of IGFBP-5. Our results not only establish a disulfide bond map of IGFBP-5 but also define a general approach that takes advantage of the specificity of ETD and the scalability of tandem MS, and the predictive power of ab initio molecular modeling to characterize unknown disulfide linkages in proteins. PMID:22117064

Nili, Mahta; Mukherjee, Aditi; Shinde, Ujwal; David, Larry; Rotwein, Peter

2012-01-01

66

Ionization energy of methylene revisited: Improved values for the enthalpy of formation of CHâ and the bond dissociation energy of CHâ via simultaneous solution of the local thermochemical network  

Microsoft Academic Search

The appearance energy of the CHâ{sup +} fragment from CHâCO has been carefully remeasured and fitted by a model curve, producing EAâ(CHâ{sup +}\\/CHâCO) = 13.743 and 0.005 eV. This value can be sequentially propagated through selected thermochemical cycles to yield individual values for EI(CHâ), Dâ(H-CHâ), ÎH°{sub f0}(CHâ), and ÎH°{sub f0}(CHâCO). A set of values with a statistically larger weight is

B. Ruscic; M. Litorja; R. L. Asher

1999-01-01

67

Mass spectrometric and theoretical studies on dissociation of the Ssbnd S bond in the allicin: Homolytic cleavage vs heterolytic cleavage  

NASA Astrophysics Data System (ADS)

On the basis of the tandem mass spectrometry (ESI-MS/MS) technique and DFT calculations, an experimental and theoretical investigation has been conducted into the gas-phase dissociation of the S1sbnd S1' bond in the allicin as well as that of the Ssbnd C (S1sbnd C2, S1'sbnd C2') bond. Meanwhile, the influence of protonation, alkali metal ion and electron transfer on the dissociation of the S1sbnd S1' bond has been taken into account. ESI-MS/MS experiments and DFT calculations show that in the neutral allicin, [allicin + Li]+ and [allicin + Na]+, the S1sbnd S1' bond favors homolytic cleavage, while in the allicin radical cation and protonated allicin, the S1sbnd S1' bond prefers heterolytic cleavage. In addition, alkali metal ions can strengthen the S1sbnd S1' bond in the allicin, while protonation or the loss of an electron will weaken the S1sbnd S1' bond.

Zhang, Xiang

2012-08-01

68

Photodissociation dynamics of thiophenol-d1: the nature of excited electronic states along the S-D bond dissociation coordinate.  

PubMed

The S-D bond dissociation dynamics of thiophenol-d1 (C6H5SD) pumped at 266, 243, and 224 nm are examined using the velocity map ion imaging technique. At both 266 and 243 nm, distinct peaks associated with X and A states of the phenylthiyl radical (C6H5S*) are observed in the D+ image at high and low kinetic energy regions, respectively. The partitioning of the available energy into the vibrational energy of the phenylthiyl radical is found to be enhanced much more strongly at 266 nm compared to that at 243 nm. This indicates that the pipi* electronic excitation at 266 nm is accompanied by significant vibrational excitation. Given the relatively large anisotropy parameter of -0.6, the S-D dissociation at 266 nm is prompt and should involve the efficient coupling to the upper-lying n(pi)sigma* repulsive potential energy surface. The optical excitation of thiophenol at 224 nm is tentatively assigned to the pisigma* transition, which leads to the fast dissociation on the repulsive potential energy surface along the S-D coordinate. The nature of the electronic transitions associated with UV absorption bands is investigated with high-level ab initio calculations. Excitations to different electronic states of thiophenol result in unique branching ratios and vibrational excitations for the fragment of the phenylthiyl radical in the two lowest electronic states. PMID:19728695

Lim, Jeong Sik; Choi, Heechol; Lim, Ivan S; Park, Seong Byung; Lee, Yoon Sup; Kim, Sang Kyu

2009-10-01

69

Dissociation of OCS by high energy highly charged ion impact  

NASA Astrophysics Data System (ADS)

Various dissociation channels of OCS q+ (where q = 2 to 4), formed in the interaction of 5 MeV u-1 Si12+ ion beam with neutral OCS, have been studied using recoil-ion momentum spectroscopy. The concerted and/or sequential nature of dissociation is inferred from the shape and slope of the coincidence islands in the 2D coincidence map. It is observed that the C+ + S+ + O channel results from concerted as well as sequential decay of OCS2+. However the other channels originate purely from the concerted process in which the two terminal fragments (oxygen and sulphur) fly back to back and the central carbon fragment is left with negligible momentum. The kinetic energy release (KER) distributions for all the fragmentation channels arising from the dissociation of OCS q+ (where q = 2 to 4) have been measured and compared with the available data in the literature. It is observed that the KER values for complete Coulomb fragmentation channels are much smaller than those of incomplete Coulomb fragmentation cases and the KER increases with the increasing charge states of the parent molecular ions. From the momentum correlation map, we estimated the geometry of the precursor molecular ion undergoing three-body dissociation and inferred that bent dissociative states are involved in most of the fragmentation channels of OCS q+.

Jana, Mridula Rani; Ghosh, Pradip N.; Ray, Biswajit; Bapat, Bhas; Kushawaha, Rajesh Kumar; Saha, Koushik; Prajapati, Ishwar A.; Safvan, C. P.

2014-09-01

70

Dissociation of OCS by high energy highly charged ion impact  

NASA Astrophysics Data System (ADS)

Various dissociation channels of OCSq+ (where q = 2 to 4), formed in the interaction of 5 MeV u-1 Si12+ ion beam with neutral OCS, have been studied using recoil-ion momentum spectroscopy. The concerted and/or sequential nature of dissociation is inferred from the shape and slope of the coincidence islands in the 2D coincidence map. It is observed that the C+ + S+ + O channel results from concerted as well as sequential decay of OCS2+. However the other channels originate purely from the concerted process in which the two terminal fragments (oxygen and sulphur) fly back to back and the central carbon fragment is left with negligible momentum. The kinetic energy release (KER) distributions for all the fragmentation channels arising from the dissociation of OCSq+ (where q = 2 to 4) have been measured and compared with the available data in the literature. It is observed that the KER values for complete Coulomb fragmentation channels are much smaller than those of incomplete Coulomb fragmentation cases and the KER increases with the increasing charge states of the parent molecular ions. From the momentum correlation map, we estimated the geometry of the precursor molecular ion undergoing three-body dissociation and inferred that bent dissociative states are involved in most of the fragmentation channels of OCSq+.

Rani Jana, Mridula; Ghosh, Pradip N.; Ray, Biswajit; Bapat, Bhas; Kushawaha, Rajesh Kumar; Saha, Koushik; Prajapati, Ishwar A.; Safvan, C. P.

2014-09-01

71

Low-energy dissociative recombination in small polyatomic molecules.  

PubMed

Indirect dissociative recombination of low-energy electrons and molecular ions often occurs through capture into vibrationally excited Rydberg states. Properties of vibrational autoionization, the inverse of this capture mechanism, are used to develop some general ideas about the indirect recombination process, and these ideas are illustrated by examples from the literature. In particular, the ?v = -1 propensity rule for vibrational autoionization, i.e., that vibrational autoionization occurs by the minimum energetically allowed change in vibrational quantum numbers, leads to the prediction of thresholds in the dissociative recombination cross sections and rates at the corresponding vibrational thresholds. Capture into rotationally excited Rydberg states is also discussed in terms of recent low-temperature studies of the dissociative recombination of H(3)(+). PMID:21142300

Jungen, Ch; Pratt, S T

2010-12-01

72

Activation Energies for Dissociation of Double Strand Oligonucleotide Anions: Evidence for Watson–Crick Base Pairing in Vacuo  

PubMed Central

The dissociation kinetics of a series of complementary and noncomplementary DNA duplexes, (TGCA)23?, (CCGG)23?, (AATTAAT)23?, (CCGGCCG)23?, A7·T73?, A7·A73?, T7·T73?, and A7·C73? were investigated using blackbody infrared radiative dissociation in a Fourier transform mass spectrometer. From the temperature dependence of the unimolecular dissociation rate constants, Arrhenius activation parameters in the zero-pressure limit are obtained. Activation energies range from 1.2 to 1.7 eV, and preexponential factors range from 1013 to 1019 s?1. Dissociation of the duplexes results in cleavage of the noncovalent bonds and/or cleavage of covalent bonds leading to loss of a neutral nucleobase followed by backbone cleavage producing sequence-specific (a – base) and w ions. Four pieces of evidence are presented which indicate that Watson–Crick (WC) base pairing is preserved in complementary DNA duplexes in the gas phase: i. the activation energy for dissociation of the complementary dimer, A7·T73?, to the single strands is significantly higher than that for the related noncomplementary A7·A73? and T7·T73? dimers, indicating a stronger interaction between strands with a specific base sequence, ii. extensive loss of neutral adenine occurs for A7·A73? and A7·C73? but not for A7·T73? consistent with this process being shut down by WC hydrogen bonding, iii. a correlation is observed between the measured activation energy for dissociation to single strands and the dimerization enthalpy (??Hd) in solution, and iv. molecular dynamics carried out at 300 and 400 K indicate that WC base pairing is preserved for A7·T73? duplex, although the helical structure is essentially lost. In combination, these results provide strong evidence that WC base pairing can exist in the complete absence of solvent. PMID:16498487

Schnier, Paul D.; Klassen, John S.; Strittmatter, Eric F.; Williams*, Evan R.

2005-01-01

73

Strength of Hydrogen Bond Network Takes Crucial Roles in the Dissociation Process of Inhibitors from the HIV-1 Protease Binding Pocket  

PubMed Central

To understand the underlying mechanisms of significant differences in dissociation rate constant among different inhibitors for HIV-1 protease, we performed steered molecular dynamics (SMD) simulations to analyze the entire dissociation processes of inhibitors from the binding pocket of protease at atomistic details. We found that the strength of hydrogen bond network between inhibitor and the protease takes crucial roles in the dissociation process. We showed that the hydrogen bond network in the cyclic urea inhibitors AHA001/XK263 is less stable than that of the approved inhibitor ABT538 because of their large differences in the structures of the networks. In the cyclic urea inhibitor bound complex, the hydrogen bonds often distribute at the flap tips and the active site. In contrast, there are additional accessorial hydrogen bonds formed at the lateral sides of the flaps and the active site in the ABT538 bound complex, which take crucial roles in stabilizing the hydrogen bond network. In addition, the water molecule W301 also plays important roles in stabilizing the hydrogen bond network through its flexible movement by acting as a collision buffer and helping the rebinding of hydrogen bonds at the flap tips. Because of its high stability, the hydrogen bond network of ABT538 complex can work together with the hydrophobic clusters to resist the dissociation, resulting in much lower dissociation rate constant than those of cyclic urea inhibitor complexes. This study may provide useful guidelines for design of novel potent inhibitors with optimized interactions. PMID:21559397

Li, Dechang; Ji, Baohua; Hwang, Keh-Chih; Huang, Yonggang

2011-01-01

74

Mutual heavy ion dissociation in peripheral collisions at ultrarelativistic energies  

NASA Astrophysics Data System (ADS)

We study mutual dissociation of heavy nuclei in peripheral collisions at ultrarelativistic energies. Earlier this process was proposed for beam luminosity monitoring via simultaneous registration of forward and backward neutrons in zero degree calorimeters at the Relativistic Heavy Ion Collider (RHIC) at Brookhaven National Laboratory. Electromagnetic dissociation of heavy ions is considered in the framework of the Weizsäcker-Williams method and simulated by the RELDIS code. Photoneutron cross sections measured in different experiments and calculated by the GNASH code are used as input for the calculations of dissociation cross sections. The difference in results obtained with different inputs provides a realistic estimation for the systematic uncertainty of the luminosity monitoring method. Contributions to simultaneous neutron emission due to grazing nuclear interactions is calculated within the abrasion model. A good description of the CERN SPS experimental data on Au and Pb dissociation gives confidence in the predictive power of the model for AuAu and PbPb collisions at the RHIC and the Large Hadron Collider at CERN.

Pshenichnov, I. A.; Bondorf, J. P.; Mishustin, I. N.; Ventura, A.; Masetti, S.

2001-08-01

75

The Dissociative Energy of Ne_2^+ Obtained by Measurement of the Kinetic Energy Released by Dissociative Recombination  

NASA Astrophysics Data System (ADS)

Time-of-Flight spectroscopy has been used to study the final product states of the dissociative recombination reaction of Ne_2^+. The reaction takes place in a low pressure, low voltage, hot cathode glow discharge surrounded by a magnetic field. The discharge products are collimated into a beam, which passes through a electric field of about 500V/cm to remove charged products and Rydberg atoms, and is then chopped by a rotary beam chopper. The flight path of 1.227 M gives sufficient velocity resolution to resolve the s and p states at the high velocity end of the time spectra. The low velocity energy resolution allows a new and better determination of the dissociation energy of the molecular ion. Preliminary analysis of the data indicates that twenty final product states have been observed, including the ground state, and that the dissociation energy of Ne_2^+ is 1.26±.02eV. ^1Currently at University of Connecticut, Storrs ^2Supported by AFOSR F49620-93-1-0159

Ramos, Gloria; Sheldon, J. W.; Hardy, K. A.; Peterson, J. R.

1996-11-01

76

Adhesive bonding using variable frequency microwave energy  

SciTech Connect

Methods of facilitating the adhesive bonding of various components with variable frequency microwave energy are disclosed. The time required to cure a polymeric adhesive is decreased by placing components to be bonded via the adhesive in a microwave heating apparatus having a multimode cavity and irradiated with microwaves of varying frequencies. Methods of uniformly heating various articles having conductive fibers disposed therein are provided. Microwave energy may be selectively oriented to enter an edge portion of an article having conductive fibers therein. An edge portion of an article having conductive fibers therein may be selectively shielded from microwave energy.

Lauf, Robert J. (Oak Ridge, TN); McMillan, April D. (Knoxville, TN); Paulauskas, Felix L. (Oak Ridge, TN); Fathi, Zakaryae (Cary, NC); Wei, Jianghua (Raleigh, NC)

1998-01-01

77

Mechanistic examination of C?-C? bond cleavages of tryptophan residues during dissociations of molecular peptide radical cations.  

PubMed

In this study, we used collision-induced dissociation (CID) to examine the gas-phase fragmentations of [G(n)W](•+) (n = 2-4) and [GXW](•+) (X = C, S, L, F, Y, Q) species. The C(?)-C(?) bond cleavage of a C-terminal decarboxylated tryptophan residue ([M - CO(2)](•+)) can generate [M - CO(2) - 116](+), [M - CO(2) - 117](•+), and [1H-indole](•+) (m/z 117) species as possible product ions. Competition between the formation of [M - CO(2) - 116](+) and [1H-indole](•+) systems implies the existence of a proton-bound dimer formed between the indole ring and peptide backbone. Formation of such a proton-bound dimer is facile via a protonation of the tryptophan ?-carbon atom as suggested by density functional theory (DFT) calculations. DFT calculations also suggested the initially formed ion 2, the decarboxylated species that is active against C(?)-C(?) bond cleavage, can efficiently isomerize to form a more stable ?-radical isomer (ion 9) as supported by Rice-Ramsperger-Kassel-Marcus (RRKM) modeling. The C(?)-C(?) bond cleavage of a tryptophan residue also can occur directly from peptide radical cations containing a basic residue. CID of [WG(n)R](•+) (n = 1-3) radical cations consistently resulted in predominant formation of [M - 116](+) product ions. It appears that the basic arginine residue tightly sequesters the proton and allows the charge-remote C(?)-C(?) bond cleavage to prevail over the charge-directed one. DFT calculations predicted that the barrier for the former is 6.2 kcal mol(-1) lower than that of the latter. Furthermore, the pathway involving a salt-bridge intermediate also was accessible during such a bond cleavage event. PMID:22697598

Song, Tao; Ma, Ching-Yung; Chu, Ivan K; Siu, Chi-Kit; Laskin, Julia

2013-02-14

78

Hydrogen Bond Dissociation and Reformation in Methanol Oligomers Following Hydroxyl Stretch Relaxation  

E-print Network

, 2002 Vibrational relaxation and hydrogen bond dynamics in methanol-d dissolved in CCl4 have been and .10 ns time constants. Experiments conducted on ethanol-d solutions in CCl4 demonstrate that the same

Fayer, Michael D.

79

Dissociation of internal energy-selected methyl bromide ion revealed from threshold photoelectron-photoion coincidence velocity imaging  

SciTech Connect

Dissociative photoionization of methyl bromide (CH{sub 3}Br) in an excitation energy range of 10.45–16.90 eV has been investigated by using threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging. The coincident time-of-flight mass spectra indicate that the ground state X{sup 2}E of CH{sub 3}Br{sup +} is stable, and both A{sup 2}A{sub 1} and B{sup 2}E ionic excited states are fully dissociative to produce the unique fragment ion of CH{sub 3}{sup +}. From TPEPICO 3D time-sliced velocity images of CH{sub 3}{sup +} dissociated from specific state-selected CH{sub 3}Br{sup +} ion, kinetic energy release distribution (KERD) and angular distribution of CH{sub 3}{sup +} fragment ion are directly obtained. Both spin-orbit states of Br({sup 2}P) atom can be clearly observed in fast dissociation of CH{sub 3}Br{sup +}(A{sup 2}A{sub 1}) ion along C–Br rupture, while a KERD of Maxwell-Boltzmann profile is obtained in dissociation of CH{sub 3}Br{sup +}(B{sup 2}E) ion. With the aid of the re-calculated potential energy curves of CH{sub 3}Br{sup +} including spin-orbit coupling, dissociation mechanisms of CH{sub 3}Br{sup +} ion in A{sup 2}A{sub 1} and B{sup 2}E states along C–Br rupture are revealed. For CH{sub 3}Br{sup +}(A{sup 2}A{sub 1}) ion, the CH{sub 3}{sup +} + Br({sup 2}P{sub 1/2}) channel is occurred via an adiabatic dissociation by vibration, while the Br({sup 2}P{sub 3/2}) formation is through vibronic coupling to the high vibrational level of X{sup 2}E state followed by rapid dissociation. C–Br bond breaking of CH{sub 3}Br{sup +}(B{sup 2}E) ion can occur via slow internal conversion to the excited vibrational level of the lower electronic states and then dissociation.

Tang, Xiaofeng [Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China) [Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Zhou, Xiaoguo, E-mail: xzhou@ustc.edu.cn, E-mail: yanbing@jlu.edu.cn; Liu, Shilin [Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China) [Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Sun, Zhongfa [Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China)] [Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 (China); Liu, Fuyi; Sheng, Liusi [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China)] [National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei 230029 (China); Yan, Bing, E-mail: xzhou@ustc.edu.cn, E-mail: yanbing@jlu.edu.cn [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China)] [Institute of Atomic and Molecular Physics, Jilin University, Changchun 130012 (China)

2014-01-28

80

Energy-Dependent Electron Activated Dissociation of Metal-Adducted Permethylated Oligosaccharides  

PubMed Central

The effects of varying the electron energy and cationizing agents on electron activated dissociation (ExD) of metal-adducted oligosaccharides were explored, using permethylated maltoheptaose as the model system. Across the examined range of electron energy, the metal-adducted oligosaccharide exhibited several fragmentation processes, including electron capture dissociation (ECD) at low energies, hot-ECD at intermediate energies, and electronic excitation dissociation (EED) at high energies. The dissociation threshold depended on the metal charge carrier(s), whereas the types and sequence spans of product ions were influenced by the metal-oligosaccharide binding pattern. Theoretical modeling contributed insight into the metal-dependent behavior of carbohydrates during low-energy ECD. When ExD was applied to a permethylated high mannose N-linked glycan, EED provided more structural information than either collision-induced dissociation (CID) or low-energy ECD, thus demonstrating its potential for oligosaccharide linkage analysis. PMID:22881449

Yu, Xiang; Huang, Yiqun; Lin, Cheng; Costello, Catherine E.

2013-01-01

81

Quantum Monte Carlo calculations of the dissociation energies of three-electron hemibonded radical cationic dimers.  

PubMed

We report variational and diffusion quantum Monte Carlo (VMC and DMC) calculations of the dissociation energies of the three-electron hemibonded radical cationic dimers of He, NH3, H2O, HF, and Ne. These systems are particularly difficult for standard density-functional methods such as the local-density approximation and the generalized gradient approximation. We have performed both all-electron (AE) and pseudopotential (PP) calculations using Slater-Jastrow wave functions with Hartree-Fock single-particle orbitals. Our results are in good agreement with coupled-cluster CCSD(T) calculations. We have also studied the relative stability of the hemibonded and hydrogen-bonded water radical dimer isomers. Our calculations indicate that the latter isomer is more stable, in agreement with post-Hartree-Fock methods. The excellent agreement between our AE and PP results demonstrates the high quality of the PPs used within our VMC and DMC calculations. PMID:16422594

Gurtubay, I G; Drummond, N D; Towler, M D; Needs, R J

2006-01-14

82

Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide  

NASA Technical Reports Server (NTRS)

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

Scott, Carl D.; Smalley, Richard E.

2003-01-01

83

Formation, structure and bond dissociation thresholds of gas-phase vanadium oxide cluster ions  

Microsoft Academic Search

The formation and structure of gas-phase vanadium oxide cluster anions are examined using a guided ion beam mass spectrometer coupled with a laser vaporization source. The dominant peaks in the anion total mass distribution correspond to clusters having stoichiometries of the form (VO2)n(VO3)m(O2)q-. Collision-induced dissociation studies of the vanadium oxide species V2O4-6-, V3O6-9-, V4O8-10-, V5O11-13-, V6O13-15-, and V7O16-18- indicate that

R. C. Bell; K. A. Zemski; D. R. Justes; A. W. Castleman

2001-01-01

84

Low-energy electron-induced chemistry of condensed-phase hexamethyldisiloxane: Initiating dissociative process and subsequent reactions  

NASA Astrophysics Data System (ADS)

Thin films of condensed hexamethyldisiloxane (HMDSO) have been exposed to electron irradiation at incident energies between 5 and 15 eV and analysed afterwards by thermal desorption spectrometry (TDS). Formation of products is observed at energies at and above 11 eV and quantified at 15 eV by comparison with reference samples of known composition. Gas-phase measurements aiming at detection of dissociative electron attachment (DEA) were, in addition, performed to obtain more insight into the dominant electron-induced dissociation channel expected to initiate further reactions in the condensed phase. Apart from CH4 which is the most obvious product present in exposed films of HMDSO, tetramethylsilane (TMS) and smaller amounts of C2H6 have been detected. The quantity of the products is by one to two orders of magnitude smaller than the amount of decomposed HMDSO. In addition, signals ascribed to unquantified amounts of larger siloxanes have been observed. The present results together with previous gas-phase results from literature suggest that dissociative ionisation leading to Si-C bond rupture and release of a methyl radical is the most important electron-driven initial reaction step. Possible mechanisms of the subsequent reactions induced by the fragments of the initial dissociation reaction are reviewed and discussed in relation to the observed product quantities.

Ipolyi, I.; Burean, E.; Hamann, T.; Cingel, M.; Matejcik, S.; Swiderek, P.

2009-05-01

85

First-row hydrides: Dissociation and ground state energies using quantum Monte Carlo  

E-print Network

First-row hydrides: Dissociation and ground state energies using quantum Monte Carlo Arne Lu to or better than the best previous ab initio results can be obtained using the fixed-node quantum Monte Carlo, the dissociation energies are consistent with experimental values. The fixed-node quantum Monte Carlo method can

Anderson, James B.

86

Formation, structure and bond dissociation thresholds of gas-phase vanadium oxide cluster ions  

Microsoft Academic Search

The formation and structure of gas-phase vanadium oxide cluster anions are examined using a guided ion beam mass spectrometer coupled with a laser vaporization source. The dominant peaks in the anion total mass distribution correspond to clusters having stoichiometries of the form (VO2)n(VO3)m(O2)q?. Collision-induced dissociation studies of the vanadium oxide species V2O4–6?,V3O6–9?,V4O8–10?,V5O11–13?,V6O13–15?, and V7O16–18? indicate that VO2,VO3, and V2O5 units

R. C. Bell; K. A. Zemski; D. R. Justes

2001-01-01

87

Autocatalytic cathodic dehalogenation triggered by dissociative electron transfer through a C-H···O hydrogen bond.  

PubMed

A combined action of the C-H···Oalkoxide hydrogen bonding and Cl···?pyrazolyl dispersive interactions facilitates intramolecular electron transfer (ET) in the transient {Mo(I)(NO)(Tp(Me2))(Oalkoxide)}?(-)···HCCl3 adduct ([Tp(Me2)](-) = ?(3)-hydrotris(3,5-dimethylpyrazol-1-yl)borate), setting off a radical autocatalytic process, eventually leading to chloroform degradation. In the voltammetric curve, this astonishingly fast process is seen as an almost vertical drop-down. The potential at which it occurs is favorably shifted by ca. 1 V in comparison with uncatalyzed reduction. As predicted by DFT calculations, crucial in the initial step is a close and prolonged contact between the electron donor (Mo(I) 4d-based SOMO) and acceptor (?(*)(C-Cl)-based LUMO). This occurs owing to the exceptionally short (dH···O = 1.82 Å) and nearly linear C-H···Oalkoxide bonding, which is reflected by a large ??C-H red-shift of 380 cm(-1) and a noticeable reorganization of electronic density along the H-bond axis. The advantageous noncovalent interactions inside the cavity formed by two pyrazolyl (pz) rings are strengthened during the C-Cl bond elongation coupled with the ET, giving rise to possible transition state stabilization. After the initial period, the reaction proceeds as a series of consecutive alternating direct or Mo(II/I)-mediated electron and proton transfers. Alcohols inhibit the electrocatalysis by binding with the {Mo(I)-Oalkoxide}?(-) active site, and olefins by trapping transient radicals. The proximity and stabilization effects, and competitive inhibition in the studied system may be viewed as analogous to those operating in enzymatic catalysis. PMID:24030591

Roma?czyk, Piotr P; Rado?, Mariusz; Noga, Klemens; Kurek, Stefan S

2013-10-28

88

The vibrational energies of ozone up to the dissociation threshold: Dynamics calculations on an accurate potential energy surface  

E-print Network

The vibrational energies of ozone up to the dissociation threshold: Dynamics calculations present an ab initio potential energy surface for the ground electronic state of ozone. It is global, i. All bound states of nonrotating ozone up to more than 99% of the dissociation energy are calculated

Farantos, Stavros C.

89

Municipal bond financing for renewable energy systems: Community Renewable Energy Guidebook series  

Microsoft Academic Search

A general introduction to the financing of developing local renewable energy resources is presented. This handbook describes three major types of bonds: general obligation bonds, revenue bonds, and special assessment bonds. An innovative way to market bonds - directly marketed small-denomination bonds, or mini-bonds - is described. (MCW)

Levine

1981-01-01

90

A complete look at the multi-channel dissociation of propenal photoexcited at 193 nm: branching ratios and distributions of kinetic energy.  

PubMed

We observed fifteen photofragments upon photolysis of propenal (acrolein, CH(2)CHCHO) at 193 nm using photofragment translational spectroscopy and selective vacuum-ultraviolet (VUV) photoionization. All the photoproducts arise from nine primary and two secondary dissociation pathways. We measured distributions of kinetic energy of products and determined branching ratios of dissociation channels. Dissociation to CH(2)CHCO + H and CH(2)CH + HCO are two major primary channels with equivalent branching ratios of 33%. The CH(2)CHCO fragment spontaneously decomposes to CH(2)CH + CO. A proportion of primary products CH(2)CH from the fission of bond C-C of propenal further decompose to CHCH + H but secondary dissociation HCO ? H + CO is negligibly small. Binary dissociation to CH(2)CH(2) (or CH(3)CH) + CO and concerted three-body dissociation to C(2)H(2) + CO + H(2) have equivalent branching ratios of 14%-15%. The other channels have individual branching ratios of ?1%. The production of HCCO + CH(3) indicates the formation of intermediate methyl ketene (CH(3)CHCO) and the production of CH(2)CCH + OH and CH(2)CC + H(2)O indicate the formation of intermediate hydroxyl propadiene (CH(2)CCHOH) from isomerization of propenal. Distributions of kinetic energy release and dissociation mechanisms are discussed. This work provides a complete look and profound insight into the multi-channel dissociation mechanisms of propenal. The combination of a molecular beam apparatus and synchrotron VUV ionization allowed us to untangle the complex mechanisms of nine primary and two secondary dissociation channels. PMID:21423979

Chaudhuri, Chanchal; Lee, Shih-Huang

2011-04-28

91

Potential energy surface for C2H4I2+ dissociation including spin-orbit effects  

SciTech Connect

Previous experiments [Baer, et al. J. Phys. Chem. A 116, 2833 (2012)] have studied the dissociation of 1,2-diiodoethane radical cation (C2H4I2+•) and found a one-dimensional distribution of translational energy; an odd finding considering most product relative translational energy distributions are two-dimensional. The goal of this study is to obtain an accurate understanding of the potential energy surface (PES) topology for the unimolecular decomposition reaction C2H4I2+• - C2H4I+ + I•. This is done through comparison of many single-reference electronic structure methods, coupled-cluster single point (energy) calculations, and multi-reference calculations used to quantify spin-orbit (SO) coupling effects. We find that the structure of the C2H4I2+• reactant has a substantial effect on the role of SO coupling on the reaction energy. Both the BHandH and MP2 theories with an ECP/6-31++G** basis set, and without SO coupling corrections, provide accurate models for the reaction energetics. MP2 theory gives an unsymmetric structure with different C-I bond lengths, resulting in a SO energy for C2H4I2+• similar to that for the product I-atom and a negligible SO correction to the reaction energy. In contrast, DFT gives a symmetric structure for C2H4I2+•, similar to that of the neutral C2H4I2 parent, resulting in a substantial SO correction and increasing the reaction energy by 6.0-6.5 kcal/mol. Also, we find that for this system single point energy calculations are inaccurate, since a small change in geometry can lead to a large change in energy.

Siebert, Matthew R.; Aquino, Adelia J.; De Jong, Wibe A.; Granucci, Giovanni; Hase, William L.

2012-10-24

92

Effect of ultrasonic energy on interfacial structure and bond strength in copper wire bonding  

Microsoft Academic Search

The effect of ultrasonic energy on the interfacial microstructure in Cu-Al bonds is investigated to establish a relationship between ultrasonic energy, interfacial structure and bonding strength. It is shown that formation of intermetallic compounds (IMCs) at a Cu\\/Al interface is strongly dependent on the character of ultrasonic vibration; higher levels of ultrasonic energy enhance fragmentation of an oxide layer, resulting

H. Xu; C. Liu; V. V. Silberschmidt; M. Sivakumar; Z. Chen

2010-01-01

93

A method for measurements of neutral fragments kinetic energies released to a specific dissociation threshold: optical translational spectroscopy  

Microsoft Academic Search

The optical translational spectroscopy technique, based on the principles of fast ion beam laser spectroscopy (FIBLAS) and translational spectroscopy, allows the kinetic energies study of neutral fragments released through free dissociation of a neutral molecule. This method presents interesting features such as near-threshold energy measurements and selection of a specific dissociation limit. The fragments resulting from free dissociation (not induced)

A. Roney; C. Frigon; M. Larzillière

1999-01-01

94

Enthalpy of formation of anisole: implications for the controversy on the O-H bond dissociation enthalpy in phenol.  

PubMed

Significant discrepancies in the literature data for the enthalpy of formation of gaseous anisole, ?fHmo(PhOCH3, g), have fueled an ongoing controversy regarding the most reliable enthalpy of formation of the phenoxy radical and of the gas phase O-H bond dissociation enthalpy, DHo(PhO-H), in phenol. In the present work ?fHmo(PhOCH3, g) was reassessed using a combination of calorimetric determinations and high-level (W2-F12) ab initio calculations. Static-bomb combustion calorimetry led to the standard molar enthalpy of formation of liquid anisole at 298.15 K, ?fHmo(PhOCH3, l) = ?(117.1 ± 1.4) kJ·mol(-1). The corresponding enthalpy of vaporization was obtained as, ?vapHmo(PhOCH3) = 46.41 ± 0.26 kJ·mol(-1), by Calvet-drop microcalorimetry. These results give ?fHmo(PhOCH3, g) = ?(70.7 ± 1.4) kJ·mol(-1), in excellent agreement with ?fHmo(PhOCH3, g) = ?(70.8 ± 3.2) kJ·mol(-1), obtained from the W2-F12 calculations. The ?fHmo(PhOCH3, g) here recommended leads to ?fHmo(PhO•, g) = 55.5 ± 2.4 kJ·mol(-)1 and DH°(PhO-H) = 368.1 ± 2.6 kJ·mol(-1). PMID:25340952

Simões, Ricardo G; Agapito, Filipe; Diogo, Hermínio P; da Piedade, Manuel E Minas

2014-11-20

95

Analytical approach to molecular liquids. V. Symmetric dissociative dipolar dumbbells with the bonding length ?/3 <= L <= ?/2 and related systems  

NASA Astrophysics Data System (ADS)

The exact asymptotic behavior of the particle-particle direct correlation function for dissociative dipolar dumbbells is discussed. It reveals the sense in which the complete association limit is like a critical point and suggests several approximations as well as the conditions under which they can be expected to be useful. The simplest of these is an extended mean spherical approximation (EMSA) that can be solved analytically for a model liquid of symmetric dissociative dipolar dumbbells with two centers (each bearing a point charge of opposite sign) a distance L apart, when ?/3?L??/2, where ? is the diameter of the spheres that consistute the dumbbells. The analytical expressions for the Born solvation free energy of a symmetric dipolar dumbbell in a symmetric dipolar dumbbell solvent and in a dipolar hard-sphere solvent are also obtained. Such expressions can be expected to be useful in investigating intramolecular electron-transfer reactions. Results for ?/2?L?? that have a somewhat different conceptual status are obtained as well. They suggest a new interpretation of the Percus-Yevick solution to the sticky-sphere model considered by Baxter.

Zhou, Yaoqi; Stell, George

1993-04-01

96

Electron-nuclear energy sharing in above-threshold multiphoton dissociative ionization of H2.  

PubMed

We report experimental observation of the energy sharing between electron and nuclei in above-threshold multiphoton dissociative ionization of H2 by strong laser fields. The absorbed photon energy is shared between the ejected electron and nuclei in a correlated fashion, resulting in multiple diagonal lines in their joint energy spectrum governed by the energy conservation of all fragment particles. PMID:23889391

Wu, J; Kunitski, M; Pitzer, M; Trinter, F; Schmidt, L Ph H; Jahnke, T; Magrakvelidze, M; Madsen, C B; Madsen, L B; Thumm, U; Dörner, R

2013-07-12

97

Electron-Nuclear Energy Sharing in Above-Threshold Multiphoton Dissociative Ionization of H2  

NASA Astrophysics Data System (ADS)

We report experimental observation of the energy sharing between electron and nuclei in above-threshold multiphoton dissociative ionization of H2 by strong laser fields. The absorbed photon energy is shared between the ejected electron and nuclei in a correlated fashion, resulting in multiple diagonal lines in their joint energy spectrum governed by the energy conservation of all fragment particles.

Wu, J.; Kunitski, M.; Pitzer, M.; Trinter, F.; Schmidt, L. Ph. H.; Jahnke, T.; Magrakvelidze, M.; Madsen, C. B.; Madsen, L. B.; Thumm, U.; Dörner, R.

2013-07-01

98

On the differentiation of diffusion bond strength using the total acoustic energy reflected from the bond  

SciTech Connect

Single frequency reflection coefficients and reflected energy over a broad acoustic band (2-15 MHz), and the mechanical bond strength were evaluated on diffusion bonds in Cu/Cu, Cu/Ni, and Ti-6Al-4V/self. Results indicate that energy data are more sensitive to small bond strength changes as predicted by Parseval`s theorem. In all cases, the energy reflected mainly originates at voids still present at the original interface location. Other microstructural features caused by the interdiffusion appear to diminish the reflected energy. 7 refs., 4 figs.

Ojard, G.C. [Pratt and Whitney, West Palm Beach, FL (United States); Buck, O.; Rehbein, D.K.; Hughes, M.S. [Iowa State Univ. of Science and Technology, Ames, IA (United States). Center for NDE

1992-12-31

99

Energy and pressure dependence of the CO 2 laser induced dissociation of sulfur hexafluoride  

Microsoft Academic Search

Low pressure SF6 with its isotopes in natural abundance was irradiated by a pulsed CO2 laser operated on theP20 line (10.6 ?m band). Dissociation yields of32SF6 and34SF6 were measured separately. If the radiation is focussed into the cell, the dissociation yield is proportional to the 3\\/2 power\\u000a of the laser energy, as was derived under general conditions and confirmed experimentally.

W. Fuss; T. P. Cotter

1977-01-01

100

Trajectory study of energy partition in CF 3CN ? CF 3 + CN dissociation dynamics  

NASA Astrophysics Data System (ADS)

The classical trajectory method has been used to study the internal dynamics and unimolecular dissociation of CF 3CN at energies consistent with infrared multiphoton excitation conditions. A model potential energy function consisting of Morse stretches and attenuated bending terms is used in the trajectory study. At an excitation energy of 150 kcal/mol the CN K. The vibrational and rotational distributions are approximately Boltzmann. This energy partitioning is in good agreement with recent experimental results. The trajectory unimolecular rate constants and lifetime distributions for CF 3CN dissociation are consistent with intrinsic RRKM behaviour.

Nyman, Gunnar; Rynefors, Kjell; Hase, William L.

1986-12-01

101

Electron-Nuclear Energy Sharing in Above-Threshold Multiphoton Dissociative Ionization of H2  

E-print Network

Electron-Nuclear Energy Sharing in Above-Threshold Multiphoton Dissociative Ionization of H2 J. Wu­4], where the photon energy is shared by the freed electrons and the nuclear fragments. For the molecular ionization [10­15], and the imaging of inter- nuclear distance using nuclear kinetic energy release spec- tra

Thumm, Uwe

102

Toward understanding the dissociation of weak acids in water: 1. Using ir spectroscopy to identify proton-shared hydrogen-bonded ion-pair intermediates.  

PubMed

Cryogenic conditions favor the formation of ion-pair dissociation intermediates in amorphous mixtures of HF and H(2)O, making possible their characterization by means of infrared spectroscopy. The experimental infrared spectra show a structurally rich "continuous" absorption ranging from 1000 to 3400 cm(-1), which, in principle, contains important information regarding the microscopic structure of the aforementioned dissociation intermediates. Herein, we demonstrate that this microscopic information can be extracted by comparing and contrasting experimental spectra with those obtained by means of carefully designed first-principles molecular dynamics calculations. Very good, systematic agreement between theoretical and experimental spectra can be obtained for HF/H(2)O mixtures of various compositions, revealing the presence of proton-shared, dissociation intermediates F(delta-) * * * H * * * (delta+)OH(2). The existence of similar proton-shared, hydrogen-bonded intermediates of ionization, that are stable in solution, but not in the gas phase, has been previously suggested by other groups, using, among other techniques, low temperature NMR data and aprotic, dipolar, solvents. Our investigation reveals that similar structures are also stable in aqueous solutions of HF. We discuss some of the implications of the present findings as far as the mechanism of dissociation of weak acids is concerned. PMID:19425221

Thomas, Vibin; Iftimie, Radu

2009-04-01

103

Breaking the carbon dimer: The challenges of multiple bond dissociation with full configuration interaction quantum Monte Carlo methods  

NASA Astrophysics Data System (ADS)

The full configuration interaction quantum Monte Carlo (FCIQMC) method, as well as its "initiator" extension (i-FCIQMC), is used to tackle the complex electronic structure of the carbon dimer across the entire dissociation reaction coordinate, as a prototypical example of a strongly correlated molecular system. Various basis sets of increasing size up to the large cc-pVQZ are used, spanning a fully accessible N-electron basis of over 1012 Slater determinants, and the accuracy of the method is demonstrated in each basis set. Convergence to the FCI limit is achieved in the largest basis with only O[10^7] walkers within random errorbars of a few tenths of a millihartree across the binding curve, and extensive comparisons to FCI, CCSD(T), MRCI, and CEEIS results are made where possible. A detailed exposition of the convergence properties of the FCIQMC methods is provided, considering convergence with elapsed imaginary time, number of walkers and size of the basis. Various symmetries which can be incorporated into the stochastic dynamic, beyond the standard abelian point group symmetry and spin polarisation are also described. These can have significant benefit to the computational effort of the calculations, as well as the ability to converge to various excited states. The results presented demonstrate a new benchmark accuracy in basis-set energies for systems of this size, significantly improving on previous state of the art estimates.

Booth, George H.; Cleland, Deidre; Thom, Alex J. W.; Alavi, Ali

2011-08-01

104

ZEKE photoelectron spectroscopy of p-fluorophenol···H2S/H2O complexes and dissociation energy measurement using the Birge-Sponer extrapolation method.  

PubMed

In this work we have shown that the Birge-Sponer extrapolation method can be successfully used to determine the dissociation energies (D0) of noncovalently bound complexes. The O-H···S hydrogen-bonding interaction in the cationic state of the p-fluorophenol···H2S complex was characterized using zero kinetic energy (ZEKE) photoelectron spectroscopy. This is the first ZEKE report on the O-H···S hydrogen-bonding interaction. The adiabatic ionization energy (AIE) of the complex was determined as 65?542 cm(-1). Various intermolecular and intramolecular vibrational modes of the cation were assigned. A long progression was observed in the intermolecular stretching mode (?) of the complex with significant anharmonicity along this mode. The anharmonicity information was used to estimate the dissociation energy (D0) in the cationic state using the Birge-Sponer extrapolation method. The D0 was estimated as 9.72 ± 1.05 kcal mol(-1). The ZEKE photoelectron spectra of analogous complex FLP···H2O was also recorded for the sake of comparison. The AIE was determined as 64?082 cm(-1). The intermolecular stretching mode in this system, however, was found to be quite harmonic, unlike that in the H2S complex. The dissociation energies of both the complexes, along with those of a few benchmark systems, such as phenol···H2O and indole···benzene complexes, were computed at various levels of theory such as MP2 at the complete basis set limit, ?B97X-D, and CCSD(T). It was found that only the ?B97X-D level values were in excellent agreement with the experimental results for the benchmark systems for the ground as well as the cationic states. The dissociation energy of the (FLP···H2S)(+) complex determined by the Birge-Sponer extrapolation was about ?18% lower than that computed at the ?B97X-D level. PMID:25250474

Bhattacharyya, Surjendu; Wategaonkar, Sanjay

2014-10-01

105

Surface Energy Effect on Polymers Adhesive Bonding at Room Temperature  

NASA Astrophysics Data System (ADS)

The effect of different surface energies of substrate on adhesive bonding at room temperature is investigated in this paper. Comparing to the RCA cleaning procedure, the improved cleaning procedure increases surface energies of wafers which were detected by water contact angle (WCA) measured with JY-82 contact angle goniometer. This higher surface energy leads to stronger bonding properties between Si and glass with epoxy (TS814) at room temperature. The bonding strength was detected by Series IX Automated Materials Testing System. Compared with the RCA cleaning simples, the one with high surface energy of wafers reached 8.56Mpa, more than seven times stronger than the others.

Jin, Yingxia; Yin, Xiaoling; Li, Liang; Wang, Chong; Yang, Yu

2011-06-01

106

Do Bond Functions Help for the Calculation of Accurate Bond Energies?  

NASA Technical Reports Server (NTRS)

The bond energies of 8 chemically bound diatomics are computed using several basis sets with and without bond functions (BF). The bond energies obtained using the aug-pVnZ+BF basis sets (with a correction for basis set superposition error, BSSE) tend to be slightly smaller that the results obtained using the aug-pV(n+I)Z basis sets, but slightly larger than the BSSE corrected aug-pV(n+I)Z results. The aug-cc-pVDZ+BF and aug-cc-pVTZ+BF basis sets yield reasonable estimates of bond energies, but, in most cases, these results cannot be considered highly accurate. Extrapolation of the results obtained with basis sets including bond functions appears to be inferior to the results obtained by extrapolation using atom-centered basis sets. Therefore bond functions do not appear to offer a path for obtaining highly accurate results for chemically bound systems at a lower computational cost than atom centered basis sets.

Bauschlicher, Charles W., Jr.; Arnold, James (Technical Monitor)

1998-01-01

107

Facilitating protein disulfide mapping by a combination of pepsin digestion, electron transfer higher energy dissociation (EThcD), and a dedicated search algorithm SlinkS.  

PubMed

Disulfide bond identification is important for a detailed understanding of protein structures, which directly affect their biological functions. Here we describe an integrated workflow for the fast and accurate identification of authentic protein disulfide bridges. This novel workflow incorporates acidic proteolytic digestion using pepsin to eliminate undesirable disulfide reshuffling during sample preparation and a novel search engine, SlinkS, to directly identify disulfide-bridged peptides isolated via electron transfer higher energy dissociation (EThcD). In EThcD fragmentation of disulfide-bridged peptides, electron transfer dissociation preferentially leads to the cleavage of the S-S bonds, generating two intense disulfide-cleaved peptides as primary fragment ions. Subsequently, higher energy collision dissociation primarily targets unreacted and charge-reduced precursor ions, inducing peptide backbone fragmentation. SlinkS is able to provide the accurate monoisotopic precursor masses of the two disulfide-cleaved peptides and the sequence of each linked peptide by matching the remaining EThcD product ions against a linear peptide database. The workflow was validated using a protein mixture containing six proteins rich in natural disulfide bridges. Using this pepsin-based workflow, we were able to efficiently and confidently identify a total of 31 unique Cys-Cys bonds (out of 43 disulfide bridges present), with no disulfide reshuffling products detected. Pepsin digestion not only outperformed trypsin digestion in terms of the number of detected authentic Cys-Cys bonds, but, more important, prevented the formation of artificially reshuffled disulfide bridges due to protein digestion under neutral pH. Our new workflow therefore provides a precise and generic approach for disulfide bridge mapping, which can be used to study protein folding, structure, and stability. PMID:24980484

Liu, Fan; van Breukelen, Bas; Heck, Albert J R

2014-10-01

108

Bonding  

NSDL National Science Digital Library

Bonding Purpose: To review the 3 Types of Bonds and the 4 Intermolecular Forces. Assignment: Answer the following questions on a separate piece of paper: 1) List the 3 types of bonding, give descriptions and one example of each 2) List the 4 intermolecular forces and draw examples of each. Be ...

Cutting, Mrs.

2008-03-08

109

Dynamics of dissociative scattering: Hyperthermal energy collisions of state-selected OCS+ on Ag(111)  

Microsoft Academic Search

The dynamics of dissociation and negative ion formation have been investigated for the hyperthermal energy scattering of state-selected OCS+(X 2&Pgr;x, &ugr;1, &ugr;2, &ugr;3) on Ag(111). Experiments reveal the effect that collision energy and internal energy have on the formation of scattered ionic products. An analysis of the appearance threshold and fragment velocity distribution for each scattered product channel [S?(2P), O?(2P),

J. R. Morris; G. Kim; T. L. O. Barstis; R. Mitra; D. C. Jacobs

1997-01-01

110

N+ charge transfer and N+2 dissociation in N2 at swarm energies.  

PubMed

This paper reports a drift-tube-mass-spectrometer measurement of the relative abundances of N+ and N+2 in pure nitrogen, over a ratio of electric field to gas density, E/N, from 800 to 7200 Td [1 townsend (Td)=10(-17) V cm(2)]. A proposed charge transfer dissociation scheme between the above two ions and N2 allowed us to obtain spatial rate coefficients for charge transfer and dissociation over the E/N range 800-2800 Td. Using previously measured cross sections for the above processes, and assuming a Maxwellian distribution of ion velocities, we calculated the reaction coefficients, which were found to be in good agreement with our measured values. In particular, the present results support the trend toward fairly high charge transfer cross section values for N+ energies above 10 eV. In the overlap range between 2.4 and 7.2 kTd, our concentration ratio [N(+)/N(+)(2)] is about five times smaller than that measured previously from a diffuse Townsend discharge in which electron impact is involved in addition to N+2 collisional dissociation with N2, but has the same trend. Thus it seems that, besides N+2 dissociation by electron impact, collisional dissociation becomes important at elevated values of E/N. In connection with previous discharge work in nitrogen, the present study may help explain the enhanced cathode yields observed. PMID:11304365

Basurto, E; de Urquijo, J; Cisneros, C; Alvarez, I

2001-01-01

111

Origin of bond energy effects in hot atom chemistry  

Microsoft Academic Search

Six-particle T+CDâ trajectory studies show that bond energy ; effects on H abstraction, previously explored with a 3-particle LEPS potential, ; arise from correlation of barrier height with exoergicity. (AIP);

Sally Chapman; Trina Valencich; Don L. Bunker

1974-01-01

112

Stochastic Theory of Vibrational Relaxation and Dissociation  

Microsoft Academic Search

The familiar theories of unimolecular reactions are based on the assumptions of strong collisions, a randomizing redistribution of internal energy, and an a posteriori choice of a single dissociation coordinate. In this paper we replace these starting points by introducing a model with a set of transition probabilities defining a Markov chain whose time evolution describes the individual bond breaking

William M. Gelbart; Stuart A. Rice; Karl F. Freed

1970-01-01

113

Boltzmann rovibrational collisional coarse-grained model for internal energy excitation and dissociation in hypersonic flows  

NASA Astrophysics Data System (ADS)

A Boltzmann rovibrational collisional coarse-grained model is proposed to reduce a detailed kinetic mechanism database developed at NASA Ames Research Center for internal energy transfer and dissociation in N2-N interactions. The coarse-grained model is constructed by lumping the rovibrational energy levels of the N2 molecule into energy bins. The population of the levels within each bin is assumed to follow a Boltzmann distribution at the local translational temperature. Excitation and dissociation rate coefficients for the energy bins are obtained by averaging the elementary rate coefficients. The energy bins are treated as separate species, thus allowing for non-Boltzmann distributions of their populations. The proposed coarse-grained model is applied to the study of nonequilibrium flows behind normal shock waves and within converging-diverging nozzles. In both cases, the flow is assumed inviscid and steady. Computational results are compared with those obtained by direct solution of the master equation for the rovibrational collisional model and a more conventional multitemperature model. It is found that the proposed coarse-grained model is able to accurately resolve the nonequilibrium dynamics of internal energy excitation and dissociation-recombination processes with only 20 energy bins. Furthermore, the proposed coarse-grained model provides a superior description of the nonequilibrium phenomena occurring in shock heated and nozzle flows when compared with the conventional multitemperature models.

Munafò, A.; Panesi, M.; Magin, T. E.

2014-02-01

114

Boltzmann rovibrational collisional coarse-grained model for internal energy excitation and dissociation in hypersonic flows.  

PubMed

A Boltzmann rovibrational collisional coarse-grained model is proposed to reduce a detailed kinetic mechanism database developed at NASA Ames Research Center for internal energy transfer and dissociation in N(2)-N interactions. The coarse-grained model is constructed by lumping the rovibrational energy levels of the N(2) molecule into energy bins. The population of the levels within each bin is assumed to follow a Boltzmann distribution at the local translational temperature. Excitation and dissociation rate coefficients for the energy bins are obtained by averaging the elementary rate coefficients. The energy bins are treated as separate species, thus allowing for non-Boltzmann distributions of their populations. The proposed coarse-grained model is applied to the study of nonequilibrium flows behind normal shock waves and within converging-diverging nozzles. In both cases, the flow is assumed inviscid and steady. Computational results are compared with those obtained by direct solution of the master equation for the rovibrational collisional model and a more conventional multitemperature model. It is found that the proposed coarse-grained model is able to accurately resolve the nonequilibrium dynamics of internal energy excitation and dissociation-recombination processes with only 20 energy bins. Furthermore, the proposed coarse-grained model provides a superior description of the nonequilibrium phenomena occurring in shock heated and nozzle flows when compared with the conventional multitemperature models. PMID:25353565

Munafò, A; Panesi, M; Magin, T E

2014-02-01

115

Collision-induced dissociation dynamics of the acetone cation: intraconversion of translational and electronic energy  

NASA Astrophysics Data System (ADS)

Collisional activation and dissociation of low-energy acetone ions have been studied using a crossed-beam tandem mass spectrometer. A small but significant fraction of acetone ions from 70 eV electron ionization are formed in long-lived excited A state. Ground state acetone ions are also collisionally excited to the A state via conversion of translational into internal energy. Two populations of collisionally excited ions are formed, one which is stable on the time scale of our experiments and one which dissociates into an acetyl ion and a methyl radical. These microscopically related reaction pathways demonstrate the unexpectedly facile interconversion of translational and electronic energy in low-energy collisions.

Qian, Kuangnan; Shukla, Anil; Futrell, Jean

1990-11-01

116

A Unified Kinetics and Equilibrium Experiment: Rate Law, Activation Energy, and Equilibrium Constant for the Dissociation of Ferroin  

ERIC Educational Resources Information Center

Tris(1,10-phenanthroline)iron(II) is the basis of a suite of four experiments spanning 5 weeks. Students determine the rate law, activation energy, and equilibrium constant for the dissociation of the complex ion in acid solution and base dissociation constant for phenanthroline. The focus on one chemical system simplifies a daunting set of…

Sattar, Simeen

2011-01-01

117

Role of translational and vibrational energy in the dissociative chemisorption of methane on Pd{1 1 0}  

NASA Astrophysics Data System (ADS)

Dissociative adsorption of methane has been investigated on Pd {1 1 0} by using molecular beam surface scattering. The initial sticking probability has been determined in the translational energy range of 7-95 kJ/mol and at selected vibrational energies from 300 to 700 K. The measured initial sticking probability is found to increase strongly with both translational and vibrational energy of CH 4 molecules. The activation of the dissociative chemisorption of CH 4 induced by the vibrational energy is shown to depend on the translational energy and is attributed to the excitation of the bending modes of the incident molecule. We have also performed molecular dynamics simulations to investigate the dissociation mechanism theoretically. The simulations clearly demonstrate that an efficient energy transfer occurs upon adsorption between the translational and vibrational energies of the incident CH 4 molecule, which thereby facilitates the deformation of the molecular structure of CH 4 resulting in dissociation.

Hirsimäki, M.; Paavilainen, S.; Nieminen, J. A.; Valden, M.

2001-06-01

118

Analysis of liquid metal embrittlement from a bond energy viewpoint  

Microsoft Academic Search

Absorption induced embrittlement of solid metals by certain liquid metals is analyzed through an Engel-Brewer calculation\\u000a of the solid-liquid interaction energy, and the effect of the latter in reducing fracture surface energy. The reduction in\\u000a fracture surface energy is estimated by comparison of the electronic contribution to the solid-liquid interaction energy with\\u000a solid-solid bond energy for some 40 liquid-solid couples.

M. J. Kelley; N. S. Stoloff

1975-01-01

119

Analysis of liquid metal embrittlement from a bond energy viewpoint  

Microsoft Academic Search

Absorption induced embrittlement of solid metals by certain liquid metals is analyzed through an Engel-Brewer calculation of the solid-liquid interaction energy, and the effect of the latter in reducing fracture surface energy. The reduction in fracture surface energy is estimated by comparison of the electronic contribution to the solid-liquid interaction energy with solid-solid bond energy for some 40 liquid-solid couples.

M. J. Kelley; N. S. Stoloff

1975-01-01

120

Novel 2-alkyl-1-ethylpyridinium ionic liquids: synthesis, dissociation energies and volatility.  

PubMed

This work presents the synthesis, volatility study and electrospray ionization mass spectrometry with energy-variable collision induced dissociation of the isolated [(cation)2(anion)](+) of a novel series of 2-alkyl-1-ethyl pyridinium based ionic liquids, [(2)CN-2(1)C2Py][NTf2]. Compared to the imidazolium based ionic liquids, the new ionic liquid series presents a higher thermal stability and lower volatility. The [(cation)2(anion)](+) collision induced dissociation energies of both [(2)CN-2(1)C2Py][NTf2] and [CNPy][NTf2] pyridinium series show an identical trend with a pronounced decrease of the relative cation-anion interaction energy towards an almost constant value for N = 6. It was found that the lower volatility of [(2)CN-2(1)C2Py][NTf2] with a shorter alkyl chain length is due to its higher enthalpy of vaporization. Starting from [(2)C3(1)C2Py][NTf2], the lower volatility is governed by the combination of slightly lower entropies and higher enthalpies of vaporization, an indication of a higher structural disorder of the pyridinium based ionic liquids than the imidazolium based ionic liquids. Dissociation energies and volatility trends support the cohesive energy interpretation model based on the overlapping of the electrostatic and van der Waals functional interaction potentials. PMID:25493639

Vilas, Miguel; Rocha, Marisa A A; Fernandes, Ana M; Tojo, Emilia; Santos, Luís M N B F

2015-01-28

121

Experimental and theoretical investigations of energy transfer and hydrogen-bond breaking in small water and HCl clusters.  

PubMed

Water is one of the most pervasive molecules on earth and other planetary bodies; it is the molecule that is searched for as the presumptive precursor to extraterrestrial life. It is also the paradigm substance illustrating ubiquitous hydrogen bonding (H-bonding) in the gas phase, liquids, crystals, and amorphous solids. Moreover, H-bonding with other molecules and between different molecules is of the utmost importance in chemistry and biology. It is no wonder, then, that for nearly a century theoreticians and experimentalists have tried to understand all aspects of H-bonding and its influence on reactivity. It is somewhat surprising, therefore, that several fundamental aspects of H-bonding that are particularly important for benchmarking theoretical models have remained unexplored experimentally. For example, even the binding strength between two gas-phase water molecules has never been determined with sufficient accuracy for comparison with high-level electronic structure calculations. Likewise, the effect of cooperativity (nonadditivity) in small H-bonded networks is not known with sufficient accuracy. An even greater challenge for both theory and experiment is the description of the dissociation dynamics of H-bonded small clusters upon acquiring vibrational excitation. This is because of the long lifetimes of many clusters, which requires running classical trajectories for many nanoseconds to achieve dissociation. In this Account, we describe recent progress and ongoing research that demonstrates how the combined and complementary efforts of theory and experiment are enlisted to determine bond dissociation energies (D0) of small dimers and cyclic trimers of water and HCl with unprecedented accuracy, describe dissociation dynamics, and assess the effects of cooperativity. The experimental techniques rely on IR excitation of H-bonded X-H stretch vibrations, measuring velocity distributions of fragments in specific rovibrational states, and determining product state distributions at the pair-correlation level. The theoretical methods are based on high-level ab initio potential energy surfaces used in quantum and classical dynamical calculations. We achieve excellent agreement on D0 between theory and experiments for all of the clusters that we have compared, as well as for cooperativity in ring trimers of water and HCl. We also show that both the long-range and the repulsive parts of the potential must be involved in bond breaking. We explain why H-bonds are so resilient and hard to break, and we propose that a common motif in the breaking of cyclic trimers is the opening of the ring following transfer of one quantum of stretch excitation to form open-chain structures that are weakly bound. However, it still takes many vibrational periods to release one monomer fragment from the open-chain structures. Our success with water and HCl dimers and trimers led us to embark on a more ambitious project: studies of mixed water and HCl small clusters. These clusters eventually lead to ionization of HCl and serve as prototypes of acid dissociation in water. Measurements and calculations of such ionizations are yet to be achieved, and we are now characterizing these systems by adding monomers one at a time. We describe our completed work on the HCl-H2O dimer and mention our recent theoretical results on larger mixed clusters. PMID:25072730

Samanta, Amit K; Czakó, Gábor; Wang, Yimin; Mancini, John S; Bowman, Joel M; Reisler, Hanna

2014-08-19

122

Photo-mechanical energy conversion using polymer brush dissociation  

E-print Network

A device is investigated that continuously and directly converts light into mechanical energy, using polymers and photodissociation. A polymer brush tethered to a surface, is brought into contact with a parallel plate a small distance above it that contains reaction sites where photodissociation of bound polymer and light can occur. Under the appropriate conditions, the collective effect of these polymers is to apply a force parallel to the plates, converting incoming light into mechanical work. Numerical work is carried out to understand this effect, a three dimensional Langevin simulation, solution to the Fokker Planck equation, and a one dimensional Monte Carlo simulation. Theoretical analysis of the Fokker Planck equation is used to study a model where equilibration of the unbound state occurs and equilibration to a metastable equilibrium is achieved in the bound state. It is shown that the work per cycle can be made much larger than the thermal energy but at the expense of requiring a greatly diminished photodissociation rate. Parameters are discussed in order optimize mechanical energy conversion.

J. M. Deutsch

2013-01-03

123

Theoretical study of the dissociation energy and the red and violet band systems of CN  

NASA Technical Reports Server (NTRS)

The dissociation energy D0 is determined here for the CN ground-state and radiative lifetimes for the A 2Pi and B 2Sigma(+) states. D0 is found to be 7.65 + or - 0.06 eV, corresponding to Delta Hf (CN) = 105.3 + or - 1.5 kcal/mole. These results are compared with current experimental estimates and with previous theoretical calculations.

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

1988-01-01

124

Dissociation energy of alkali metal clusters related to inhomogeneous electron gas theory  

Microsoft Academic Search

A pseudopotential model, combined with a one-centre expansion, is set up to calculate the dissociation energies D of alkali metal atom clusters LiN to CsN, when 2 ˇ- N ˇ- 10. This central field model is solved for the valence electrons using the Slater-Kohn-Sham (SKS) equations, with a local density approximation for the exchange-correlation one-body potential. Inhomogeneous electron gas theory,

N. A. Cordero; J. A. Alonso; J. M. López; N. H. March

1993-01-01

125

Dissociation energy of alkali metal clusters related to inhomogeneous electron gas theory  

Microsoft Academic Search

A pseudopotential model, combined with a one-centre expansion, is set up to calculate the dissociation energies D of alkali metal atom clusters LiN to CsN, when 2 ?- N ?- 10. This central field model is solved for the valence electrons using the Slater-Kohn-Sham (SKS) equations, with a local density approximation for the exchange-correlation one-body potential. Inhomogeneous electron gas theory,

N. A. Cordero; J. A. Alonso; J. M. López; N. H. March

1993-01-01

126

Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy  

DOEpatents

Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

McGrail, B. Peter; Brown, Daryl R.; Thallapally, Praveen K.

2014-08-05

127

Dissociative double photoionization of benzene molecules in the 26-33 eV energy range.  

PubMed

A time-of-flight mass spectrometer with a position sensitive ion detector was used to study the dissociative double ionization of benzene by UV synchrotron radiation. The threshold energy for the main dissociative processes, leading to CH(3)(+) + C(5)H(3)(+), C(2)H(3)(+) + C(4)H(3)(+) and C(2)H(2)(+) + C(4)H(4)(+) ion pairs were characterized by exploiting a photoelectron-photoion-photoion-coincidence technique, giving 27.8 ± 0.1, 29.5 ± 0.1, and 30.2 ± 0.1 eV, respectively. The first reaction also proceeds via the formation of a metastable C(6)H(6)(2+) dication. The translational kinetic energy of the ionic products was evaluated by measuring the position of ions arriving to the detector. Theoretical calculations of the energy and structure of dissociation product ions were performed to provide further information on the dynamics of the charge separation reactions following the photoionization event. PMID:21437307

Alagia, Michele; Candori, Pietro; Falcinelli, Stefano; Pirani, Fernando; Mundim, Maria S Pedrosa; Richter, Robert; Rosi, Marzio; Stranges, Stefano; Vecchiocattivi, Franco

2011-05-14

128

Anisotropy and molecular rotation in resonant low-energy dissociative recombination.  

PubMed

Angular fragment distributions from the dissociative recombination (DR) of HD(+) were measured with well directed monochromatic low-energy electrons over a dense grid of collision energies from 7 to 35 meV, where pronounced rovibrational Feshbach resonances occur. Significant higher-order anisotropies are found in the distributions, whose size varies along energy in a partial correlation with the relative DR rate from fast-rotating molecules. This may indicate a breakdown of the nonrotation assumption so far applied to predict angular DR fragment distributions. PMID:18518450

Novotny, S; Rubinstein, H; Buhr, H; Novotný, O; Hoffmann, J; Mendes, M B; Orlov, D A; Krantz, C; Berg, M H; Froese, M; Jaroshevich, A S; Jordon-Thaden, B; Lange, M; Lestinsky, M; Petrignani, A; Shafir, D; Zajfman, D; Schwalm, D; Wolf, A

2008-05-16

129

Effects of density functionals and dispersion interactions on geometries, bond energies and harmonic frequencies of Etbnd UX3 (E = N, P, CH; X = H, F, Cl)  

NASA Astrophysics Data System (ADS)

Quantum-chemical calculations have been performed to evaluate the geometries, bonding nature and harmonic frequencies of the compounds [Etbnd UX3] at DFT, DFT-D3, DFT-D3(BJ) and DFT-dDSc levels using different density functionals BP86, BLYP, PBE, revPBE, PW91, TPSS and M06-L. The stretching frequency of Utbnd N bond in [Ntbnd UF3] calculated with DFT/BLYP closely resembles with the experimental value. The performance of different density functionals for accurate Utbnd N vibrational frequencies follows the order BLYP > revPBE > BP86 > PW91 > TPSS > PBE > M06-L. The BLYP functional gives accurate value of the Utbnd E bond distances. The uranium atom in the studied compounds [Etbnd UX3] is positively charged. Upon going from [Etbnd UF3] to [Etbnd UCl3], the partial Hirshfeld charge on uranium atom decreases because of the lower electronegativity of chlorine compared to flourine. The Gopinathan-Jug bond order for Utbnd E bonds ranges from 2.90 to 3.29. The Utbnd E bond dissociation energies vary with different density functionals as M06-L < TPSS < BLYP < revPBE < BP86 < PBE ? PW91. The orbital interactions ?Eorb, in all studied compounds [Etbnd UX3] are larger than the electrostatic interaction ?Eelstat, which means the Utbnd N bonds in these compound have greater degree of covalent character (in the range 63.8-77.2%). The Usbnd E ?-bonding interaction is the dominant bonding interaction in the nitride and methylidyne complexes while it is weaker in [Ptbnd UX3]. The dispersion energy contributions to the total bond dissociation energies are rather small. Compared to the Grimme's D3(BJ) corrections, the Corminboeuf's dispersion corrections are larger with metaGGA functionals (TPSS, M06-L) while smaller with GGA functionals.

Pandey, Krishna Kumar; Patidar, Pankaj; Patidar, Sunil Kumar; Vishwakarma, Ravi

2014-12-01

130

Dissociation of methanol by ion-impact  

NASA Astrophysics Data System (ADS)

The dissociation dynamics of multiply charged methanol molecules formed in collision with 1.2 MeV Ar8+projectiles is studied. Using coincidence mapping techniques, we can separate out the different dissociation pathways between carbon, oxygen and hydrogen ionic fragments as well as two- and three-body breakup events. Reactions involving intramolecular bond rearrangements within the CH3 group of the dissociative molecule are discussed in detail. A signature of hydrogen migration in doubly charged methanol is observed. Kinetic energy releases of different breakup channels are reported here and compared with values calculated from a Coulomb explosion model. The shape and orientation of the islands in the coincidence map give further information about the momentum balance in the fragmentation process of two- or many-body dissociation pathways.

de, Sankar; Roy, A.; Rajput, Jyoti; Ghosh, P. N.; Safvan, C. P.

2008-09-01

131

Mass spectrometry study and infrared spectroscopy of the complex between camphor and the two enantiomers of protonated alanine: the role of higher-energy conformers in the enantioselectivity of the dissociation rate constants.  

PubMed

The properties of the protonated complexes built from S camphor and R or S alanine were studied in a Paul ion trap at room temperature by collision-induced dissociation (CID) and infrared multiple-photon dissociation spectroscopy (IRMPD), as well as molecular dynamics and ab initio calculations. While the two diastereomer complexes display very similar vibrational spectra in the fingerprint region, in line with similar structures, and almost identical calculated binding energies, their collision-induced dissociation rates are different. Comparison of the IRMPD results to computed spectra shows that the SS and SR complexes both contain protonated alanine strongly hydrogen-bonded to the keto group of camphor. The floppiness of this structure around the NH?...O=C hydrogen bond results in a complex potential energy surface showing multiple minima. Calculating the dissociation rate constant within the frame of the transition state theory shows that the fragmentation rate larger for the heterochiral SR complex than the homochiral SS complex can be explained in terms of two almost isoenergetic low-energy conformers in the latter that are not present for the former. PMID:23740577

Sen, Ananya; Le Barbu-Debus, Katia; Scuderi, Debora; Zehnacker-Rentien, Anne

2013-08-01

132

Simultaneous Glycan-Peptide Characterization Using Hydrophilic Interaction Chromatography and Parallel Fragmentation by CID, Higher Energy Collisional Dissociation, and Electron Transfer Dissociation MS Applied to the N-Linked Glycoproteome of Campylobacter jejuni*  

PubMed Central

Campylobacter jejuni is a gastrointestinal pathogen that is able to modify membrane and periplasmic proteins by the N-linked addition of a 7-residue glycan at the strict attachment motif (D/E)XNX(S/T). Strategies for a comprehensive analysis of the targets of glycosylation, however, are hampered by the resistance of the glycan-peptide bond to enzymatic digestion or ?-elimination and have previously concentrated on soluble glycoproteins compatible with lectin affinity and gel-based approaches. We developed strategies for enriching C. jejuni HB93-13 glycopeptides using zwitterionic hydrophilic interaction chromatography and examined novel fragmentation, including collision-induced dissociation (CID) and higher energy collisional (C-trap) dissociation (HCD) as well as CID/electron transfer dissociation (ETD) mass spectrometry. CID/HCD enabled the identification of glycan structure and peptide backbone, allowing glycopeptide identification, whereas CID/ETD enabled the elucidation of glycosylation sites by maintaining the glycan-peptide linkage. A total of 130 glycopeptides, representing 75 glycosylation sites, were identified from LC-MS/MS using zwitterionic hydrophilic interaction chromatography coupled to CID/HCD and CID/ETD. CID/HCD provided the majority of the identifications (73 sites) compared with ETD (26 sites). We also examined soluble glycoproteins by soybean agglutinin affinity and two-dimensional electrophoresis and identified a further six glycosylation sites. This study more than doubles the number of confirmed N-linked glycosylation sites in C. jejuni and is the first to utilize HCD fragmentation for glycopeptide identification with intact glycan. We also show that hydrophobic integral membrane proteins are significant targets of glycosylation in this organism. Our data demonstrate that peptide-centric approaches coupled to novel mass spectrometric fragmentation techniques may be suitable for application to eukaryotic glycoproteins for simultaneous elucidation of glycan structures and peptide sequence. PMID:20360033

Scott, Nichollas E.; Parker, Benjamin L.; Connolly, Angela M.; Paulech, Jana; Edwards, Alistair V. G.; Crossett, Ben; Falconer, Linda; Kolarich, Daniel; Djordjevic, Steven P.; Højrup, Peter; Packer, Nicolle H.; Larsen, Martin R.; Cordwell, Stuart J.

2011-01-01

133

Hydride dissociation energies of six-membered heterocyclic organic hydrides predicted by ONIOM-G4Method.  

PubMed

Hydride dissociation energy is of great importance in understanding the hydride-donating abilities of organic hydrides. Although the hydride dissociation energies of some organic hydrides have been experimentally measured, much less attention has been focused on the investigation of these quantities from the first principles of physics. Herein, we developed an ONIOM-G4 method and carefully benchmarked this new method against 48 experimental hydride dissociation energies of diverse bulky molecules. It was found that with the combined methods of the HF/6-31+G(d,p)//IEFPCM/Bondi1.15 solvation model, the ONIOM-G4 method can predict the hydride dissociation energies with an error bar of only 1.7 kcal/mol. With the newly developed ONIOM-G4 method, we then systematically studied the hydride dissociation energies of six categories of biologically and pharmaceutically important six-membered heterocyclic organic hydrides, namely, the organic hydrides containing 1,4-dihydropyridine, 1,4-dihydropyrazine, 1,4-oxazine, 1,4-thiazine, 4H-pyran, and 4H-thiopyran ring structures. An extensive hydride dissociation energy scale containing over 100 six-memebered heterocyclic organic hydrides has been established, which may find applications in both synthetic organic chemistry and mechanistic studies of various chemical or biological processes involving transferring of the hydride anion. PMID:22146106

Shi, Jing; Huang, Xiong-Yi; Wang, Hua-Jing; Fu, Yao

2012-01-23

134

Energy decomposition analysis of covalent bonds and intermolecular interactions  

NASA Astrophysics Data System (ADS)

An energy decomposition analysis method is implemented for the analysis of both covalent bonds and intermolecular interactions on the basis of single-determinant Hartree-Fock (HF) (restricted closed shell HF, restricted open shell HF, and unrestricted open shell HF) wavefunctions and their density functional theory analogs. For HF methods, the total interaction energy from a supermolecule calculation is decomposed into electrostatic, exchange, repulsion, and polarization terms. Dispersion energy is obtained from second-order Møller-Plesset perturbation theory and coupled-cluster methods such as CCSD and CCSD(T). Similar to the HF methods, Kohn-Sham density functional interaction energy is decomposed into electrostatic, exchange, repulsion, polarization, and dispersion terms. Tests on various systems show that this algorithm is simple and robust. Insights are provided by the energy decomposition analysis into H2, methane C-H, and ethane C-C covalent bond formation, CH3CH3 internal rotation barrier, water, ammonia, ammonium, and hydrogen fluoride hydrogen bonding, van der Waals interaction, DNA base pair formation, BH3NH3 and BH3CO coordinate bond formation, Cu-ligand interactions, as well as LiF, LiCl, NaF, and NaCl ionic interactions.

Su, Peifeng; Li, Hui

2009-07-01

135

Students' interdisciplinary reasoning about "high-energy bonds" and ATP  

NSDL National Science Digital Library

Students' sometimes contradictory ideas about ATP (adenosine triphosphate) and the nature of chemical bonds have been studied in the biology and chemistry education literatures, but these topics are rarely part of the introductory physics curriculum. We present qualitative data from an introductory physics course for undergraduate biology majors that seeks to build greater interdisciplinary coherence and therefore includes these topics. In these data, students grapple with the apparent contradiction between the energy released when the phosphate bond in ATP is broken and the idea that an energy input is required to break a bond. We see that students' perceptions of how each scientific discipline bounds the system of interest can influence how they justify their reasoning about a topic that crosses disciplines. This has consequences for a vision of interdisciplinary education that respects disciplinary perspectives while bringing them into interaction in ways that demonstrate consistency amongst the perspectives

Dreyfus, Benjamin W.; Geller, Benjamin D.; Sawtelle, Vashti; Svoboda, Julia; Turpen, Chandra; Redish, Edward F.

2013-09-07

136

Guided ion beam studies of the reactions of Con+ (n=1-18) with N2: Cobalt cluster mononitride and dinitride bond energies  

NASA Astrophysics Data System (ADS)

The reactions of Con+ (n=1-18) with N2 are measured as a function of kinetic energy over a range of 0-15eV in a guided ion beam tandem mass spectrometer. A variety of Com+, ComN+, and ComN2+ (m?n) product ions are observed, all in endothermic processes, with collision-induced dissociation dominating the products for all clusters. Bond dissociation energies for both cobalt cluster nitrides and dinitrides are derived from threshold analysis of the energy dependence of the endothermic reactions using several different approaches. These values show only a mild dependence on cluster size over the range studied, although the Co13+-N bond energy is relatively weak. The bond energies of Con+-N for larger clusters suggest that a reasonable value for the desorption energy of atomic nitrogen from bulk phase cobalt is 6.3±0.2eV, which is somewhat lower than the only available value in the literature, an estimate based on the enthalpy of formation of bulk cobalt nitride. The trends in the cobalt nitride thermochemistry are also compared to previously determined metal-metal bond energies, D0(Con+-Co), and to D0(Fen+-N). Implications for catalytic ammonia production using cobalt versus iron are discussed.

Liu, Fuyi; Li, Ming; Tan, Lin; Armentrout, P. B.

2008-05-01

137

The chemical bond in external electric fields: Energies, geometries, and vibrational Stark shifts of diatomic molecules  

NASA Astrophysics Data System (ADS)

It is shown that the response of molecular properties of diatomics such as the total energy, the bond length, and the vibrational Stark shift to an external homogenous electric field (EF) can be predicted from field-free observable properties such as the equilibrium bond length, the bond dissociation energy, the polarizability and dipole moment functions, and the vibrational frequency. Delley [J. Mol. Struct.: THEOCHEM 434, 229 (1998)] suggested to approximate the potential energy surface under an EF by a Morse function augmented with a EF term proportional to the internuclear separation. In this work, this term is replaced by the expression of the field-induced energy change which yields a field-perturbed Morse potential that tends to a constant asymptotic limit when the EF term itself become proportional to the sum of the polarizabilities of the separated atoms. The model is validated by comparison with direct calculations on nine diatomics, five homo-nuclear (H2, N2, O2, F2, and Cl2) and four hetero-nuclear (HF, HCl, CO, and NO), covering a range and combinations of dipole moments and polarizabilities. Calculations were conducted at the quadratic configuration interaction with single and double excitations (QCISD) and density functional theory (DFT)-B3LYP levels of theory using the 6-311++G(3df,2pd) basis set. All results agree closely at the two levels of theory except for the Stark effect of NO which is not correctly predicted by QCISD calculations as further calculations, including at the coupled cluster with single and double excitation (CCSD) level of theory, demonstrate.

Sowlati-Hashjin, Shahin; Matta, Chérif F.

2013-10-01

138

The chemical bond in external electric fields: energies, geometries, and vibrational Stark shifts of diatomic molecules.  

PubMed

It is shown that the response of molecular properties of diatomics such as the total energy, the bond length, and the vibrational Stark shift to an external homogenous electric field (EF) can be predicted from field-free observable properties such as the equilibrium bond length, the bond dissociation energy, the polarizability and dipole moment functions, and the vibrational frequency. Delley [J. Mol. Struct.: THEOCHEM 434, 229 (1998)] suggested to approximate the potential energy surface under an EF by a Morse function augmented with a EF term proportional to the internuclear separation. In this work, this term is replaced by the expression of the field-induced energy change which yields a field-perturbed Morse potential that tends to a constant asymptotic limit when the EF term itself become proportional to the sum of the polarizabilities of the separated atoms. The model is validated by comparison with direct calculations on nine diatomics, five homo-nuclear (H2, N2, O2, F2, and Cl2) and four hetero-nuclear (HF, HCl, CO, and NO), covering a range and combinations of dipole moments and polarizabilities. Calculations were conducted at the quadratic configuration interaction with single and double excitations (QCISD) and density functional theory (DFT)-B3LYP levels of theory using the 6-311++G(3df,2pd) basis set. All results agree closely at the two levels of theory except for the Stark effect of NO which is not correctly predicted by QCISD calculations as further calculations, including at the coupled cluster with single and double excitation (CCSD) level of theory, demonstrate. PMID:24116597

Sowlati-Hashjin, Shahin; Matta, Chérif F

2013-10-14

139

Storing Renewable Energy in Chemical Bonds  

SciTech Connect

With nearly 7 billion people, the world's population is demanding more electricity every year. Improved technologies are bringing wind and solar power to our electrical grid. However, wind turbines and solar panels only work when the wind blows or the sun shines. PNNL scientists discuss catalysis approaches for storing and releasing energy on demand.

Helm, Monte; Bullock, Morris

2013-03-27

140

Storing Renewable Energy in Chemical Bonds  

ScienceCinema

With nearly 7 billion people, the world's population is demanding more electricity every year. Improved technologies are bringing wind and solar power to our electrical grid. However, wind turbines and solar panels only work when the wind blows or the sun shines. PNNL scientists discuss catalysis approaches for storing and releasing energy on demand.

Helm, Monte; Bullock, Morris

2014-06-13

141

Collision-induced dissociation of fatty acid [M - 2H + Na]- ions: charge-directed fragmentation and assignment of double bond position.  

PubMed

The collision-induced dissociation (CID) of cationic fatty acid-metal ion complexes has been extensively studied and, in general, provides rich structural information. In particular, charge-remote fragmentation processes are commonly observed allowing the assignment of double bond position. In a previous manuscript, we presented two methods to doubly deprotonate polyunsaturated fatty acids to form anionic fatty acid-sodium ion complexes, referred to as [M - 2H + Na]?(-) ions. In the current manuscript, the CID behavior of these [M - 2H + Na]?(-) ions is investigated for the first time. Significantly, we also present a deuterium-labeling experiment, which excludes the possibility that deprotonation occurs predominately at the ?-carbon in the formation of fatty acid [M - H + NaF](-) ions. This supports our original proposal where deprotonation occurs at the bis-allylic positions of polyunsaturated fatty acids. CID spectra of polyunsaturated fatty acid [M - 2H + Na](-) ions display abundant product ions arising from acyl chain cleavages. Through the examination of fatty acid isomers, it is demonstrated that double bond position may be unequivocally determined for methylene-interrupted polyunsaturated fatty acids with three or more carbon-carbon double bonds. In addition, CID of [M - 2H + Na](-) ions was applied to 18:3 isomers of Nannochloropsis oculata and three isomers were tentatively identified: ?(9,12,15)18:3, ?(6,9,12)18:3, and ?(5,8,11)18:3. We propose that structurally-informative product ions are formed via charge-driven fragmentation processes at the site of the resonance-stabilized carbanion as opposed to charge-remote fragmentation processes, which could be inferred if deprotonation occurred predominately at the ?-carbon. PMID:25142324

Thomas, Michael C; Altvater, Jens; Gallagher, Thomas J; Nette, Geoffrey W

2014-11-01

142

Collision-Induced Dissociation of Fatty Acid [M - 2H + Na]- Ions: Charge-Directed Fragmentation and Assignment of Double Bond Position  

NASA Astrophysics Data System (ADS)

The collision-induced dissociation (CID) of cationic fatty acid-metal ion complexes has been extensively studied and, in general, provides rich structural information. In particular, charge-remote fragmentation processes are commonly observed allowing the assignment of double bond position. In a previous manuscript, we presented two methods to doubly deprotonate polyunsaturated fatty acids to form anionic fatty acid-sodium ion complexes, referred to as [M - 2H + Na] - ions. In the current manuscript, the CID behavior of these [M - 2H + Na] - ions is investigated for the first time. Significantly, we also present a deuterium-labeling experiment, which excludes the possibility that deprotonation occurs predominately at the ?-carbon in the formation of fatty acid [M - H + NaF]- ions. This supports our original proposal where deprotonation occurs at the bis-allylic positions of polyunsaturated fatty acids. CID spectra of polyunsaturated fatty acid [M - 2H + Na]- ions display abundant product ions arising from acyl chain cleavages. Through the examination of fatty acid isomers, it is demonstrated that double bond position may be unequivocally determined for methylene-interrupted polyunsaturated fatty acids with three or more carbon-carbon double bonds. In addition, CID of [M - 2H + Na]- ions was applied to 18:3 isomers of Nannochloropsis oculata and three isomers were tentatively identified: ?9,12,1518:3, ?6,9,1218:3, and ?5,8,1118:3. We propose that structurally-informative product ions are formed via charge-driven fragmentation processes at the site of the resonance-stabilized carbanion as opposed to charge-remote fragmentation processes, which could be inferred if deprotonation occurred predominately at the ?-carbon.

Thomas, Michael C.; Altvater, Jens; Gallagher, Thomas J.; Nette, Geoffrey W.

2014-08-01

143

Activation of Peptide Ions by Blackbody Radiation: Factors That Lead to Dissociation Kinetics in the Rapid Energy Exchange Limit  

PubMed Central

Unimolecular rate constants for blackbody infrared radiative dissociation (BIRD) were calculated for the model protonated peptide (AlaGly)n (n = 2–32) using a variety of dissociation parameters. Combinations of dissociation threshold energies ranging from 0.8 to 1.7 eV and transition entropies corresponding to Arrhenius preexponential factors ranging from very “tight” (A? = 109.9 s?1) to “loose” (A? = 1016.8 s?1) were selected to represent dissociation parameters within the experimental temperature range (300–520 K) and kinetic window (kuni = 0.001–0.20 s?1) typically used in the BIRD experiment. Arrhenius parameters were determined from the temperature dependence of these values and compared to those in the rapid energy exchange (REX) limit. In this limit, the internal energy of a population of ions is given by a Boltzmann distribution, and kinetics are the same as those in the traditional high-pressure limit. For a dissociation process to be in this limit, the rate of photon exchange between an ion and the vacuum chamber walls must be significantly greater than the dissociation rate. Kinetics rapidly approach the REX limit either as the molecular size or threshold dissociation energy increases or as the transition-state entropy or experimental temperature decreases. Under typical experimental conditions, peptide ions larger than 1.6 kDa should be in the REX limit. Smaller ions may also be in the REX limit depending on the value of the threshold dissociation energy and transition-state entropy. Either modeling or information about the dissociation mechanism must be known in order to confirm REX limit kinetics for these smaller ions. Three principal factors that lead to the size dependence of REX limit kinetics are identified. With increasing molecular size, rates of radiative absorption and emission increase, internal energy distributions become relatively narrower, and the microcanonical dissociation rate constants increase more slowly over the energy distribution of ions. Guidelines established here should make BIRD an even more reliable method to obtain information about dissociation energetics and mechanisms for intermediate size molecules. PMID:16604162

Price, William D.

2005-01-01

144

Exploring high-energy doubly excited states of NH by dissociative recombination of NH+  

NASA Astrophysics Data System (ADS)

We have investigated electron capture by NH+ resulting in dissociative recombination (DR). The impact energies studied of ˜4-12 eV extend over the range below the two lowest predicted NH+ dissociative states in the Franck-Condon (FC) region of the ion. Our focus has been on the final state populations of the resulting N and H atoms. The neutral DR fragments are detected downstream of a merged electron and ion beam interaction zone in the TSR storage ring, which is located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. Transverse fragment distances were measured on a recently developed high count-rate imaging detector. The distance distributions enabled a detailed tracking of the final state populations as a function of the electron collision energy. These can be correlated with doubly excited neutral states in the FC region of the ion. At low electron energy of ˜5 eV, the atomic product final levels are nitrogen Rydberg states together with ground-state hydrogen. In a small electron energy interval near 7 eV, a significant part of the final state population forms hydrogen Rydberg atoms with nitrogen atoms in the first excited (^2D) term, showing the effect of Rydberg doubly excited states below the predicted 2?2? ionic potential. The distance distributions above ˜10 eV are compatible with nitrogen Rydberg states correlating to the doubly excited Rydberg state manifold below the ionic 2?4?- level.

Yang, B.; Novotný, O.; Krantz, C.; Buhr, H.; Mendes, M.; Nordhorn, C.; Geppert, W. D.; Grieser, M.; Repnow, R.; Berg, M.; Bing, D.; Domesle, C.; Grussie, F.; Savin, D. Wolf; Schwalm, D.; Cai, X.; Wolf, A.

2014-02-01

145

Performance of an integrated approach for prediction of bond dissociation enthalpies of phenols extracted from ginger and tea  

NASA Astrophysics Data System (ADS)

Integration of the (RO)B3LYP/6-311++G(2df,2p) with the PM6 method into a two-layer ONIOM is found to produce reasonably accurate BDE(O-H)s of phenolic compounds. The chosen ONIOM model contains only two atoms of the breaking bond as the core zone and is able to provide reliable evaluation for BDE(O-H) for phenols and tocopherol. Deviation of calculated values from experiment is ±(1-2) kcal/mol. BDE(O-H) of several curcuminoids and flavanoids extracted from ginger and tea are computed using the proposed model. The BDE(O-H) values of enol curcumin and epigallocatechin gallate are predicted to be 83.3 ± 2.0 and 76.0 ± 2.0 kcal/mol, respectively.

Nam, Pham Cam; Chandra, Asit K.; Nguyen, Minh Tho

2013-01-01

146

Compact two-electron wave function for bond dissociation and Van der Waals interactions: A natural amplitude assessment  

SciTech Connect

Electron correlations in molecules can be divided in short range dynamical correlations, long range Van der Waals type interactions, and near degeneracy static correlations. In this work, we analyze for a one-dimensional model of a two-electron system how these three types of correlations can be incorporated in a simple wave function of restricted functional form consisting of an orbital product multiplied by a single correlation function f?(r{sub 12}) depending on the interelectronic distance r{sub 12}. Since the three types of correlations mentioned lead to different signatures in terms of the natural orbital (NO) amplitudes in two-electron systems, we make an analysis of the wave function in terms of the NO amplitudes for a model system of a diatomic molecule. In our numerical implementation, we fully optimize the orbitals and the correlation function on a spatial grid without restrictions on their functional form. Due to this particular form of the wave function, we can prove that none of the amplitudes vanishes and moreover that it displays a distinct sign pattern and a series of avoided crossings as a function of the bond distance in agreement with the exact solution. This shows that the wave function ansatz correctly incorporates the long range Van der Waals interactions. We further show that the approximate wave function gives an excellent binding curve and is able to describe static correlations. We show that in order to do this the correlation function f?(r{sub 12}) needs to diverge for large r{sub 12} at large internuclear distances while for shorter bond distances it increases as a function of r{sub 12} to a maximum value after which it decays exponentially. We further give a physical interpretation of this behavior.

Giesbertz, Klaas J. H. [Theoretical Chemistry, Faculty of Exact Sciences, VU University, De Boelelaan 1083, 1081 HV Amsterdam (Netherlands)] [Theoretical Chemistry, Faculty of Exact Sciences, VU University, De Boelelaan 1083, 1081 HV Amsterdam (Netherlands); Leeuwen, Robert van [Department of Physics, Nanoscience Center, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Survontie 9, Jyväskylä (Finland)] [Department of Physics, Nanoscience Center, University of Jyväskylä, P.O. Box 35, 40014 Jyväskylä, Survontie 9, Jyväskylä (Finland)

2014-05-14

147

Heats of Formation and Bond Energies in Group III Compounds  

NASA Technical Reports Server (NTRS)

We present heats of formation and bond energies for Group-III compounds obtained from calculations of molecular ground-state I electronic energies. Data for compounds of the form MXn are presented, where M = B, Al, Ga, and In, X = He H, Cl, and CH3, and n = 1-3. Energies for the B, Al, and Ga compounds are obtained from G2 predictions, while those for the In compounds are obtained from CCSD(T)/CBS calculations; these are the most accurate calculations for indium-containing compounds published to date. In most cases, the calculated thermochemistry is in good agreement with published values derived from experiments for those species that have well-established heats of formation. Bond energies obtained from the heats of formation follow the expected trend (Cl much greater than CH3 approx. H). However, the CH3M-(CH3)2 bond energies obtained for trimethylgallium and trimethylindium are considerably stronger (greater than 15 kcal/mol) than currently accepted values.

Bauschlicher, Charles W., Jr.; Allendorf, Mark D.; Melius, Carl F.; Arnold, James O. (Technical Monitor)

1999-01-01

148

Ab initio calculations on accurate dissociation energy, equilibrium geometry, and analytic potential energy function for the b3? state of 7LiH molecule  

Microsoft Academic Search

The accurate dissociation energy and equilibrium geometry of the b3? state of 7LiH molecule is calculated using a symmetry-adapted-cluster configuration-interaction method in full active space. And the calculated results are 0.2580 eV and 0.1958 nm for the dissociation energy and equilibrium geometry, respectively. The whole potential energy curve for the b3? state is also calculated over the internuclear separation range

Deheng Shi; Yufang Liu; Jinfeng Sun; Zunlue Zhu; Xiangdong Yang

2005-01-01

149

Argon hydrochloride, Ar.HCl, bond energy by infrared spectroscopy  

NASA Technical Reports Server (NTRS)

The infrared absorption of argon (200 to 760 torr) and hydrogen chloride (2 to 6 torr) mixtures is reexamined in the missing Q branch region (spectral region between 2860 and 3010 wavelength/cm) at temperatures ranging from 195 to 298 K. The temperature dependence of two absorption features of the argon hydrogen chloride complex, at 2887 and 2879 wavelength/cm, leads to a bond energy estimate that depends on the assumptions made about the internal degrees of freedom of the complex. It is shown that agreement with experiment can be reached for well depths near 1.2 kcal/mole. This result is relatively insensitive to the choice of the vibrational frequencies and anharmonicities, but does depend on the extent to which the energy level manifolds are truncated to avoid molecular excitation in excess of the bond energy. The bond energy is found to deviate from the commonly accepted value of 0.4 kcal/mole. Possible causes for the discrepancy are considered.

Miziolek, A. W.; Pimentel, G. C.

1976-01-01

150

Analysis of liquid metal embrittlement from a bond energy viewpoint  

NASA Technical Reports Server (NTRS)

Absorption induced embrittlement of solid metals by certain liquid metals is analyzed through an Engel-Brewer calculation of the solid-liquid interaction energy, and of the effect of the latter in reducing fracture surface energy. The reduction in fracture surface energy is estimated by comparison of the electronic contribution to the solid-liquid interaction energy with solid-solid bond energy for some 40 liquid-solid couples. Regular solution theory is used to estimate mutual solubility as the relative difference in parameter values. Embrittlement can be predicted by using reduction in fracture surface energy and solubility parameter difference as critical variables. The effect of solute additions to the liquid on the degree of embrittlement is interpreted via the same two variables; the principal effect of solutes is to modify solubility relationships at the solid-liquid interface.

Kelley, M. J.; Stoloff, N. S.

1975-01-01

151

Structures, energies, and bonding in the water heptamer  

NASA Astrophysics Data System (ADS)

In this paper we report the geometries and properties of 38 distinct geometrical motifs located on the B3LYP/6-31+G(d), MP2/6-311++G(d, p) potential energy surfaces of the water heptamer. Binding energies of up to 45 kcal/mol are calculated. All motifs fall within 10 kcal/mol of the most stable conformation, with at least 13 structural patterns located no more than 3 kcal/mol above, leading to a very complex potential energy surface, populated by a multitude of motifs each one allowing large numbers of conformations. Cluster stability does not seem to be correlated with the number of hydrogen bonds. Compact structures are energetically favored by electronic energies with zero-point energy corrections, while more open structures are preferred when temperature and entropy are accounted for. The molecular interactions holding the clusters as discrete units lead to large binding energies but are not strong enough to cause significant changes in the geometries of the interacting monomers. Our results indicate that bonding in the water heptamers can be considered as largely non-shared interactions with contributions from intermediate character of increasing covalency.

Acelas, Nancy; Hincapié, Gina; Guerra, Doris; David, Jorge; Restrepo, Albeiro

2013-07-01

152

Dissociation energy for C(2) loss from fullerene cations in a storage ring.  

PubMed

We have stored positively charged fullerene ions C(+)(n) (n even, from 48 to 70 and 76), C(2+)(60) and C(2+)(70) in an electrostatic storage ring and have measured the rate of emission of neutral fragments as a function of time. In the time range of the measurements, 50 micros to a few milliseconds, the rate decreases strongly due to radiative cooling of the molecules. Using the cooling rate predicted from a dielectric model, we have extracted the dissociation energies for C(2) loss from the measurements. As expected, the energies are largest for the "magic" fullerenes, C(50), C(60), and C(70), and the value of 9.8+/-0.1 eV for C(2) loss from C(+)(60) is in reasonable agreement with theory and with other recent experiments. PMID:11497890

Tomita, S; Andersen, J U; Gottrup, C; Hvelplund, P; Pedersen, U V

2001-08-13

153

Dissociation Energy for C2 Loss from Fullerene Cations in a Storage Ring  

NASA Astrophysics Data System (ADS)

We have stored positively charged fullerene ions C+n (n even, from 48 to 70 and 76), C2+60 and C2+70 in an electrostatic storage ring and have measured the rate of emission of neutral fragments as a function of time. In the time range of the measurements, 50 ?s to a few milliseconds, the rate decreases strongly due to radiative cooling of the molecules. Using the cooling rate predicted from a dielectric model, we have extracted the dissociation energies for C2 loss from the measurements. As expected, the energies are largest for the ``magic'' fullerenes, C50, C60, and C70, and the value of 9.8+/-0.1 eV for C2 loss from C+60 is in reasonable agreement with theory and with other recent experiments.

Tomita, S.; Andersen, J. U.; Gottrup, C.; Hvelplund, P.; Pedersen, U. V.

2001-08-01

154

Effects of Exchange Energy and Spin-Orbit Coupling on Bond Energies  

ERIC Educational Resources Information Center

Since chemical reactions involve the breaking and making of bonds, understanding the relative strengths of bonds is of paramount importance in the study, teaching, and practice of chemistry. Further, it is showed that free atoms having p(super n) configuration with n = 2,3, or 4 are stabilized by exchange energy, and by spin-orbit coupling for n =…

Smith, Derek W.

2004-01-01

155

The Role of Translational, Vibrational, and Rotational Energy in the Dissociative Adsorption of Hydrogen on Copper Surfaces  

NASA Astrophysics Data System (ADS)

This dissertation presents a study of the role of translational, vibrational, and rotational energy in the dissociative adsorption and associative desorption of hydrogen and deuterium at single-crystal copper surfaces. It begins with a historical account of the work that lead to the current status of the H_2/Cu system as a model system for the study of gas-surface dynamics. This review is followed by a description of a model developed to investigate the role of vibration in the adsorption of hydrogen on copper. The model, which is based on a quantitative description of the variation of the adsorption probability with vibrational state, kinetic energy, and angle of the incident molecules, is used to resolve some of the apparent discrepancies in adsorption and desorption experiments. Direct adsorption measurements covering a wide range of incidence angles, energies, and vibrational temperatures are presented for D_2 on Cu(111). The model described above is used to establish from these data the dependence of the adsorption probability on incidence energy and angle for each vibrational state from v = 0 to 3. These results demonstrate that vibrational energy is effective in promoting adsorption. Angular distributions of D_2 desorbed from Cu(111) at several surface temperatures (370, 600, and 800 K) are then presented and analyzed in the context of the model described above. The results suggest that increasing surface temperature influences the adsorption through enhanced surface motion. The results of state-resolved inelastic scattering measurements of H_2 and D _2 from Cu(111) are also given and show that molecules with sufficient kinetic energy to access the barrier to adsorption have a high probability of being vibrationally excited upon scattering from the surface. These results support the picture of a transition state to adsorption characterized by a stretched intramolecular bond. State-resolved kinetic energy distributions of D_2 desorbed from Cu(111) are then presented. It is shown that rotational energy hinders adsorption for low rotational states and enhances adsorption for high rotational states. These results highlight the need to describe this system with a multidimensional picture that includes the effect of rotation on adsorption.

Michelsen, Hope Andrea

156

Dissociative double photoionization of singly deuterated benzene molecules in the 26-33 eV energy range  

NASA Astrophysics Data System (ADS)

This work provides new experimental and theoretical results about the formation and dissociation of benzene dication. The experiment has been carried out by using a vacuum ultraviolet radiation from a synchrotron source together with a time-of-flight spectrometer and a position sensitive ion detector. Isotopically labeled benzene molecules with a single deuterium atom have been used in order to study the symmetric dissociation of the benzene dication, not well evident in previous experiments. A threshold of 30.1 ± 0.1 eV has been observed for this dissociation reaction. Moreover, the lifetime of the dissociation of the benzene metastable dication producing CH3+ and C5H3+ has been obtained as a function of the photon energy, by the use of a Monte Carlo trajectory analysis of the coincidence distributions. The determined lifetime is independent of the photon energy and has an average value of 0.75 ± 0.22 ?s. Theoretical calculations of the energy and structure of dissociation product ions have been also performed to provide crucial information about the dynamics of the charge separation reactions following the photoionization event.

Alagia, M.; Candori, P.; Falcinelli, S.; Mundim, M. S. P.; Pirani, F.; Richter, R.; Rosi, M.; Stranges, S.; Vecchiocattivi, F.

2011-10-01

157

Dissociative double photoionization of singly deuterated benzene molecules in the 26-33 eV energy range.  

PubMed

This work provides new experimental and theoretical results about the formation and dissociation of benzene dication. The experiment has been carried out by using a vacuum ultraviolet radiation from a synchrotron source together with a time-of-flight spectrometer and a position sensitive ion detector. Isotopically labeled benzene molecules with a single deuterium atom have been used in order to study the symmetric dissociation of the benzene dication, not well evident in previous experiments. A threshold of 30.1 ± 0.1 eV has been observed for this dissociation reaction. Moreover, the lifetime of the dissociation of the benzene metastable dication producing CH(3)(+) and C(5)H(3)(+) has been obtained as a function of the photon energy, by the use of a Monte Carlo trajectory analysis of the coincidence distributions. The determined lifetime is independent of the photon energy and has an average value of 0.75 ± 0.22 ?s. Theoretical calculations of the energy and structure of dissociation product ions have been also performed to provide crucial information about the dynamics of the charge separation reactions following the photoionization event. PMID:22010715

Alagia, M; Candori, P; Falcinelli, S; Mundim, M S P; Pirani, F; Richter, R; Rosi, M; Stranges, S; Vecchiocattivi, F

2011-10-14

158

Measuring the energy landscape of complex bonds using AFM  

NASA Astrophysics Data System (ADS)

We measured rupture force of a complex bond of two interacting proteins with atomic force microscopy. Proteins of interest were active and latent Matrix metalloproteinases (MMPs), type 2 and 9, and their tissue inhibitors TIMP1 and TIMP2. Measurements show that the rupture force depends on the pulling speed; it ranges from 30 pN to 150 pN at pulling speeds 30nm/s to 48000nm/s. Analyzing data using an extended theory enabled us to understand the mechanism of MMP-TIMP interaction; we determined all physical parameters that form the landscape energy of the interaction, in addition to the life time of the bond and its length. Moreover, we used the pulling experiment to study the interaction of TIMP2 with the receptor MT1-MMP on the surface of living cells.

Mayyas, Essa; Hoffmann, Peter; Runyan, Lindsay

2009-03-01

159

Bond and site selectivity in dissociative electron attachment to gas phase and condensed phase ethanol and trifluoroethanol.  

PubMed

The formation of negative ions following electron impact to ethanol (CH(3)CH(2)OH) and trifluoroethanol (CF(3)CH(2)OH) is studied in the gas phase by means of a crossed electron-molecular beam experiment and in the condensed phase via Electron Stimulated Desorption (ESD) of fragment ions from the corresponding molecular films under UHV conditions. Gas phase ethanol exhibits two pronounced resonances, located at 5.5 eV and 8.2 eV, associated with a remarkable selectivity in the decomposition of the precursor ion. While the low energy resonance exclusively decomposes into O(-), that at higher energy generates OH(-) and a comparatively small signal of [CH(3)CH(2)O](-) due to the loss of a neutral hydrogen. CF(3)CH(2)OH shows a completely different behaviour, as now an intense feature at 1.7 eV appears associated with the loss of a neutral hydrogen atom exclusively occurring at the O site. The H(-) formation from the gas phase compounds is below the detection limit of the present experiment, while in ESD from 3 MonoLayer (ML) films of CH(3)CH(2)OH and CF(3)CH(2)OH the most intense fragment is H(-), appearing from a broad resonant feature between 7 and 12 eV. With CF(3)CH(2)OH, by using the isotopically-labelled analogues CF(3)CD(2)OH and CF(3)CH(2)OD it can be shown that this feature consists of two resonances, one located at 8 eV leading to H(-)/D(-) loss from the O site and a second resonance located at 10 eV leading to the loss of H(-)/D(-) from the CH(2) site. PMID:17664966

Orzol, Mario; Martin, Isabel; Kocisek, Jaroslav; Dabkowska, Iwona; Langer, Judith; Illenberger, Eugen

2007-07-14

160

Dissociative Tendencies and Dissociative Disorders  

Microsoft Academic Search

Although dissociative disorders are relatively rare, dissociative experiences are rather common in everyday life. Dissociative tendencies appear to be modestly related to other dimensions of personality, such as hypnotizability, absorption, fantasy proneness, and some facets of openness to experience. These dispositional variables may constitute diatheses, or risk factors, for dissociative psychopathology, but more complex models relating personality to psychopathology may

John F. Kihlstrom; Martha L. Glisky; Michael J. Angiulo

1994-01-01

161

Controlling the bond scission sequence of oxygenates for energy applications  

NASA Astrophysics Data System (ADS)

The so called "Holy Grail" of heterogeneous catalysis is a fundamental understanding of catalyzed chemical transformations which span multidimensional scales of both length and time, enabling rational catalyst design. Such an undertaking is realizable only with an atomic level understanding of bond formation and destruction with respect to intrinsic properties of the metal catalyst. In this study, we investigate the bond scission sequence of small oxygenates (methanol, ethanol, ethylene glycol) on bimetallic transition metal catalysts and transition metal carbide catalysts. Oxygenates are of interest both as hydrogen carriers for reforming to H2 and CO and as fuels in direct alcohol fuel cells (DAFC). To address the so-called "materials gap" and "pressure gap" this work adopted three parallel research approaches: (1) ultra high vacuum (UHV) studies including temperature programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) on polycrystalline surfaces; (2) DFT studies including thermodynamic and kinetic calculations; (3) electrochemical studies including cyclic voltammetry (CV) and chronoamperometry (CA). Recent studies have suggested that tungsten monocarbide (WC) may behave similarly to Pt for the electrooxidation of oxygenates. TPD was used to quantify the activity and selectivity of oxygenate decomposition for WC and Pt-modifiedWC (Pt/WC) as compared to Pt. While decomposition activity was generally higher on WC than on Pt, scission of the C-O bond resulted in alkane/alkene formation on WC, an undesired product for DAFC. When Pt was added to WC by physical vapor deposition C-O bond scission was limited, suggesting that Pt synergistically modifies WC to improve the selectivity toward C-H bond scission to produce H2 and CO. Additionally, TPD confirmed WC and Pt/WC to be more CO tolerant than Pt. HREELS results verified that surface intermediates were different on Pt/WC as compared to Pt or WC and evidence of aldehyde intermediates was observed on the Pt and Pt/WC surfaces. For CH3OH decomposition, DFT calculations suggested that the bond scission sequence could be controlled using monolayer coverage of Pt on WC. The Ni/Pt bimetallic system was studied as an example for using oxygenates as a hydrogen source. There are two well characterized surface structures for the Ni/Pt system: the surface configuration, in which the Ni atoms reside primarily on the surface of the Pt bulk, and the subsurface configuration, in which the second atomic layer is enriched in Ni atoms and the surface is enriched in Pt atoms. These configurations are denoted NiPtPt and PtNiPt, respectively. DFT results revealed that trends established for the Ni/Pt(111) system extend to the Ni/Pt(100) analogue. TPD studies revealed that the NiPtPt surface was more active for oxygenate reforming than the Pt or PtNiPt surfaces. HREELS confirmed the presence of strongly bound reaction intermediates, including aldehyde-like species, and suggested that the first decomposition step was likely O-H bond scission. Thus, the binding energies of the deprotonated reaction intermediates are important parameters in controlling the decomposition pathways of oxygenates. These studies have demonstrated that the bond scission sequence of oxygenate decomposition can be controlled using bimetallic and transition metal carbide catalysts. While this study has focused on oxygenate decomposition for energy applications, the principles and methodology applied herein are universally applicable to the development of novel and marketable value-added products. The value in such a methodology is in the combination of both calculations to predict catalytic and chemical properties, and experiments to fine-tune theoretical predictions.

Stottlemyer, Alan L.

162

The molecular dissociation of formaldehyde at medium photoexcitation energies: A quantum chemistry and direct quantum dynamics study  

NASA Astrophysics Data System (ADS)

The mechanisms of radiationless decay involved in the photodissociation of formaldehyde into H2 and CO have been investigated using complete active space self-consistent field (CASSCF) calculations and direct dynamics variational multiconfiguration Gaussian (DD-vMCG) quantum dynamics in the S1, T1, and S0 states. A commonly accepted scheme involves Fermi Golden Rule internal conversion from S1 followed by dissociation of vibrationally hot H2CO in S0. We recently proposed a novel mechanism [M. Araujo et al., J. Phys. Chem. A 112, 7489 (2008)] whereby internal conversion and dissociation take place in concert through a seam of conical intersection between S1 and S0 after the system has passed through an S1 transition barrier. The relevance of this mechanism depends on the efficiency of tunneling in S1. At lower energy, an alternative scheme to internal conversion involves intersystem crossing via T1 to regenerate the reactant before the S0 barrier to dissociation. We propose here a previously unidentified mechanism leading directly to H2 and CO products via T1. This channel opens at medium energies, near or above the T1 barrier to dissociation and still lower than the S1 barrier, thus making T1 a possible shortcut to molecular dissociation.

Araújo, Marta; Lasorne, Benjamin; Magalhães, Alexandre L.; Worth, Graham A.; Bearpark, Michael J.; Robb, Michael A.

2009-10-01

163

Organic Solar Cells with Graded Exciton-dissociation Interfaces.................................................................................................................EN.1 Luminescent Solar Concentrators for Energy-harvesting in Displays ........  

E-print Network

Energy Organic Solar Cells with Graded Exciton-dissociation Interfaces.................................................................................................................EN.1 Luminescent Solar Concentrators for Energy-harvesting in Displays ...................................................................................EN.3 Nano-engineered Organic Solar-energy-harvesting System

Reif, Rafael

164

Prediction of the bond lengths, vibrational frequencies, and bond dissociation energy of octahedral seaborgium hexacarbonyl, Sg(CO)â  

Microsoft Academic Search

The recent syntheses of several new elements (including the recent reports of elements 116 and 118), coupled with the controversy surrounding the naming of elements 104--109, have stimulated a great interest in the chemistry of the transactinide elements. This contribution addresses hypothetical hexacarbonyl complex of seaborgium (Sg, element 106), which is predicted to be a 6d-block transition element with six

Clinton S. Nash; Bruce E. Bursten

1999-01-01

165

Presolvated Low Energy Electron Attachment to Peptide Methyl esters in Aqueous Solution: C-O Bond Cleavage at 77K  

PubMed Central

In this study, the reactions of presolvated electrons with glycine methyl ester and N-acetylalanylalanine methyl ester (N-aAAMe) are investigated by electron spin resonance (ESR) spectroscopy and DFT calculations. Electrons were produced by gamma irradiation in neutral 7.5 M LiCl-D2O aqueous glasses at low temperatures. For glycine methyl ester electron addition at 77K results in both N-terminal deamination to form a glycyl radical and C-O ester bond cleavage to form methyl radicals. For samples of N-acetylalanylalanine methyl ester electrons are found to add to the peptide bonds at 77K and cleave the carboxyl ester groups to produce methyl radicals. On annealing to 160K electron adducts at the peptide links undergo chain scission to produce alanyl radicals and further annealing to 170K ?-carbon peptide backbone radicals are produced by hydrogen abstraction. DFT calculations for electron addition to the methyl ester portion of N-aAAMe show the cleavage reaction is highly favorable (free energy equals to ?30.7 kcal/mol) with the kinetic barrier of only 9.9 kcal/mol. A substantial electron affinity of the ester link (38.0 kcal/mol) provides more than sufficient energy to overcome this small barrier. Protonated peptide bond electron adducts, also show favorable N-C chain cleavage reactions of ?12.7 to ?15.5 kcal/mol with a barrier from 7.4 to 10.0 kcal/mol. The substantial adiabatic electron affinity (AEA) of the peptide bond and ester groups provides sufficient energy for the bond dissociation. PMID:23406302

Kheir, Jeanette; Chomicz, Lidia; Engle, Alyson; Rak, Janusz; Sevilla, Michael D.

2013-01-01

166

Unambiguous Phosphosite Localization using Electron-Transfer/Higher-Energy Collision Dissociation (EThcD)  

PubMed Central

We recently introduced a novel scheme combining electron-transfer and higher-energy collision dissociation (termed EThcD), for improved peptide ion fragmentation and identification. We reasoned that phosphosite localization, one of the major hurdles in high-throughput phosphoproteomics, could also highly benefit from the generation of such EThcD spectra. Here, we systematically assessed the impact on phosphosite localization utilizing EThcD in comparison to methods employing either ETD or HCD, respectively, using a defined synthetic phosphopeptide mixture and also using a larger data set of Ti4+-IMAC enriched phosphopeptides from a tryptic human cell line digest. In combination with a modified version of phosphoRS, we observed that in the majority of cases EThcD generated richer and more confidently identified spectra, resulting in superior phosphosite localization scores. Our data demonstrates the distinctive potential of EThcD for PTM localization, also beyond protein phosphorylation. PMID:23347405

2013-01-01

167

A test structure for characterization of the interface energy of anodically bonded silicon-glass wafers  

Microsoft Academic Search

In this paper a test structure is introduced, which allows the evaluation of the quality of an anodic bond interface in terms of surface energy. It is based on the creation of small non-bonded areas in the vicinity of small steps in the bond interface. Using finite element analysis simulations it was possible to calculate the surface energy of the

R. Knechtel; M. Knaup; J. Bagdahn

2006-01-01

168

Using dissociation energies to predict observability of b? and y? peaks in mass spectra of short peptides  

PubMed Central

RATIONALE Peptide identification reliability can be improved by excluding from analysis those m/z peaks of candidate peptides, which can not be observed in practice due to various physical, chemical or thermodynamic considerations. We propose using dissociation energies (as opposed to proton affinities) as a predictor of observability of different m/z peaks in spectra of short peptides. METHODS Experiment Mass spectra of tetrapeptides AAAA, AAFA, AAVA, AFAA, AVAA, AFFA, AVVA have been measured in the CID activation mode on a grid of activation times 0.05 to 100 ms and normalized collision energy 10 to 35 %. Computations Lowest energy geometries and vibrational spectra were calculated for the precursor ions and their charged and neutral fragments using DFT at the TPSS/6-31G(d,p) level. Dissociation energies were calculated for all fragmentation channels leading to b? or y? fragments. RESULTS It is demonstrated that m/z peaks observed in the mass spectra correspond to the fragmentation channels with the lowest dissociation energies. Using 50 kcal/mol as the cut off value of dissociation energy, it was predicted that 28 out of 42 possible peaks in the b? and y? series of the seven tetrapeptides cab be observed in mass spectra. In the experiments, 26 b? or y? peaks were observed, all of which are among the 28 predicted ones. CONCLUSIONS The use of dissociation energies generalizes the use of proton affinities for semi-quantitative predictions of relative intensities of different m/z peaks of short peptides. Further advances in this direction will pave the way for reliable quantitative predictions and, hence, for a significant improvement in robustness and accuracy of peptide and protein identification tools. PMID:22396027

Obolensky, O. I.; Wu, Wells W.; Shen, R.-F.; Yu, Yi-Kuo

2012-01-01

169

Dissociation mechanisms of the Ar trimer induced by a third atom in high-energy electron-impact ionization  

NASA Astrophysics Data System (ADS)

We experimentally studied the dissociation dynamics of a highly charged Ar3 cluster initiated by a high-energy electron. The dissociation patterns of the correlated ions from a two-body and a three-body Coulombic explosion (CE) of (Ar3)2+ suggest that predissociation alters the evolution of radiative charge transfer. The three-body CE in (Ar3)4+ and (Ar3)5+ is driven, after double ionization of one constituent Ar atom, by single ionization with a simultaneous interatomic Coulombic decay process.

Yan, S.; Zhang, P.; Ma, X.; Xu, S.; Tian, S. X.; Li, B.; Zhu, X. L.; Feng, W. T.; Zhao, D. M.

2014-06-01

170

The Trouble with Chemical Energy: Why Understanding Bond Energies Requires an Interdisciplinary Systems Approach  

ERIC Educational Resources Information Center

Helping students understand "chemical energy" is notoriously difficult. Many hold inconsistent ideas about what energy is, how and why it changes during the course of a chemical reaction, and how these changes are related to bond energies and reaction dynamics. There are (at least) three major sources for this problem: 1) the way biologists talk…

Cooper, Melanie M.; Klymkowsky, Michael W.

2013-01-01

171

Comparison of the collision-induced dissociation of duplex DNA at different collision regimes: evidence for a multistep dissociation mechanism.  

PubMed

The dissociation mechanism of duplex DNA has been investigated in detail by collision-induced dissociation experiments at different collision regimes. MS/MS experiments were performed either in a quadrupole collision cell (hybrid quadrupole-TOF instrument) or in a quadrupole ion trap with different activation times and energies. In addition to the noncovalent dissociation of the duplex into the single strands, other covalent bond fragmentation channels were observed. Neutral base loss from the duplex is favored by slow activation. In fast activation conditions, however, the major reaction channel is the noncovalent dissociation into single strands, which is highly entropy-favored. Fast activation regimes can favor the entropy-driven noncovalent dissociation, while in slow heating conditions the competition with enthalpy-driven covalent fragmentation can completely hinder the dissociation of the complex. We also evidence that the noncovalent dissociation of DNA duplex is a multistep process involving a progressive unzipping, preferentially at terminal positions. This is proposed to be a general feature for complexes containing a high number of contributing interactions organized at the interface of the ligands. The overall (observed) dissociation kinetics of noncovalent complexes can therefore depend on a complicated mechanism for which a single transition state description of the kinetics is too simplistic. PMID:11777205

Gabelica, Valérie; De, Pauw Edwin

2002-01-01

172

"Surface-Induced Dissociation of Acetone Cations from Self-Assembled Monolayer Surface of Flourinated Alkyl Thiol on Au (111) Substrate at Low Collision Energies"  

SciTech Connect

We have studied the dissociation of acetone molecular cations to acetyl cations following collision with a monolayer surface of fluorinated alkyl thiol (FC12) self-assembled on Au (111) substrate at 13, 25.2 and 49.6 eV kinetic energies. Three energetically distinct dissociation processes contribute to total dissociation in this energy range. At all energies there is a common dissociation pathway involving loss of nearly all of the parent ions kinetic energy in the collision process. Fragment ions resulting from this dissociation mechanism are scattered over a wide range of angles. The second pathway, observed at 25.2 and 49.6 eV kinetic energy is delayed dissociation of collisionally excited acetone cations after only a small fraction of the ions kinetic energy is lost in the collision process. Fragment ions resulting from this unique dynamics feature are scattered close to the surface parallel. These dissociations take place after the excited ions have passed through the collision region and the energy analyzer and prior to their entering the mass analyzer. At 49.6 eV kinetic energy, a small intensity fragment ion peak appears at intermediate kinetic energy spectra between the low energy loss and the highly inelastic scattering peaks.

Shukla, Anil K. (BATTELLE (PACIFIC NW LAB)); Futrell, Jean H. (BATTELLE (PACIFIC NW LAB))

2003-08-15

173

Low-energy collision-induced dissociation of deprotonated dinucleotides: determination of the energetically favored dissociation pathways and the relative acidities of the nucleic acid bases  

Microsoft Academic Search

Fourier transform ion cyclotron resonance mass spectroscopy has been used to examine the collision-induced dissociation pathways of all 16 of the possible deprotonated dinucleotides. These quasimolecular ions were generated by cesium ion bombardment of a mixture of triethanolamine, ammonium hydroxide and the dinucleotide. Collisional activation using continuous off-resonance excitation permits observation of energetically-favorable dissociation pathways. Dissociation products were examined over

M. T. Rodgers; Sherrie Campbell; Elaine M. Marzluff; J. L. Beauchamp

1994-01-01

174

A variational algebraic method used to study the full vibrational spectra and dissociation energies of some specific diatomic systems.  

PubMed

The algebraic method (AM) proposed by Sun et al. is improved to be a variational AM (VAM) to offset the possible experimental errors and to adapt to the individual energy expansion nature of different molecular systems. The VAM is used to study the full vibrational spectra {E?} and the dissociation energies De of (4)HeH(+)-X(1)?(+), (7)Li2-1(3)?g,Na2-C(1)?u,NaK-7(1)?, Cs2-B(1)?u and (79)Br2-?1g((3)P2) diatomic electronic states. The results not only precisely reproduce all known experimental vibrational energies, but also predict correct dissociation energies and all unknown high-lying levels that may not be given by the original AM or other numerical methods or experimental methods. The analyses and the skill suggested here might be useful for other numerical simulations and theoretical fittings using known data that may carry inevitable errors. PMID:24013115

Zhang, Yi; Sun, Weiguo; Fu, Jia; Fan, Qunchao; Ma, Jie; Xiao, Liantuan; Jia, Suotang; Feng, Hao; Li, Huidong

2014-01-01

175

Bond energy effects on strength, cooperativity and robustness of molecular structures.  

PubMed

A fundamental challenge in engineering biologically inspired materials and systems is the identification of molecular structures that define fundamental building blocks. Here, we report a systematic study of the effect of the energy of chemical bonds on the mechanical properties of molecular structures, specifically, their strength and robustness. By considering a simple model system of an assembly of bonds in a cluster, we demonstrate that weak bonding, as found for example in H-bonds, results in a highly cooperative behaviour where clusters of bonds operate synergistically to form relatively strong molecular clusters. The cooperative effect of bonding results in an enhanced robustness since the drop of strength owing to the loss of a bond in a larger cluster only results in a marginal reduction of the strength. Strong bonding, as found in covalent interactions such as disulphide bonds or in the backbone of proteins, results in a larger mechanical strength. However, the ability for bonds to interact cooperatively is lost, and, as a result, the overall robustness is lower since the mechanical strength hinges on individual bonds rather than a cluster of bonds. The systematic analysis presented here provides general insight into the interplay of bond energy, robustness and other geometric parameters such as bond spacing. We conclude our analysis with a correlation of structural data of natural protein structures, which confirms the conclusions derived from our study. PMID:23050078

Chou, Chia-Ching; Buehler, Markus J

2011-10-01

176

Does Nitric Acid Dissociate at the Aqueous Solution Surface?  

SciTech Connect

Nitric acid is a prevalent component of atmospheric aerosols, and the extent of nitric acid dissociation at aqueous interfaces is relevant to its role in heterogeneous atmospheric chemistry. Several experimental and theoretical studies have suggested that the extent of dissociation of nitric acid near aqueous interfaces is less than in bulk solution. Here, dissociation of HNO3 at the surface of aqueous nitric acid is quantified using X-ray photoelectron spectroscopy of the nitrogen local electronic structure. The relative amounts of undissociated HNO3(aq) and dissociated NO3-(aq) are identified by the distinguishable N1s core-level photoelectron spectra of the two species, and we determine the degree of dissociation, ?int, in the interface (the first ~3 layers of solution) as a function of HNO3 concentration. Our measurements show that dissociation is decreased by approximately 20% near the solution interface compared with bulk, and furthermore that dissociation occurs even in the top-most solution layer. The experimental results are supported by first-principles MD simulations, which show that hydrogen-bonds between HNO3 and water molecules at the solution surface stabilize the molecular form at low concentration, in analogy to the stabilization of molecular HNO3 that occurs in bulk solution at high concentration. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

2011-11-03

177

Direct evaluation of individual hydrogen bond energy in situ in intra- and intermolecular multiple hydrogen bonds system.  

PubMed

The results of evaluating the individual hydrogen bond (H-bond) strength are expected to be helpful for the rational design of new strategies for molecular recognition or supramolecular assemblies. Unfortunately, there is few obvious and unambiguous means of evaluating the energy of a single H-bond within a multiple H-bonds system. We present a local analytic model, ABEEM?? H-bond energy (HBE) model based on ab initio calculations (MP2) as benchmark, to directly and rapidly evaluate the individual HBE in situ in inter- and intramolecular multiple H-bonds system. This model describes the HBE as the sum of electrostatic and van der Waals (vdW) interactions which all depend upon the geometry and environment, and the ambient environment of H-bond in the model is accounted fairly. Thus, it can fairly consider the cooperative effect and secondary effect. The application range of ABEEM?? HBE model is rather wide. This work has discussed the individual H-bond in DNA base pair and protein peptide dimers. The results indicate that the interactions among donor H atom, acceptor atom as well as those atoms connected to them with 1,2 or 1,3 relationships are all important for evaluating the HBE, although the interaction between the donor H atom and the acceptor atom is large. Furthermore, our model quantitatively indicates the polarization ability of N, O, and S in a new style, and gives the percentage of the polarization effect in HBE, which can not be given by fixed partial charge force field. PMID:22170234

Liu, Cui; Zhao, Dong-Xia; Yang, Zhong-Zhi

2012-02-01

178

Vibrationally resolved structure in O2+ dissociation induced by intense ultrashort laser pulses  

NASA Astrophysics Data System (ADS)

Laser-induced dissociation of O2+ is studied in the strong-field limit using two independent methods, namely a crossed laser-ion-beam coincidence 3D momentum imaging method and a supersonic gas jet velocity map imaging technique (790 and 395 nm, 8-40 fs, ~1015 W/cm2). The measured kinetic energy release spectra from dissociation of O2+ and dissociative ionization of O2 reveal vibrational structure which persists over a wide range of laser intensities. The vibrational structure is similar for O2+ produced incoherently in an ion source and coherently by laser pulses. By evaluation of the potential energy curves, we assign the spectral energy peaks to dissociation of the v=10-15 vibrational states of the metastable a4?u state via the dissociation pathway |a4?u>?|f4?g-1?>—a mechanism equivalent to bond softening in H2+.

Zohrabi, M.; McKenna, J.; Gaire, B.; Johnson, Nora G.; Carnes, K. D.; de, S.; Bocharova, I. A.; Magrakvelidze, M.; Ray, D.; Litvinyuk, I. V.; Cocke, C. L.; Ben-Itzhak, I.

2011-05-01

179

Full-dimensional diabatic potential energy surfaces including dissociation: The 2E? state of NO3  

NASA Astrophysics Data System (ADS)

A scheme to produce accurate full-dimensional coupled diabatic potential energy surfaces including dissociative regions and suitable for dynamical calculations is proposed. The scheme is successfully applied to model the two-sheeted surface of the 2E? state of the NO3 radical. An accurate potential energy surface for the NO_3^- anion ground state is developed as well. Both surfaces are based on high-level ab initio calculations. The model consists of a diabatic potential matrix, which is expanded to higher order in terms of symmetry polynomials of symmetry coordinates. The choice of coordinates is key for the accuracy of the obtained potential energy surfaces and is discussed in detail. A second central aspect is the generation of reference data to fit the expansion coefficients of the model for which a stochastic approach is proposed. A third ingredient is a new and simple scheme to handle problematic regions of the potential energy surfaces, resulting from the massive undersampling by the reference data unavoidable for high-dimensional problems. The final analytical diabatic surfaces are used to compute the lowest vibrational levels of NO_3^- and the photo-electron detachment spectrum of NO_3^- leading to the neutral radical in the 2E? state by full dimensional multi-surface wave-packet propagation for NO3 performed using the Multi-Configuration Time Dependent Hartree method. The achieved agreement of the simulations with available experimental data demonstrates the power of the proposed scheme and the high quality of the obtained potential energy surfaces.

Eisfeld, Wolfgang; Vieuxmaire, Olivier; Viel, Alexandra

2014-06-01

180

Full-dimensional diabatic potential energy surfaces including dissociation: the ²E? state of NO?.  

PubMed

A scheme to produce accurate full-dimensional coupled diabatic potential energy surfaces including dissociative regions and suitable for dynamical calculations is proposed. The scheme is successfully applied to model the two-sheeted surface of the (2)E? state of the NO3 radical. An accurate potential energy surface for the NO?? anion ground state is developed as well. Both surfaces are based on high-level ab initio calculations. The model consists of a diabatic potential matrix, which is expanded to higher order in terms of symmetry polynomials of symmetry coordinates. The choice of coordinates is key for the accuracy of the obtained potential energy surfaces and is discussed in detail. A second central aspect is the generation of reference data to fit the expansion coefficients of the model for which a stochastic approach is proposed. A third ingredient is a new and simple scheme to handle problematic regions of the potential energy surfaces, resulting from the massive undersampling by the reference data unavoidable for high-dimensional problems. The final analytical diabatic surfaces are used to compute the lowest vibrational levels of NO?? and the photo-electron detachment spectrum of NO?? leading to the neutral radical in the (2)E? state by full dimensional multi-surface wave-packet propagation for NO3 performed using the Multi-Configuration Time Dependent Hartree method. The achieved agreement of the simulations with available experimental data demonstrates the power of the proposed scheme and the high quality of the obtained potential energy surfaces. PMID:24929376

Eisfeld, Wolfgang; Vieuxmaire, Olivier; Viel, Alexandra

2014-06-14

181

Zero Kinetic Energy Photofragment Spectroscopy: The Threshold Dissociation of NO2 J. A. Mueller, S. A. Rogers, and Paul L. Houston*  

E-print Network

to the fragment recoil velocity.4-9 Values of the anisotropy parameter in the range from 0.6 to 1.8 were obtainedZero Kinetic Energy Photofragment Spectroscopy: The Threshold Dissociation of NO2 J. A. Mueller, S be useful in the accurate identification of the dissociation threshold. The technique is demonstrated

Houston, Paul L.

182

Rovibrational internal energy transfer and dissociation of N2(1?g+)-N(4Su) system in hypersonic flows  

NASA Astrophysics Data System (ADS)

A rovibrational collisional model is developed to study energy transfer and dissociation of N_2(^1? _g^+) molecules interacting with N(^4S_u) atoms in an ideal isochoric and isothermal chemical reactor. The system examined is a mixture of molecular nitrogen and a small amount of atomic nitrogen. This mixture, initially at room temperature, is heated by several thousands of degrees Kelvin, driving the system toward a strong non-equilibrium condition. The evolution of the population densities of each individual rovibrational level is explicitly determined via the numerical solution of the master equation for temperatures ranging from 5000 to 50 000 K. The reaction rate coefficients are taken from an ab initio database developed at NASA Ames Research Center. The macroscopic relaxation times, energy transfer rates, and dissociation rate coefficients are extracted from the solution of the master equation. The computed rotational-translational (RT) and vibrational-translational (VT) relaxation times are different at low heat bath temperatures (e.g., RT is about two orders of magnitude faster than VT at T = 5000 K), but they converge to a common limiting value at high temperature. This is contrary to the conventional interpretation of thermal relaxation in which translational and rotational relaxation timescales are assumed comparable with vibrational relaxation being considerable slower. Thus, this assumption is questionable under high temperature non-equilibrium conditions. The exchange reaction plays a very significant role in determining the dynamics of the population densities. The macroscopic energy transfer and dissociation rates are found to be slower when exchange processes are neglected. A macroscopic dissociation rate coefficient based on the quasi-stationary distribution, exhibits excellent agreement with experimental data of Appleton et al. [J. Chem. Phys. 48, 599-608 (1968)], 10.1063/1.1668690. However, at higher temperatures, only about 50% of dissociation is found to take place under quasi-stationary state conditions. This suggest the necessity of explicitly including some rovibrational levels, when solving a global kinetic rate equation.

Panesi, Marco; Jaffe, Richard L.; Schwenke, David W.; Magin, Thierry E.

2013-01-01

183

Metallic bond effects on mean excitation energies for stopping powers  

NASA Technical Reports Server (NTRS)

Mean excitation energies for first row metals are evaluated by means of the local plasma approximation. Particle corrections based on Pines' (1953) procedure and the Wigner Seitz (1934) model of the metallic state are included. The agreement with experimental values is remarkably good. In contrast to previous work, the calculations given here estimate shifts in the plasma frequency according to the theory for plane wave states in an extended plasma as calculated by Pines. It is demonstrated that the effects of the metallic bond in lithium and beryllium are quite large and that they appear mainly as a result of collective oscillations in the 'free' electron gas formed from the valence electrons. The usefulness of the plasma frequency shift derived for a degenerate electron gas in predicting the plasma frequency shift within the ion core is considered surprising.

Wilson, J. W.; Xu, Y. J.

1982-01-01

184

Calculation of activation energies for hydrogen-atom abstractions by radicals containing carbon triple bonds  

NASA Technical Reports Server (NTRS)

Activation energies are calculated by the bond-energy-bond-order (BEBO) and the bond-strength-bond-length (BSBL) methods for the reactions of C2H radicals with H2, CH4, and C2H6 and for the reactions of CN radicals with H2 and CH4. The BSBL technique accurately predicts the activation energies for these reactions while the BEBO method yields energies averaging 9 kcal higher than those observed. A possible reason for the disagreement is considered.

Brown, R. L.; Laufer, A. H.

1981-01-01

185

Dissociative electron attachment, electron transmission, and electron energy-loss study of the temporary negative ion of acetylene  

SciTech Connect

The three title electron-impact techniques are used to study the ground and excited states of acetylene negative ion and their decay processes. The ..pi..* resonance at 2.6 eV predissociates into C/sub 2/H/sup -/ and H. Four narrow resonances are observed in the transmission spectrum in the 7.5--9.5 eV region and assigned to Feshbach and core-excited shape resonances with double occupation of Rydberg orbitals and ground state positive ion core. These four resonances decay into low-lying Rydberg states of neutral acetylene, the first two undergo quasiresonant autodetachment ejecting low energy (<0.7 eV) electrons, and the lowest also dissociates to yield C/sup -//sub 2/. One additional resonance is observed in the C/sup -//sub 2/ yield, which is not observable in other decay channels. The shapes of the dissociative attachment bands differ qualitatively from the band shapes of the parent and grandparent states, indicating either a strong v dependence of the dissociation rate or the admixture of sigma* orbitals in some of the dissociating anion states.

Dressler, R.; Allan, M.

1987-10-15

186

Role of vibrational and translational energy in the activated dissociative adsorption of D2 on Cu(111)  

NASA Astrophysics Data System (ADS)

We report the relative efficacy of vibrational and translational energy in overcoming the barrier to dissociative adsorption of D2 on a Cu(111) surface. This is determined by measuring variation of adsorption probability with kinetic energies, Ei, and vibrational temperature. At the highest energy (Ei=0.83 eV) adsorption is predominantly due to ground-state D2; molecules in excited vibrational states play the dominant role for Ei below ~0.5 eV. A detailed analysis provides estimated adsorption probability versus energy functions for D2 in vibrational states v=0 to v=3.

Rettner, C. T.; Auerbach, D. J.; Michelsen, H. A.

1992-02-01

187

Methanol Oxidative Dehydrogenation on Oxide Catalysts: Molecular and Dissociative Routes and Hydrogen Addition Energies as  

E-print Network

dissociative routes for methanol reactions on polyoxometalate (POM) clusters at all practical reaction. 1. INTRODUCTION Keggin polyoxometalate (POM, HnXM12O40) clusters are materials with known structures

Iglesia, Enrique

188

Resonant structure of low-energy H{sub 3}{sup +} dissociative recombination  

SciTech Connect

High-resolution dissociative recombination rate coefficients of rotationally cool and hot H{sub 3}{sup +} in the vibrational ground state have been measured with a 22-pole trap setup and a Penning ion source, respectively, at the ion storage-ring TSR. The experimental results are compared with theoretical calculations to explore the dependence of the rate coefficient on ion temperature and to study the contributions of different symmetries to probe the rich predicted resonance spectrum. The kinetic energy release was investigated by fragment imaging to derive internal temperatures of the stored parent ions under differing experimental conditions. A systematic experimental assessment of heating effects is performed which, together with a survey of other recent storage-ring data, suggests that the present rotationally cool rate-coefficient measurement was performed at 380{sub -130}{sup +50} K and that this is the lowest rotational temperature so far realized in storage-ring rate-coefficient measurements on H{sub 3}{sup +}. This partially supports the theoretical suggestion that temperatures higher than assumed in earlier experiments are the main cause for the large gap between the experimental and the theoretical rate coefficients. For the rotationally hot rate-coefficient measurement a temperature of below 3250 K is derived. From these higher-temperature results it is found that increasing the rotational ion temperature in the calculations cannot fully close the gap between the theoretical and the experimental rate coefficients.

Petrignani, Annemieke; Altevogt, Simon; Berg, Max H.; Bing, Dennis; Grieser, Manfred; Hoffmann, Jens; Jordon-Thaden, Brandon; Krantz, Claude; Mendes, Mario B.; Novotny, Oldrich; Novotny, Steffen [Max-Planck-Institut fuer Kernphysik, Saupfercheckweg 1, D-69117 Heidelberg (Germany); Buhr, Henrik [Department of Particle Physics, Weizmann Institute of Science, 76100 Rehovot (Israel); Kreckel, Holger [Columbia University, 550 West 120th Street, New York, New York 10027 (United States); Kokoouline, Viatcheslav [Department of Physics, University of Central Florida, Orlando, Florida 32816, USA, and Laboratoire Aime Cotton, CNRS, Universite Paris-Sud XI, F-91405 Orsay (France); Greene, Chris H. [Department of Physics and JILA, University of Colorado, Boulder, Colorado 80309-0440 (United States); Orlov, Dmitry A.; Repnow, Roland; Sorg, Tobias; Stuetzel, Julia; Wolf, Andreas

2011-03-15

189

Theoretical study of the dissociation energy and the red and violet band systems of CN  

NASA Technical Reports Server (NTRS)

The dissociation energy (D sub O) of CN is determined to be 7.65 + or - 0.06 eV. This corresponds to delta H sub f (CN) = 105.3 + or - 1.5 kcal/mole, in excellent agreement with Engleman and Rouse (1975), but considerably larger than the recent value deduced from shock-tube studies by Colket (1984). The result is obtained not only from extensive ab initio MRCI calculations using a very large Gaussian basis set, but also from extrapolation of the directly computed value by comparison of computed and experimental results fo NO, C2, and N2. As an additional calibration of the methods, the D sub O value for CN was computed from the corresponding value for CN(-) using the experimental electron affinity data. The lifetime of the nu prime = 0 level of the violet (B 2 sigma + yields X 2 sigma +) system was computed to be 62.4 ns, in good agreement with both experiment and previous calculations. Lifetimes for the red (A 2 pi yields X 2 sigma +) system decrease with increasing nu prime, which is consistent both with the recent experiment and calculations. While the computed lifetimes are significantly longer that those obtained from the experiment, they are shorter than those deduced from an analysis of the solar spectrum. However the D sub O and f (sub OO) are consistent with Lambert's model for the solar spectrum.

Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

1987-01-01

190

Trajectory studies of model H–C–C?H+C = C dissociation. II. Angular momenta and energy partitioning and their relation to non-RRKM dynamics  

Microsoft Academic Search

The model alkyl dissociation reaction H–C–C?H+C = C has been studied on a potential energy surface derived from an analytic potential energy function for ethyl radical dissociation. Nonrandom excitation of H–C–C is simulated by the chemical activation reaction H+C = C?H–C–C, and different initial relative translational, rotational, and vibrational energies are investigated. Comparisons are made between the unimolecular dynamics of

William L. Hase; Ralph J. Wolf

1981-01-01

191

Energy and temperature dependent dissociation of the Na+(benzene)1,2 clusters: Importance of anharmonicity  

NASA Astrophysics Data System (ADS)

Chemical dynamics simulations were performed to study the unimolecular dissociation of randomly excited Na+(Bz) and Na+(Bz)2 clusters; Bz = benzene. The simulations were performed at constant energy, and temperatures in the range of 1200-2200 K relevant to combustion, using an analytic potential energy surface (PES) derived in part from MP2/6-311+G* calculations. The clusters decompose with exponential probabilities, consistent with RRKM unimolecular rate theory. Analyses show that intramolecular vibrational energy redistribution is sufficiently rapid within the clusters that their unimolecular dynamics is intrinsically RRKM. Arrhenius parameters, determined from the simulations of the clusters, are unusual in that Ea is ˜10 kcal/mol lower the Na+(Bz) ? Na+ + Bz dissociation energy and the A-factor is approximately two orders-of-magnitude too small. Analyses indicate that temperature dependent anharmonicity is important for the Na+(Bz) cluster's unimolecular rate constants k(T). This is consistent with the temperature dependent anharmonicity found for the Na+(Bz) cluster from a Monte Carlo calculation based on the analytic PES used for the simulations. Apparently temperature dependent anharmonicity is quite important for unimolecular dissociation of the Na+(Bz)1,2 clusters.

Kolakkandy, Sujitha; Paul, Amit K.; Pratihar, Subha; Kohale, Swapnil C.; Barnes, George L.; Wang, Hai; Hase, William L.

2015-01-01

192

Reactions in 1,1,1-trifluoroacetone triggered by low energy electrons (0-10 eV): from simple bond cleavages to complex unimolecular reactions.  

PubMed

The impact of low energy electrons (0-10 eV) to 1,1,1-trifluoroacetone yields a variety of fragment anions which are formed via dissociative electron attachment (DEA) through three pronounced resonances located at 0.8 eV, near 4 eV, and in the energy range 8-9 eV. The fragment ions arise from different reactions ranging from the direct cleavage of one single or double bond (formation of F(-), CF3(-), O(-), (M-H)(-), and M-F)(-)) to remarkably complex unimolecular reactions associated with substantial geometric and electronic rearrangement in the transitory intermediate (formation of OH(-), FHF(-), (M-HF)(-), CCH(-), and HCCO(-). The ion CCH(-), for example, is formed by an excision of unit from the target molecule through the concerted cleavage of four bonds and recombination to H2O within the neutral component of the reaction. PMID:24828451

Illenberger, Eugen; Meinke, Martina C

2014-08-21

193

Dissociative disorders.  

PubMed

The dissociative disorders, including "psychogenic" or "functional" amnesia, fugue, dissociative identity disorder (DID, also known as multiple personality disorder), and depersonalization disorder, were once classified, along with conversion disorder, as forms of hysteria. The 1970s witnessed an "epidemic" of dissociative disorder, particularly DID, which may have reflected enthusiasm for the diagnosis more than its actual prevalence. Traditionally, the dissociative disorders have been attributed to trauma and other psychological stress, but the existing evidence favoring this hypothesis is plagued by poor methodology. Prospective studies of traumatized individuals reveal no convincing cases of amnesia not attributable to brain insult, injury, or disease. Treatment generally involves recovering and working through ostensibly repressed or dissociated memories of trauma; at present, there are few quantitative or controlled outcome studies. Experimental studies are few in number and have focused largely on state-dependent and implicit memory. Depersonalization disorder may be in line for the next "epidemic" of dissociation. PMID:17716088

Kihlstrom, John F

2005-01-01

194

Mode specificity and the influence of rotation in cis-trans isomerization and dissociation in HONO  

NASA Astrophysics Data System (ADS)

The results of a classical trajectory study of intramoleeular vibrational energy redistribution, cis-trans isomerization, and unimolecular dissociation in HONO are presented. The calculations were carried out on a realistic potential-energy surface that was constructed by using the available kinetic, thermochemical, spectroscopic, and ab initio quantum mechanical information. The influence of the total energy, initial normal-mode excitations, initial OH-stretch overtone excitations, rotation, and potential-energysurface on intramolecular vibrational redistribution and the initial rates of isomerization and dissociation is discussed. The results show significant mode-specific behavior, particularly for the isomerization. Excitations of overtones of the OH or N?O bond stretching modes yield the lowest initial rates for both isomerization and dissociation. Excitation of the HON bending mode yields the largest isomerization rates while excitation of the ONO bending mode yields the largest dissociation rate. At a fixed total energy, placing a small amount of rotational energy in the molecule causes a significant increase in the isomerization and dissociation initial rates over those computed for nonrotating HONO, however, when the rotational energy is increased above 0. 1 eV, the rates decrease as expected on the basis of RRKM theory. The orientation of the rotation is an important factor for the intramolecular energy transfer and reaction rates. Rotating the molecule along the torsional axis causes a significant increase of the initial rate of isomerization. Rotating the molecule perpendicular to the ON bond causes significant increases in the dissociation rates.

Guan, Yuhua; Thompson, Donald L.

1989-12-01

195

Dissociation of aliphatic hydrocarbons by controlled electron impact: Vibrational and rotational energy distributions of the excited CH radicals  

Microsoft Academic Search

Emission spectra of CH(A2?-X2?) produced in collisions of acetylene, ethyelen and ethane with electrons (17–100 eV) have been measured and the rovibrational distributions of CH(A2?) have been obtained. The rovibrational distributions of CH(A2?) apparently depended on the incident electron energy, indicating the existence of more than two dissociation processes. The ratio of the vibrational populations, (P(?? = 1)\\/P(?? = 0)),

Manabu Tokeshi; Keiji Nakashima; Teiichiro Ogawa

1996-01-01

196

Characterization of intact N- and O-linked glycopeptides using higher energy collisional dissociation.  

PubMed

Simultaneous elucidation of the glycan structure and the glycosylation site are needed to reveal the biological function of protein glycosylation. In this study, we employed a recent type of fragmentation termed higher energy collisional dissociation (HCD) to examine fragmentation patterns of intact glycopeptides generated from a mixture of standard glycosylated proteins. The normalized collisional energy (NCE) value for HCD was varied from 30 to 60% to evaluate the optimal conditions for the fragmentation of peptide backbones and glycoconjugates. Our results indicated that HCD with lower NCE values preferentially fragmented the sugar chains attached to the peptides to generate a ladder of neutral loss of monosaccharides, thereby enabling the putative glycan structure characterization. In addition, detection of the oxonium ions enabled unambiguous differentiation of glycopeptides from non-glycopeptides. In contrast, HCD with higher NCE values preferentially fragmented the peptide backbone and, thus, provided information needed for confident peptide identification. We evaluated the HCD approach with alternating NCE parameters for confident characterization of intact N- and O-linked glycopeptides in a single liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. In addition, we applied a novel data analysis pipeline, so-called GlycoFinder, to form a basis for automated data analysis. Overall, 38 unique intact glycopeptides corresponding to eight glycosylation sites (six N-linked and two O-linked sites) were confidently identified from a standard protein mixture. This approach provided concurrent characterization of both the peptide and the glycan, thereby enabling comprehensive structural characterization of glycoproteins in a single LC-MS/MS analysis. PMID:24440233

Cao, Li; Toli?, Nikola; Qu, Yi; Meng, Da; Zhao, Rui; Zhang, Qibin; Moore, Ronald J; Zink, Erika M; Lipton, Mary S; Paša-Toli?, Ljiljana; Wu, Si

2014-05-01

197

Characterization of intact N- and O-linked glycopeptides using higher energy collisional dissociation  

SciTech Connect

Simultaneous elucidation of the glycan structure and the glycosylation site are needed to reveal the biological function of protein glycosylation. In this study, we employed a recent type of fragmentation termed higher energy collisional dissociation (HCD) to examine fragmentation patterns of intact glycopeptides generated from a mixture of standard glycosylated proteins. The normalized collisional energy (NCE) value for HCD was varied from 30% to 60% to evaluate the optimal conditions for the fragmentation of peptide backbones and glycoconjugates. Our results indicated that HCD with lower NCE valuespreferentially fragmented the sugar chains attached to the peptides to generate a ladder of neutral loss of monosaccharides, thus enabling the putative glycan structure characterization. Also, detection of the oxonium ions enabled unambiguous differentiation of glycopeptides from non-glycopeptides. On the contrary, HCD with higher NCE values preferentially fragmented the peptide backbone and thus provided information needed for confident peptide identification. We evaluated the HCD approach with alternating NCE parameters for confident characterization of intact N-linked and O-linked glycopeptides in a single liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis. In addition, we applied a novel data analysis pipeline, so-called GlycoFinder, to form a basis for automated data analysis. Overall, 38 unique intact glycopeptides corresponding to eight glycosylation sites (including six N-linked and two O-linked sites) were confidently identified from a standard protein mixture. This approach provided concurrent characterization of both, the peptide and the glycan, thus enabling comprehensive structural characterization of glycoproteins in a single LC-MS/MS analysis.

Cao, Li; Tolic, Nikola; Qu, Yi; Meng, Da; Zhao, Rui; Zhang, Qibin; Moore, Ronald J.; Zink, Erika M.; Lipton, Mary S.; Pasa-Tolic, Ljiljana; Wu, Si

2014-01-15

198

Chemical control through dissociative electron attachment - A study on pentafluorotoluene, pentafluoroaniline and pentafluorophenol  

NASA Astrophysics Data System (ADS)

In a combined experimental and theoretical study on dissociative electron attachment (DEA) to pentafluorotoluene, pentafluoroaniline and pentafluorophenol in the energy range 0-3 eV we reveal the role of rearrangement and hydrogen bonded intermediates in the DEA process and show that HF formation can be used to enable otherwise inaccessible, efficient low energy DEA processes.

Ómarsson, Benedikt; Bjarnason, Elías H.; Ingólfsson, Oddur; Haughey, Sean; Field, Thomas A.

2012-06-01

199

Dynamics on the HOCO potential energy surface studied by dissociative photodetachment of HOCO{sup -} and DOCO{sup -}  

SciTech Connect

An experimental study of the dissociative photodetachment (DPD) dynamics of HOCO{sup -} and DOCO{sup -} at a photon energy of 3.21 eV has been carried out to probe the potential energy surface of the HOCO free radical and the dynamics of the OH+CO{yields}H+CO{sub 2} reaction. These photoelectron-photofragment coincidence experiments allow the identification of photodetachment processes leading to the production of stable HOCO free radicals and both the H+CO{sub 2} and OH+CO dissociation channels on the neutral surface. Isotopic substitution by deuterium in the parent ion is observed to reduce the product branching ratio for the D+CO{sub 2} channel, consistent with tunneling playing a role in this dissociation pathway. Other isotope effects on the detailed partitioning of kinetic energy between photoelectrons and photofragments are also discussed. The results are compared to recent theoretical predictions of this DPD process, and evidence for the involvement of vibrationally excited HOCO{sup -} anions is discussed.

Lu, Zhou; Hu, Qichi; Oakman, Jonathan E.; Continetti, Robert E. [Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093-0340 (United States)

2007-05-21

200

Using dissociation energies to predict observability of b- and y-peaks in mass spectra of short peptides. II. Results for hexapeptides with non-polar side chains  

PubMed Central

RATIONALE The hypothesis that dissociation energies can serve as a predictor of observability of b- and y-peaks is tested for seven hexapeptides. If the hypothesis holds true for large classes of peptides, one would be able to improve the scoring accuracy of peptide identification tools by excluding theoretical peaks that cannot be observed in practical product ion spectra due to various physical, chemical or thermodynamic considerations. METHODS Product ion m/z spectra of hexapeptides AAAAAA, AAAFAA, AAAVAA, AAFAAA, AAVAAA, AAFFAA and AAVVAA have been acquired on a Finnigan LTQ XL mass spectrometer in the collision-induced dissociation (CID) activation mode on a grid of activation times 0.05 to 100 ms and normalized collision energy 10 to 35%. Dissociation energies were calculated for all fragmentation channels leading to b- and y-fragments at the TPSS/6–31G(d,p) level of the density functional theory. RESULTS It was demonstrated that the m/z peaks observed in the product ion spectra correspond to the fragmentation channels with dissociation energies below a certain threshold value. However, there is no direct correlation between the most intense m/z peaks and the lowest dissociation energies. Using the dissociation energies, it was predicted that out of 63 theoretically possible peaks in the b- and y-series of the seven hexapeptides, 19 should not be observable in practical spectra. In the experiments, 24 peaks were not observed, including all 19 predicted. CONCLUSIONS Dissociation energies alone are not sufficient for predicting ion intensity relationships in product ion m/z spectra. Nevertheless, the present data suggest that dissociation energies appear to be good predictors of observability of b- and y-peaks and potentially very useful for filtering theoretical peaks of each candidate peptide in peptide identification tools. PMID:23239328

Obolensky, O. I.; Wu, Wells W.; Shen, Rong-Fong; Yu, Yi-Kuo

2013-01-01

201

Middle School Chemistry: Energy Levels, Electrons, and Ionic Bonding  

NSDL National Science Digital Library

This multimedia lesson for Grades 7-8 features six animations, one video, and a hands-on lab to explore the process of ionic bonding. Learners can visualize what happens when positive and negative ions attract each other and form a bond, build 2D and 3D models, and perform a hands-on activity to observe sodium chloride crystals and relate their shape to the molecular model. Editor's Note: Ionic bonding occurs when electrons are transferred between atoms through electrostatic attraction between two oppositely charged ions. Covalent bonding occurs when electrons are shared between atoms. The processes are quite different. This module very effectively explores the atomic processes that underlie ionic bonding.

Galvan, Patti; Kessler, Jim

2011-08-17

202

Dissociative recombination dynamics of the ozone cation  

SciTech Connect

The dissociative recombination of the ozone cation has been studied at the heavy-ion storage ring CRYRING. The total cross section and branching fractions have been measured. The cross section from 0 eV to 0.2 eV follows a nearly E 1 dependence, which was theoretically predicted to be a characteristic of the direct dissociative recombination mechanism. The thermal rate coefficient has been deduced from the cross section to be 7.3710 7T/300 0.55 cm3 s 1. The branching fraction analysis carried out at 0 eV interaction energy has shown a strong propensity 94% to dissociate through the three-body channel. Due to the overwhelming dominance of this channel it has been investigated in more detail. Of the six energetically available three-body pathways only three are significantly populated, such that the production of O1S is highly unfavored and all atomic oxygen fragments are predominantly formed in 3P and 1D states. Analysis of the breakup geometries has been performed by means of the Dalitz plot. It is observed that the molecules dissociating through the O3P+O3P+O3P and O3P+O3P+O1D channels have an open linear geometry where the cleavage of two valence bonds occurs preferentially in unison, while the O3P+O1D+O1D breakup might proceed partly through a sequential mechanism.

Zhaunerchyk, Vitali [Stockholm University, Stockholm, Sweden; Geppert, W. [Stockholm University, Stockholm, Sweden; Osterdahl, F [Stockholm University, Stockholm, Sweden; Larsson, Mats [Stockholm University, Stockholm, Sweden; Thomas, R. D. [Stockholm University, Stockholm, Sweden; Bahati Musafiri, Eric [ORNL; Bannister, Mark E [ORNL; Fogle, Mark R. [Oak Ridge National Laboratory (ORNL); Vane, C Randy [ORNL

2008-01-01

203

Absolute cross sections and kinetic energy release distributions for electron-impact ionization and dissociation of CD+ 4  

NASA Astrophysics Data System (ADS)

Absolute cross sections for electron-impact dissociative excitation and ionization of CD+ 4 leading to formation of ionic products (CD2+ 4, CD+ 3, CD+ 2, CD+, C+, D+ 3, D+ 2, and D+) have been measured. The animated crossed-beams method is applied in the energy range from the reaction threshold up to 2.5 keV. Around 100 eV, the maximum cross sections are found to be (3.8±0.2) ×10-19 cm2, (10.8 ± 1.5) × 10^{-17} cm2, (7.1±0.8) ×10-17 cm2, (9.0±0.8) × 10-17 cm2 and (3.7±0.4) ×10-17 cm2 for the heavy carbonaceous ions CD2+ 4, CD+ 3, CD+ 2, CD+ and C+ respectively. For the light fragments, D+ 3, D+ 2, and D+, the cross sections around the maximum are found to be (5.0±0.6) ×10-19 cm2, (1.7± 0.2) ×10-17 cm2 and (10.6±1.0) ×10-17 cm2, respectively. The cross sections are presented in closed analytic forms convenient for implementation in plasma simulation codes. The analysis of ionic product velocity distributions allows determination of the kinetic energy release distributions which are seen to extend from 0 to 9 eV for heavy fragments, and up to 14 eV for light ones. The comparison of present energy thresholds and kinetic energy release with available published data gives information about states contributing to the observed processes. Individual contributions for dissociative excitation and dissociative ionization are determined for each detected product. A complete database including cross sections and energies is compiled for use in fusion application.

Lecointre, J.; Belic, D. S.; Jureta, J. J.; Janev, R.; Defrance, P.

2008-12-01

204

Discovery and Mechanistic Studies of Facile N-Terminal C?–C Bond Cleavages in the Dissociation of Tyrosine-Containing Peptide Radical Cations  

SciTech Connect

Gas phase fragmentations of protein and peptide (M) ions in a mass spectrometer—induced by, for example, electron-capture dissociation1-2 and electron-transfer dissociation3-422 —form the foundation for top-down amino acid sequencing approaches for the rapid identification of protein components in complex biological samples. During these processes, protonated protein and peptide radicals ([M + nH]•(n – 1)+)5–8 are generated; their fragmentations are governed largely by the properties of the unpaired electron. Because of their importance in modern bioanalytical chemistry, considerable attention has been drawn recently toward understanding the radical cation chemistry behind the fragmentations of these odd-electron biomolecular ions in the gas phase.

Mu, Xiaoyan; Song, Tao; Xu, Minjie; Lai, Cheuk-Kuen; Siu, Chi-Kit; Laskin, Julia; Chu, Ivan K.

2014-03-28

205

Trajectory Study of Energy Transfer and Unimolecular Dissociation of Highly Excited Allyl with Argon  

E-print Network

with Argon Riccardo Conte,*, Paul L. Houston,*,,§ and Joel M. Bowman*, Department of Chemistry and Cherry L of allyl with argon and on allyl dissociation is investigated. About 90 000 classical scattering potential and an interaction one, and it has already been used in a previous work on allyl-argon scattering

Houston, Paul L.

206

The Trouble with Chemical Energy: Why Understanding Bond Energies Requires an Interdisciplinary Systems Approach  

PubMed Central

Helping students understand “chemical energy” is notoriously difficult. Many hold inconsistent ideas about what energy is, how and why it changes during the course of a chemical reaction, and how these changes are related to bond energies and reaction dynamics. There are (at least) three major sources for this problem: 1) the way biologists talk about chemical energy (which is also the way we talk about energy in everyday life); 2) the macroscopic approach to energy concepts that is common in physics and physical sciences; and 3) the failure of chemistry courses to explicitly link molecular with macroscopic energy ideas. From a constructivist perspective, it is unlikely that students can, without a coherent understanding of such a central concept, attain a robust and accurate understanding of new concepts. However, changes are on the horizon, guided by the increasing understanding that difficult concepts require coherent, well-designed learning progressions and the new National Research Council Framework for K–12 Science Education. We provide supporting evidence for our assertions and suggestions for an interdisciplinary learning progression designed to better approach the concept of bond energies, a first step in an understanding chemical energy and behavior of reaction systems that is central to biological systems. PMID:23737636

Cooper, Melanie M.; Klymkowsky, Michael W.

2013-01-01

207

Dissociative recombination of LiH2+  

NASA Astrophysics Data System (ADS)

In this paper, we report results regarding how LiH2+ fragments as a result of a low-energy collision with an electron (dissociative recombination), a reaction that contains only elements and particles created during the very first phase of the universe. The collision-energy-dependent reaction rate and cross sections show detailed structures, more so than predicted by theory, suggesting significant rovibrational coupling in the ion and a complex reaction surface. From the structure of the molecule, the reaction predominantly results in the formation of Li + H2. However, 23% of the reaction flux leads to more interesting products, with 17% producing Li + 2H and 6% producing LiH + H. These last two channels break the strongest molecular bond in the system and, in the case of the latter channel, form a significantly weaker ionic bond. Possible reasons behind this interesting behavior are discussed, together with the interaction between the available reaction channels.

Thomas, R. D.; Ehlerding, A.; Geppert, W. D.; Hellberg, F.; Zhaunerchyk, V.; Larsson, M.; Bahati, E.; Bannister, M. E.; Fogle, M. R.; Vane, C. R.

2014-05-01

208

Infrared multiphoton dissociation of RDX in a molecular beam  

SciTech Connect

Infrared multiphoton dissociation (IRMPD) of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) in a molecular beam has been performed in order to investigate the mechanism of RDX thermal decomposition. A beam of molecules was crossed by a pulsed TEA CO/sub 2/ laser and velocity distributions of the various products were measured by the time-of-flight (TOF) technique as a function of the laboratory angle using a mass spectrometric detector. The dissociation channels, their branching ratios, and the translational energy distributions of the products were determined. In contrast to the conventional view of simple bond rupture through loss of NO/sub 2/ as the dominant primary channel in RDX decomposition, it was found that the dominant primary channel is concerted symmetric triple fission to produce three CH/sub 2/N/sub 2/O/sub 2/ fragments which subsequently undergo secondary concerted dissociation to produce HCN, H/sub 2/CO, HONO (or HNO/sub 2/), and N/sub 2/O. A total of two primary and four secondary dissociation channels were observed. Concerted reactions predominate over simple bond rupture not only in the number of channels (four vs two) but also in the amount of products. A fair amount of translational energy release through concerted reaction channels was observed, which is significant for an explanation of the energies of RDX decomposition.

Zhao, X.; Hintsa, E.J.; Lee, Y.T.

1988-01-15

209

Diffraction Dissociation - 50 Years Later  

E-print Network

The field of Diffraction Dissociation, which is the subject of this workshop, began 50 years ago with the analysis of deuteron stripping in low energy collisions with nuclei. We return to the subject in a modern context- deuteron dissociation in $\\sqrt{s_{NN}}= 200$ GeV d-Au collisions recorded during the 2003 RHIC run in the PHENIX experiment. At RHIC energy, d$\\to$n+p proceeds predominantly (90%) through Electromagnetic Dissociation and the remaining fraction via the hadronic shadowing described by Glauber. Since the dissociation cross section has a small theoretical error we adopt this process to normalize other cross sections measured in RHIC.

Sebastian N. White

2005-07-18

210

Diffraction Dissociation - 50 Years Later  

E-print Network

The field of Diffraction Dissociation, which is the subject of this workshop, began 50 years ago with the analysis of deuteron stripping in low energy collisions with nuclei. We return to the subject in a modern context- deuteron dissociation in $\\sqrt{s_{NN}}= 200$ GeV d-Au collisions recorded during the 2003 RHIC run in the PHENIX experiment. At RHIC energy, d$\\to$n+p proceeds predominantly (90%) through Electromagnetic Dissociation and the remaining fraction via the hadronic shadowing described by Glauber. Since the dissociation cross section has a small theoretical error we adopt this process to normalize other cross sections measured in RHIC.

White, S N

2005-01-01

211

Effects of vacancy and step on dissociative dynamics of H2 on Pd (1 1 1) surfaces  

NASA Astrophysics Data System (ADS)

Based on our recently developed reactive force field, we studied dissociative dynamics of H2 molecule on Pd (1 1 1) surface with vacancy and step. The results show that vacancy results in a little higher probability than perfect surface. Further analysis shows that vacancy can hinder the diffusion of H2 molecule in the dissociation dynamics. Moreover, it is found that the probability of step is higher than that of perfect surface but it is insensitive to the height of step. The roles played by the direct dissociation at high energy and bond counting mechanism at low energy are discussed.

Huang, X.; Yan, X. H.; Xiao, Y.

2012-04-01

212

[Dissociative hysteria].  

PubMed

Under the term of dissociative hysteria are described a set of clinical syndromes characterized by behavioral disorders and psychic activity anomalies. The nature of the symptoms seems very similar to hysterical conversion. Psychogenic amnesia, psychogenic fugues and multiple personality disorder are described. There is some evidence that the symptoms are related to psychic affective traumatisms and no physiological alteration. Two mechanisms are proposed: dissociation of personality and amnesia. Clinical course generally improves spontaneously. Various forms of psychotherapy may be used. PMID:8578147

Widlöcher, D

1995-12-15

213

Cleavage of thymine N3H bonds by low-energy electrons attached Magali Theodore 1  

E-print Network

barriers to cleavage because they produce very stable anionic fragments, 0301-0104/$ - see front matter �Cleavage of thymine N3­H bonds by low-energy electrons attached to base p* orbitals Magali The the effects of base p-stacking on the rates of such bond cleavages. To date, our results suggest that sugar

Simons, Jack

214

Simple Bond-Charge Model for Potential-Energy Curves of Heteronuclear Diatomic Molecules  

Microsoft Academic Search

A model for the vibrational potential-energy functions of diatomic molecules, previously applied to homonuclear molecules only, is extended to 54 heteronuclear diatomic molecules in 93 different electronic states. Experimental Re and ke values are used to determine for each species the empirical bond-charge and bond-length parameters, q and ?, in the homopolar model potential W = W0 + (e2 ?

Raymond F. Borkman; Gary Simons; Robert G. Parr

1969-01-01

215

Is silicene stable in O2? —First-principles study of O2 dissociation and O2-dissociation-induced oxygen atoms adsorption on free-standing silicene  

NASA Astrophysics Data System (ADS)

The stability of free-standing silicene in O2 is an open question. In this letter, the O2 dissociation and O2-dissociation-induced O atoms adsorption on free-standing silicene are studied by using first-principles calculations. Our results show that the O2 molecule dissociates on the free-standing silicene surface easily from both the thermodynamic and kinetic points of view, which is different from the case of graphene. The dissociation reaction is an exothermic process, and the dissociated O atoms form strong bonds with Si atoms, which lowers the energy of the system substantially. On the other hand, the dissociation reaction occurs spontaneously on the free-standing silicene without overcoming any energy barrier. Furthermore, the migration and desorption of O atoms are relatively difficult under room temperature due to the strong Si-O bonds in the O-adsorbed silicene, which is in favor of forming silicon oxides. Our results provide convictive evidence to show that free-standing silicene is unstable in O2.

Liu, G.; Lei, X. L.; Wu, M. S.; Xu, B.; Ouyang, C. Y.

2014-05-01

216

Bond Energy Sums in Benzene, Cyclohexatriene and Cyclohexane Prove Resonance Unnecessary  

E-print Network

The recent new structure of benzene shows that it consists of three C atoms of radii as in graphite alternating with three C atoms with double bond radii. This is different from the hypothetical cyclohexatriene (Kekule structure) involving alternate double and single bonds. It was shown that the difference in the bond energy sum of the atomic structure of benzene from that of the Kekule structure is the energy (erroneously) assumed to be due to resonance. Here it is shown that the present structure of benzene also explains the energy of hydrogenation into cyclohexane and its difference from that of cyclohexatriene.

Raji Heyrovska

2008-07-25

217

Dissociation dynamics of fluorinated ethene cations: from time bombs on a molecular level to double-regime dissociators.  

PubMed

The dissociative photoionization mechanism of internal energy selected C(2)H(3)F(+), 1,1-C(2)H(2)F(2)(+), C(2)HF(3)(+) and C(2)F(4)(+) cations has been studied in the 13-20 eV photon energy range using imaging photoelectron photoion coincidence spectroscopy. Five predominant channels have been found; HF loss, statistical and non-statistical F loss, cleavage of the C-C bond post H or F-atom migration, and cleavage of the C=C bond. By modelling the breakdown diagrams and ion time-of-flight distributions using statistical theory, experimental 0 K appearance energies, E(0), of the daughter ions have been determined. Both C(2)H(3)F(+) and 1,1-C(2)H(2)F(2)(+) are veritable time bombs with respect to dissociation via HF loss, where slow dissociation over a reverse barrier is followed by an explosion with large kinetic energy release. The first dissociative ionization pathway for C(2)HF(3) and C(2)F(4) involves an atom migration across the C=C bond, giving CF-CHF(2)(+) and CF-CF(3)(+), respectively, which then dissociate to form CHF(2)(+), CF(+) and CF(3)(+). The nature of the F-loss pathway has been found to be bimodal for C(2)H(3)F and 1,1-C(2)H(2)F(2), switching from statistical to non-statistical behaviour as the photon energy increases. The dissociative ionization of C(2)F(4) is found to be comprised of two regimes. At low internal energies, CF(+), CF(3)(+) and CF(2)(+) are formed in statistical processes. At high internal energies, a long-lived excited electronic state is formed, which loses an F atom in a non-statistical process and undergoes statistical redistribution of energy among the nuclear degrees of freedom. This is followed by a subsequent dissociation. In other words only the ground electronic state phase space stays inaccessible. The accurate E(0) of CF(3)(+) and CF(+) formation from C(2)F(4) together with the now well established ?(f)H(o) of C(2)F(4) yield self-consistent enthalpies of formation for the CF(3), CF, CF(3)(+) and CF(+) species. PMID:22322889

Harvey, Jonelle; Bodi, Andras; Tuckett, Richard P; Sztáray, Bálint

2012-03-21

218

Atomistic spectrometrics of local bond-electron-energy pertaining to Na and K clusters  

NASA Astrophysics Data System (ADS)

Consistency between density functional theory calculations and photoelectron spectroscopy measurements confirmed our predications on the undercoordination-induced local bond relaxation and core level shift of Na and K clusters. It is clarified that the shorter and stronger bonds between under-coordinated atoms cause local densification and local potential well depression and shift the electron binding-energy accordingly. Numerical consistency turns out the energy levels for an isolated Na (E2p = 31.167 eV) and K (E3p = 18.034 eV) atoms and their respective bulk shifts of 2.401 eV and 2.754 eV, which is beyond the scope of conventional approaches. This strategy has also resulted in quantification of the local bond length, bond energy, binding energy density, and atomic cohesive energy associated with the undercoordinated atoms.

Bo, Maolin; Wang, Yan; Huang, Yongli; Liu, Yonghui; Li, Can; Sun, Chang Q.

2015-01-01

219

Structural determination of cerebrosides isolated from Asterias amurensis starfish eggs using high-energy collision-induced dissociation of sodium-adducted molecules.  

PubMed

Six cerebrosides were isolated from the eggs of the starfish Asterias amurensis using solvent extraction, silica gel column chromatography, and reversed-phase high-performance liquid chromatography. This study demonstrated that the structures of cerebrosides could be completely characterized, based on their sodium-adducted molecules, using fast atom bombardment (FAB) tandem mass spectrometry. The high-energy collision-induced dissociation of the sodium-adducted molecule, [M?+?Na](+), of each cerebroside molecular species generated abundant ions, providing information on the compositions of the 2-hydroxy fatty acids and long-chain sphingoid bases, as well as the sugar moiety polar head group. Each homologous ion series along the fatty acid and aliphatic chain of the sphingoid base was useful for locating the double-bond positions of both chains and the methyl branching position of the long-chain base. The N-fatty acyl portions were primarily long-chain saturated or monoenoic acids (C16 to C24) with an ?-hydroxy group. The sphingoid long-chain base portions were aliphatic chains (C18 or C22) with two or three degrees of unsaturation and with or without methyl branching. PMID:21290443

Park, Taeseong; Park, Young Seung; Rho, Jung-Rae; Kim, Young Hwan

2011-03-15

220

Dissociation energies and long-range potentials of diatomic molecules from vibrational spacings: The halogens1  

Microsoft Academic Search

A recent,ly-developed met,hod for obtaining dissociation limits and long- range internuclear potentials from the distribution of the uppermost vibra- tional levels of diatomic molecules is applied to existing data for the B 3n:, states of Clz, Brs, and IS, and the ground X 2, + state of Cl,. Values of the asympt.otic long-range potential constants (C,) are deduced from t,he

RICHARD B. BERNSTEIN

1971-01-01

221

Direct-dynamics VTST study of hydrogen or deuterium abstraction and C-C bond formation or dissociation in the reactions of CH3 + CH4, CH3 + CD4, CH3D + CD3, CH3CH3 + H, and CH3CD3 + D  

NASA Astrophysics Data System (ADS)

Direct-dynamics variational transition-state theory calculations are studied at the MPWB1K/6-311++G(d,p) level for the four parts of reactions. The first part is hydrogen or deuterium abstraction in the reactions of CH3 + CH4, CH3 + CD4, and CH3D + CH3. The second part involves C-C bond formation in these reactions. The third one is the reactions of CH3CH3 + H and CH3CD3 + D to form of H2, HD, and D2. The last one is the dissociation of C-C bonds in the last group of reactions. The ground-state vibrational adiabatic potential is plotted for all channels. We have carried out direct-dynamics calculations of the rate constants, including multidimensional tunneling in the temperature range T = 200-2200 K. The results of CVT/?OMT rate constants were in good agreement with the experimental data which were available for some reactions. Small-curvature tunneling and Large-curvature tunneling with the LCG4 version were used to include the quantum effects in calculation of the rate constants. To try to find the region of formation and dissociation of bounds we have also reported the variations of harmonic vibrational frequencies along the reaction path. The thermally averaged transmission probability (P(E)exp (-?E/RT)) and representative tunneling energy at 298 K are reported for the reactions in which tunneling is important. We have calculated kinetic isotope effect which shows tunneling and vibrational contributions are noticeable to determine the rate constant. Nonlinear least-squares fitting is used to calculate rate constant expressions in the temperature range 200-2200 K. These expressions revealed that pre-exponential factor includes two parts; the first part is a constant number which is important at low temperatures while the second part is temperature dependent which is significant at high temperatures.

Ramazani, Shapour

2013-05-01

222

Size-dependent stability toward dissociation and ligand binding energies of phosphine-ligated gold cluster ions  

SciTech Connect

The stability of sub-nanometer size gold clusters ligated with organic molecules is of paramount importance to the scalable synthesis of monodisperse size-selected metal clusters with highly tunable chemical and physical properties. For the first time, a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS) equipped with surface induced dissociation (SID) has been employed to investigate the time and collision energy resolved fragmentation behavior of cationic doubly charged gold clusters containing 7-9 gold atoms and 6-7 triphenylphosphine (TPP) ligands prepared by reduction synthesis in solution. The TPP ligated gold clusters are demonstrated to fragment through three primary dissociation pathways: (1) Loss of a neutral TPP ligand from the precursor gold cluster, (2) asymmetric fission and (3) symmetric fission and charge separation of the gold core resulting in formation of complementary pairs of singly charged fragment ions. Threshold energies and activation entropies of these fragmentation pathways have been determined employing Rice-Ramsperger-Kassel-Marcus (RRKM) modeling of the experimental SID data. It is demonstrated that the doubly charged cluster ion containing eight gold atoms and six TPP ligands, (8,6)2+, exhibits exceptional stability compared to the other cationic gold clusters examined in this study due to its large ligand binding energy of 1.76 eV. Our findings demonstrate the dramatic effect of the size and extent of ligation on the gas-phase stability and preferred fragmentation pathways of small TPP-ligated gold clusters.

Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

2014-08-01

223

On the differentiation of diffusion bond strength using the total acoustic energy reflected from the bond. [Ti-6Al-4V  

SciTech Connect

Single frequency reflection coefficients and reflected energy over a broad acoustic band (2-15 MHz), and the mechanical bond strength were evaluated on diffusion bonds in Cu/Cu, Cu/Ni, and Ti-6Al-4V/self. Results indicate that energy data are more sensitive to small bond strength changes as predicted by Parseval's theorem. In all cases, the energy reflected mainly originates at voids still present at the original interface location. Other microstructural features caused by the interdiffusion appear to diminish the reflected energy. 7 refs., 4 figs.

Ojard, G.C. (Pratt and Whitney, West Palm Beach, FL (United States)); Buck, O.; Rehbein, D.K.; Hughes, M.S. (Iowa State Univ. of Science and Technology, Ames, IA (United States). Center for NDE)

1992-01-01

224

Quantum control of photodissociation by manipulation of bond softening  

NASA Astrophysics Data System (ADS)

We present a method to control photodissociation by manipulating the bond-softening mechanism occurring in strong shaped laser fields, namely by varying the chirp sign and magnitude of an ultrashort laser pulse. Manipulation of bond softening is experimentally demonstrated for strong-field (1012-1013 W/cm2) photodissociation of H2+, exhibiting a substantial increase of dissociation by positively chirped pulses with respect to both negatively chirped and transform-limited pulses. The measured kinetic energy release and angular distributions are used to quantify the degree of dissociation control. The control mechanism is attributed to the interplay of dynamic alignment and chirped light induced potential curves.

Natan, Adi; Lev, Uri; Prabhudesai, Vaibhav S.; Bruner, Barry D.; Strasser, Daniel; Schwalm, Dirk; Ben-Itzhak, Itzik; Heber, Oded; Zajfman, Daniel; Silberberg, Yaron

2012-10-01

225

Description of molecular dynamics in intense laser fields by the time-dependent adiabatic state approach: application to simultaneous two-bond dissociation of CO2 and its control.  

PubMed

We theoretically investigated the dynamics of structural deformations of CO(2) and its cations in near-infrared intense laser fields (approximately 10(15) W cm(-2)) by using the time-dependent adiabatic state approach. To obtain "field-following" adiabatic potentials for nuclear dynamics, the electronic Hamiltonian including the interaction with the instantaneous laser electric field is diagonalized by the multiconfiguration self-consistent-field molecular orbital method. In the CO(2) and CO(2+) stages, ionization occurs before the field intensity becomes high enough to deform the molecule. In the CO(2)(2+) stage, simultaneous symmetric two-bond stretching occurs as well as one-bond stretching. Two-bond stretching is induced by an intense field in the lowest time-dependent adiabatic state |1> of CO(2)(2+), and this two-bond stretching is followed by the occurrence of a large-amplitude bending motion mainly in the second-lowest adiabatic state |2> nonadiabatically created at large internuclear distances by the field from |1>. It is concluded that the experimentally observed stretched and bent structure of CO(2)(3+) just before Coulomb explosions originates from the structural deformation of CO(2)(2+). We also show in this report that the concept of "optical-cycle-averaged potential" is useful for designing schemes to control molecular (reaction) dynamics, such as dissociation dynamics of CO(2), in intense fields. The present approach is simple but has wide applicability for analysis and prediction of electronic and nuclear dynamics of polyatomic molecules in intense laser fields. PMID:12823025

Sato, Yukio; Kono, Hirohiko; Koseki, Shiro; Fujimura, Yuichi

2003-07-01

226

Large nonstatistical branching ratio in the dissociation of pentane-2,4-dione radical cation: an ab initio direct classical trajectory study.  

PubMed

The dissociation of pentane-2,4-dione radical cation has been studied by ab initio direct classical trajectory calculations at the MP2/6-31G(d) level of theory. A bond additivity correction has been used to improve the MP2 potential energy surface (BAC-MP2). A microcanonical ensemble was constructed using quasiclassical normal-mode sampling by distributing 10 kcal/mol of excess energy above ZPE for the transition state for the tautomerization of the enol with a terminal double bond, 4-hydroxypent-4-en-2-one radical cation, to the diketo form. A total of 244 trajectories were run starting from this transition state, yielding pentane-2,4-dione radical cation and depositing energy in the terminal CC bond. As a result, the branching ratio for dissociation of the terminal CC bond versus the interior CC bonds is significantly larger than expected from RRKM theory. The branching ratio for the dissociation of the two interior CC bonds is ?20:1, with the one closest to the activated methyl breaking more often. Since the two interior bonds are equivalent and should dissociate with equal probability, this branching ratio represents a very large deviation from statistical behavior. A simple kinetic scheme has been constructed to model the dissociation rates. The nonstatistical behavior is seen because the rate of energy flow within the molecule is comparable to or less than the rates of dissociation for the activated system. In addition to the expected dissociation products, some of the trajectories also lead to the formation of an ester-like product, prop-1-en-2-yl acetate radical cation. PMID:22893922

Zhou, Jia; Schlegel, Bernhard

2009-02-26

227

Dissociative recombination cross section and branching ratios of protonated dimethyl disulfide and N-methylacetamide  

NASA Astrophysics Data System (ADS)

Dimethyl disulfide (DMDS) and N-methylacetamide are two first choice model systems that represent the disulfide bridge bonding and the peptide bonding in proteins. These molecules are therefore suitable for investigation of the mechanisms involved when proteins fragment under electron capture dissociation (ECD). The dissociative recombination cross sections for both protonated DMDS and protonated N-methylacetamide were determined at electron energies ranging from 0.001 to 0.3 eV. Also, the branching ratios at 0 eV center-of-mass collision energy were determined. The present results give support for the indirect mechanism of ECD, where free hydrogen atoms produced in the initial fragmentation step induce further decomposition. We suggest that both indirect and direct dissociations play a role in ECD.

Al-Khalili, A.; Thomas, R.; Ehlerding, A.; Hellberg, F.; Geppert, W. D.; Zhaunerchyk, V.; af Ugglas, M.; Larsson, M.; Uggerud, E.; Vedde, J.; Adlhart, C.; Semaniak, J.; Kami?ska, M.; Zubarev, R. A.; Kjeldsen, F.; Andersson, P. U.; Österdahl, F.; Bednarska, V. A.; Paál, A.

2004-09-01

228

Implementation of low-energy surface-induced dissociation (eV SID) and high-energy collision-induced dissociation (keV CID)  

E-print Network

experiments, accomplished with a surface placed after the last reflectron electrode, the electrodes energy expression, E mv2 /2. As pointed out in the foreword to Cotter's book on TOF mass spectrometry [1

Wysocki, Vicki H.

229

Dissociation of the N-C(alpha) bond and competitive formation of the [z(n) - H](+) and [c(n) + 2H](+) product ions in radical peptide ions containing tyrosine and tryptophan: the influence of proton affinities on product formation.  

PubMed

Dissociations at the N-C(alpha) bond of tryptophan and tyrosine residues are the prevalent pathways in the fragmentations of radical cations of tripeptides that contain such as residues. This process involves a proton transfer from the beta-carbon of the tryptophan or tyrosine residue to the carbonyl oxygen of the amide group, followed by cleavage of the N-C(alpha) bond, generating low-lying proton-bound dimers that dissociate to give each an ionic and a neutral product. Formation of the [z(n) - H](*+) or [c(n) + 2H](+) ion is a competition between the two incipient fragments for the proton in a dissociating proton-bound dimer. PMID:18930412

Siu, Chi-Kit; Ke, Yuyong; Orlova, Galina; Hopkinson, Alan C; Michael Siu, K W

2008-12-01

230

On the photostability of peptides after selective photoexcitation of the backbone: prompt versus slow dissociation.  

PubMed

Vulnerability of biomolecules to ultraviolet radiation is intimately linked to deexcitation pathways: photostability requires fast internal conversion to the electronic ground state, but also intramolecular vibrational redistribution and cooling on a time scale faster than dissociation. Here we present a protocol to disentangle slow and non-hazardous statistical dissociation from prompt cleavage of peptide bonds by 210 nm light based on experiments on protonated peptides isolated in vacuo and tagged by 18-crown-6 ether (CE). The weakest link in the system is between the charged site and CE, which is remote from the initial site of excitation. Hence loss of CE serves as direct proof that energy has reached the charge-site end, leaving the backbone intact. Our work demonstrates that excitation of tertiary amide moieties (proline linkages) results in both prompt dissociation and statistical dissociation after energy randomisation over all vibrational degrees of freedom. PMID:24945849

Byskov, Camilla Skinnerup; Jensen, Frank; Jørgensen, Thomas J D; Nielsen, Steen Brøndsted

2014-08-14

231

Kinetics of CH4 and CO2 hydrate dissociation and gas bubble evolution via MD simulation.  

PubMed

Molecular dynamics simulations of gas hydrate dissociation comparing the behavior of CH4 and CO2 hydrates are presented. These simulations were based on a structurally correct theoretical gas hydrate crystal, coexisting with water. The MD system was first initialized and stabilized via a thorough energy minimization, constant volume-temperature ensemble and constant volume-energy ensemble simulations before proceeding to constant pressure-temperature simulations for targeted dissociation pressure and temperature responses. Gas bubble evolution mechanisms are demonstrated as well as key investigative properties such as system volume, density, energy, mean square displacements of the guest molecules, radial distribution functions, H2O order parameter, and statistics of hydrogen bonds. These simulations have established the essential similarities between CH4 and CO2 hydrate dissociation. The limiting behaviors at lower temperature (no dissociation) and higher temperature (complete melting and formation of a gas bubble) have been illustrated for both hydrates. Due to the shift in the known hydrate stability curves between guest molecules caused by the choice of water model as noted by other authors, the intermediate behavior (e.g., 260 K) showed distinct differences however. Also, because of the more hydrogen-bonding capability of CO2 in water, as reflected in its molecular parameters, higher solubility of dissociated CO2 in water was observed with a consequence of a smaller size of gas bubble formation. Additionally, a novel method for analyzing hydrate dissociation based on H-bond breakage has been proposed and used to quantify the dissociation behaviors of both CH4 and CO2 hydrates. Activation energies Ea values from our MD studies were obtained and evaluated against several other published laboratory and MD values. Intrinsic rate constants were estimated and upscaled. A kinetic reaction model consistent with macroscale fitted kinetic models has been proposed to indicate the macroscopic consequences of this analysis. PMID:24571292

Uddin, M; Coombe, D

2014-03-20

232

Spondylopelvic dissociation.  

PubMed

Spondylopelvic dissociation is a complex injury pattern resulting in multiplanar instability of the lumbopelvis. These injuries have traditionally been known as "suicide jumper's fractures" and have recently increased in prevalence as a result of under-vehicle explosions seen in the past decade of military conflicts in the Middle East. The hallmarks of spondylopelvic dissociation are bilateral vertical sacral fractures with a horizontal component, resulting in lumbosacral instability in the sagittal and axial planes. Surgical treatment has evolved greatly and both percutaneous and open options are available, with triangular osteosynthesis being the most relied on method of fixation. PMID:24267208

Sullivan, Matthew P; Smith, Harvey E; Schuster, James M; Donegan, Derek; Mehta, Samir; Ahn, Jaimo

2014-01-01

233

Born-Oppenheimer energy surfaces of similar molecules: Interrelations between bond lengths, bond angles, and frequencies of normal vibrations in alkanes  

NASA Astrophysics Data System (ADS)

CH bond lengths, HCH and HCC bond angles, and CH symmetric and asymmetric stretching frequencies in alkane molecules are placed into four groups according to their occurrence in CH4, -CH3, CH2, and -CH, and are seen to vary in a regular fashion. The physical rationale offered for these variations relates them to balanced interactions between adjacent orbitals of CH and CC bonds, which are assumed to be common to all energy surfaces of alkane molecules. The regular variations are quantitatively reproduced by a consistent force field of alkanes, which in place of the usual harmonic stretching potentials uses only two Morse potentials, one for the CH bond, common to all four groups, and one for the CC bond. The correlated variation in bond lengths and bond angles, due to orbital interactions, is represented mainly by stretch-bend, stretch-stretch, and bend-bend cross terms. The resulting stretching frequencies, being dependent upon the second derivative of the Morse function, decrease with increasing bond length. The new force field yields bond lengths, bond angles, and vibrational frequencies, and reproduces the observed trend in their variation, mostly to within experimental accuracy. Remaining deviations are attributed to vicinal and higher order nonbonded interactions. Methane is included as a member of the alkane family and the new force field accounts successfully for its vibrational frequencies.

Lifson, Shneior; Stern, Peter S.

1982-11-01

234

Dissociative recombination of NH+  

NASA Astrophysics Data System (ADS)

We have experimentally investigated dissociative recombination of NH+ with electrons using a merged ion and electron beam configuration in a storage ring. A fast counting and position sensitive imaging detector enabled us to perform fragment imaging measurements over relative electron-ion collision energies from 0 to 12 eV. The results show unprecedented details on product excitation and on the reaction dynamics.

Yang, B.; Novotný, O.; Krantz, C.; Buhr, H.; Mended, M.; Nordhorn, C.; Geppert, W. D.; Berg, M.; Bing, D.; Domesle, C.; Grussie, F.; Savin, D. W.; Schwalm, D.; Cai, X.; Wolf, A.

2014-04-01

235

The enthalpy of formation of fullerene fluoride C60F18 and the C-F bond energy  

NASA Astrophysics Data System (ADS)

The enthalpy of combustion of crystalline fullerene fluoride C60F18 was determined in an isoperibolic calorimeter with a rotating platinized bomb, and the enthalpy of formation of the compound was calculated. The enthalpy of sublimation of C60F18 measured earlier was used to calculate the enthalpy of formation of fullerene fluoride in the gas phase and the mean enthalpy of dissociation of C-F bonds in this compound.

Papina, T. S.; Luk'yanova, V. A.; Goryunkov, A. A.; Ioffe, I. N.; Gol'Dt, I. V.; Buyanovskaya, A. G.; Kabaeva, N. M.; Sidorov, L. N.

2007-10-01

236

Using beryllium bonds to change halogen bonds from traditional to chlorine-shared to ion-pair bonds.  

PubMed

Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to investigate the structures, binding energies, and bonding characteristics of binary complexes HFBe:FCl, R2Be:FCl, and FCl:N-base, and of ternary complexes HFBe:FCl:N-base and R2Be:FCl:N-base for R = H, F, Cl; N-base = NH3, NHCH2, NCH. Dramatic synergistic cooperative effects have been found between the BeF beryllium bonds and the ClN halogen bonds in ternary complexes. The ClN traditional halogen bonds and the BeF beryllium bonds in binary complexes become significantly stronger in ternary complexes, while the F-Cl bond weakens. Charge-transfer from F to the empty p(?) orbital of Be leads to a bending of the XYBe molecule and a change in the hybridization of Be, which in the limit becomes sp(2). As a function of the intrinsic basicity of the nitrogen base and the intrinsic acidity of the Be derivative, the halogen-bond type evolves from traditional to chlorine-shared to ion-pair bonds. The mechanism by which an ion-pair complex is formed is similar to that involved in the dissociative proton attachment process. EOM-CCSD spin-spin coupling constants (1X)J(Cl-N) across the halogen bond in these complexes also provide evidence of the same evolution of the halogen-bond type. PMID:25486548

Alkorta, Ibon; Elguero, José; Mó, Otilia; Yáñez, Manuel; Del Bene, Janet E

2015-01-21

237

Photofragment translational spectroscopy of three body dissociations and free radicals  

SciTech Connect

This dissertation describes several three-body dissociations and the photodissociation of methyl radicals studied using photofragment translational spectroscopy. The first chapter provides an introduction to three body dissociation, examines current experimental methodology, and includes a discussion on the treatment of photofragment translational spectroscopy data arising from three-body fragmentation. The ultraviolet photodissociation of azomethane into two methyl radicals and nitrogen is discussed in chapter 2. Chapter 3 describes the photodissociation of acetone at 248 nm and 193 nm. At 248 nm the translational energy release from the initial C-C bond cleavage matches the exit barrier height and a comparison with results at 266 nm suggests that is invariant to the available energy. A fraction of the nascent CH{sub 3}CO radicals spontaneously dissociate following rotational averaging. The for the second C-C bond cleavage also matches the exit barrier height. At 193 nm the experimental data can be successfully fit assuming that the dynamics are analogous to those at 248 nm. A simplified model of energy partitioning which adequately describes the experimental results is discussed. Experiments on acetyl halides provide additional evidence to support the proposed acetone dissociation mechanism. A value of 17.0{+-}1.0 kcal/mole for the barrier height, CH{sub 3}CO decomposition has been determined. The photodissociation of methyl radical at 193 nm and 212.8 nm is discussed in the chapter 5. The formation of CH{sub 2} ({sup 1}A{sub l}) and H ({sup 2}S) was the only single photon dissociation pathway observed at both wavelengths.

North, S.W.

1995-04-01

238

Dissociative electron attachment studies on acetone  

NASA Astrophysics Data System (ADS)

Dissociative electron attachment (DEA) to acetone is studied in terms of the absolute cross section for various fragment channels in the electron energy range of 0-20 eV. H- is found to be the most dominant fragment followed by O- and OH- with only one resonance peak between 8 and 9 eV. The DEA dynamics is studied by measuring the angular distribution and kinetic energy distribution of fragment anions using Velocity Slice Imaging technique. The kinetic energy and angular distribution of H- and O- fragments suggest a many body break-up for the lone resonance observed. The ab initio calculations show that electron is captured in the multi-centered anti-bonding molecular orbital which would lead to a many body break-up of the resonance.

Prabhudesai, Vaibhav S.; Tadsare, Vishvesh; Ghosh, Sanat; Gope, Krishnendu; Davis, Daly; Krishnakumar, E.

2014-10-01

239

Effects of Electron Kinetic Energy and Ion-Electron Inelastic Collisions in Electron Capture Dissociation Measured using Ion Nanocalorimetry  

PubMed Central

Ion nanocalorimetry is used to measure the effects of electron kinetic energy in electron capture dissociation (ECD). With ion nanocalorimetry, the internal energy deposited into a hydrated cluster upon activation can be determined from the number of water molecules that evaporate. Varying the heated cathode potential from ?1.3 to ?2.0 V during ECD has no effect on the average number of water molecules lost from the reduced clusters of either [Ca(H2O)15]2+ or [Ca(H2O)32]2+ even when these data are extrapolated to a cathode potential of zero volts. These results indicate that the initial electron kinetic energy does not go into internal energy in these ions upon ECD. No effects of ion heating from inelastic ion-electron collisions are observed for electron irradiation times up to 200 ms, although some heating occurs for [Ca(H2O)17]2+ at longer irradiation times. In contrast, this effect is negligible for [Ca(H2O)32]2+, a cluster size typically used in nanocalorimetry experiments, indicating that energy transfer from inelastic ion-electron collisions is negligible compared to effects of radiative absorption and emission for these larger clusters. These results have significance towards establishing the accuracy with which electrochemical red-ox potentials, measured on an absolute basis in the gas phase using ion nanocalorimetry, can be related to relative potentials measured in solution. PMID:18372190

O’Brien, Jeremy T.; Prell, James S.; Holm, Anne I. S.; Williams, Evan R.

2008-01-01

240

Regulating energy transfer of excited carriers and the case for excitation-induced hydrogen dissociation on hydrogenated graphene  

PubMed Central

Understanding and controlling of excited carrier dynamics is of fundamental and practical importance, particularly in photochemistry and solar energy applications. However, theory of energy relaxation of excited carriers is still in its early stage. Here, using ab initio molecular dynamics (MD) coupled with time-dependent density functional theory, we show a coverage-dependent energy transfer of photoexcited carriers in hydrogenated graphene, giving rise to distinctively different ion dynamics. Graphene with sparsely populated H is difficult to dissociate due to inefficient transfer of the excitation energy into kinetic energy of the H. In contrast, H can easily desorb from fully hydrogenated graphane. The key is to bring down the H antibonding state to the conduction band minimum as the band gap increases. These results can be contrasted to those of standard ground-state MD that predict H in the sparse case should be much less stable than that in fully hydrogenated graphane. Our findings thus signify the importance of carrying out explicit electronic dynamics in excited-state simulations. PMID:23277576

Bang, Junhyeok; Meng, Sheng; Sun, Yi-Yang; West, Damien; Wang, Zhiguo; Gao, Fei; Zhang, S. B.

2013-01-01

241

Long time fluctuation of liquid water: l/f spectrum of energy fluctuation in hydrogen bond network rearrangement dynamics  

E-print Network

Long time fluctuation of liquid water: l/f spectrum of energy fluctuation in hydrogen bond network of hydrogen bond network relaxations in liquid water. A simple model of cellular dynamics is proposed Liquid water is a "frustrated" system with multiple random hydrogen bond network structures. Upon

Ramaswamy, Ram

242

Calculation of the Gibbs Free Energy of Solvation and Dissociation of HCl in Water via Monte Carlo Simulations and Continuum Solvation Models  

SciTech Connect

The free energy of solvation and dissociation of hydrogen chloride in water is calculated through a combined molecular simulation quantum chemical approach at four temperatures between T = 300 and 450 K. The free energy is first decomposed into the sum of two components: the Gibbs free energy of transfer of molecular HCl from the vapor to the aqueous liquid phase and the standard-state free energy of acid dissociation of HCl in aqueous solution. The former quantity is calculated using Gibbs ensemble Monte Carlo simulations using either Kohn-Sham density functional theory or a molecular mechanics force field to determine the system’s potential energy. The latter free energy contribution is computed using a continuum solvation model utilizing either experimental reference data or micro-solvated clusters. The predicted combined solvation and dissociation free energies agree very well with available experimental data. CJM was supported by the US Department of Energy,Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

McGrath, Matthew; Kuo, I-F W.; Ngouana, Brice F.; Ghogomu, Julius N.; Mundy, Christopher J.; Marenich, Aleksandr; Cramer, Christopher J.; Truhlar, Donald G.; Siepmann, Joern I.

2013-08-28

243

Dissociation of 10C nuclei in a track nuclear emulsion at an energy of 1.2 GeV per nucleon  

NASA Astrophysics Data System (ADS)

The charge topology in the fragmentation of 10C nuclei in a track nuclear emulsion at an energy of 1.2 GeV per nucleon is studied. In the coherent dissociation of 10C nuclei, about 82% of events are associated with the channel 10C ? 2 ?+ 2 p. The angular distributions and correlations of product fragments are presented for this channel. It is found that among 10C ? 2 ?+ 2 p events, about 30% are associated with the process in which dissociation through the ground state of the unstable 9Beg.s. nucleus is followed by 8Beg.s. + p decays.

Mamatkulov, K. Z.; Kattabekov, R. R.; Alikulov, S. S.; Artemenkov, D. A.; Bekmirzaev, R. N.; Bradnova, V.; Zarubin, P. I.; Zarubina, I. G.; Kondratieva, N. V.; Kornegrutsa, N. K.; Krivenkov, D. O.; Malakhov, A. I.; Olimov, K.; Peresadko, N. G.; Polukhina, N. G.; Rukoyatkin, P. A.; Rusakova, V. V.; Stanoeva, R.; Kharlamov, S. P.

2013-10-01

244

Relationships between interaction energy, intermolecular distance and electron density properties in hydrogen bonded complexes under external electric fields  

NASA Astrophysics Data System (ADS)

The hydrogen bond interaction energy (EHB) of HF⋯HR (R = H, Li, Al, Cl, CCH) complexes under external electric fields is investigated in terms of the bonding distance and of several properties at the bond critical point. All these properties can be used for the estimation of EHB, being the positive curvature along the hydrogen bond path the most suited for the application to experimental electron densities.

Mata, I.; Alkorta, I.; Espinosa, E.; Molins, E.

2011-04-01

245

Electron induced dissociation of trimethyl (methylcyclopentadienyl) platinum (IV): Total cross section as a function of incident electron energy  

NASA Astrophysics Data System (ADS)

The total cross section has been measured for the electron induced dissociation of trimethyl (methylcyclopentadienyl) platinum (IV) [MeCpPt(IV)Me3], a Pt precursor often used in focused electron beam induced processing (FEBIP), for incident electron energies ranging between 3-3 keV. Measurements were performed for the precursor in the adsorbed state under ultrahigh vacuum conditions. The techniques used in this study were temperature programmed desorption, x-ray photoelectron spectroscopy and mass spectrometry. Two surfaces were used in these experiments, amorphous carbon overlayers containing embedded Pt atoms (a:C-Pt), formed by the electron decomposition of the Pt precursor, and atomically clean Au. The results from these three experiments revealed a comparatively low total cross section at 8 eV (4.2±0.3×10-17 cm2 on the a:C-Pt and 1.4±0.1×10-17 cm2 on the Au) that increases with increasing incident electron energy, reaching a maximum at around 150 eV (4.1±0.5×10-16 cm2 on the a:C-Pt and 2.3±0.2×10-16 cm2 on the clean Au), before decreasing at higher incident electron energies, up to 3000 eV. Differences in the measured cross sections between Au and a:C-Pt surfaces demonstrate that the substrate can influence the reaction cross section of adsorbed species. Temperature programmed desorption was also used to measure the adsorption energy of MeCpPt(IV)Me3, which was found to depend on both the substrate and the adsorbate coverage. The work in this paper demonstrates that surface science techniques can be used to quantitatively determine the total cross section of adsorbed FEBIP precursors for electron induced dissociation as a function of incident electron energy. These total cross section values are necessary to obtain quantitatively accurate information from FEBIP models and to compare the reaction efficiencies of different precursors on a quantitative basis.

van Dorp, W. F.; Wnuk, J. D.; Gorham, J. M.; Fairbrother, D. H.; Madey, T. E.; Hagen, C. W.

2009-10-01

246

Photofragment Translational Spectroscopy of Three Body Dissociations and Free Radicals  

NASA Astrophysics Data System (ADS)

This dissertation describes several three-body dissociations and the photodissociation of methyl radicals studied using photofragment translational spectroscopy. The first chapter provides an introduction to three body dissociation, examines current experimental methodology, and includes a discussion on the treatment of photofragment translational spectroscopy data arising from three-body fragmentation. The ultraviolet photodissociation of azomethane into two methyl radicals and nitrogen is discussed in chapter 2. The two methyl fragments possess disparate translational energies indicating that the dissociation is non-symmetric. The angles between the asymptotic velocity vectors of the three fragments are strongly correlated implying that the CH _3N_2 intermediate dissociates in less than a rotational period, < 1 ps. Chapter 3 describes the photodissociation of acetone at 248 nm and 193 nm. At 248 nm the translational energy release from the initial C-C bond cleavage matches the exit barrier height and a comparison with results at 266 nm suggests that < E_{T }> is invariant to the available energy. A fraction of the nascent CH_3 CO radicals spontaneously dissociate following rotational averaging. The < E_{T} > for the second C-C bond cleavage also matches the exit barrier height. At 193 nm the experimental data can be successfully fit assuming that the dynamics are analogous to those at 248 nm. A simplified model of energy partitioning which adequately describes the experimental results is discussed. Experiments on acetyl halides provide additional evidence to support the proposed acetone dissociation mechanism. A value of 17.0 +/- 1.0 kcal/mole for the barrier height to CH_3 CO decomposition has been determined. The photodissociation of methyl radical at 193 nm and 212.8 nm is discussed in the chapter 5. The formation of CH_2 (^1A _1) and H (^2S) was the only single photon dissociation pathway observed at both wavelengths. Methylene internal excitation in excess of predictions from Franck-Condon or impulsive model analysis implies the presence of significant exit channel couplings and highlights the need for detailed ab initio calculations on the CH_3 excited state.

North, Simon William

1995-01-01

247

First-principles study on proton dissociation properties of fluorocarbon- and hydrocarbon-based membranes in low humidity conditions.  

PubMed

We present a theoretical study on the proton dissociation properties of the membranes for polymer electrolyte fuel cells. A density functional theory method is used to study the influence of fluorocarbon and hydrocarbon backbones on proton dissociation, the interaction of water molecules with the sulfonic acid group, and the energy barriers for proton dissociation. Better proton dissociation properties of CH(3)SO(3)H compared to CF(3)SO(3)H are observed from statistical analyses of the optimized structures for both systems. However, the calculated energy barriers for proton dissociation are lower for CF(3)SO(3)H than for the CH(3)SO(3)H system. At the same time, the interaction of water molecules is stronger for CH(3)SO(3)H than for CF(3)SO(3)H. Also, the analysis of the hydrogen-bonding network in both systems shows that the number of hydrogen bonds formed around the sulfonic acid group in CH(3)SO(3)H is larger than that in CF(3)SO(3)H. Therefore, the decrease of the energy barrier with increasing number of coordinating water molecules, pronounced in the case of CH(3)SO(3)H, may lower the barrier, which enhances good proton conductivity of a hydrocarbon-based polymer in low humidity conditions. Thus the hydration ability of a sulfonic acid group is an important factor for realizing better proton dissociation in low humidity conditions. PMID:16956275

Koyama, Michihisa; Bada, Kazunori; Sasaki, Kenji; Tsuboi, Hideyuki; Endou, Akira; Kubo, Momoji; Del Carpio, Carlos A; Broclawik, Ewa; Miyamoto, Akira

2006-09-14

248

Dissociative Recombination Dynamics of the Ozone Cation  

SciTech Connect

The dissociative recombination of the ozone cation has been studied at the heavy-ion storage ring CRYRING. The total cross section and branching fractions have been measured. The cross section from {approx}0eV to 0.2 eV follows a nearly E{sup -1} dependence, which was theoretically predicted to be a characteristic of the direct dissociative recombination mechanism. The thermal rate coefficient has been deduced from the cross section to be 7.37x10{sup -7}(T/300){sup -0.55}cm{sup 3}s{sup -1}. The branching fraction analysis carried out at {approx}0eV interaction energy has shown a strong propensity (94%) to dissociate through the three-body channel. Due to the overwhelming dominance of this channel it has been investigated in more detail. Of the six energetically available three-body pathways only three are significantly populated, such that the production of O(S1) is highly unfavored and all atomic oxygen fragments are predominantly formed in P3 and D1 states. Analysis of the breakup geometries has been performed by means of the Dalitz plot. It is observed that the molecules dissociating through the O(P3)+O(P3)+O(P3) and O(P3)+O(P3)+O(D1) channels have an open linear geometry where the cleavage of two valence bonds occurs preferentially in unison, while the O(P3)+O(D1)+O(D1) breakup might proceed partly through a sequential mechanism.

Zhaunerchyk, Vitali [Stockholm University, Stockholm, Sweden; Geppert, W. [Stockholm University, Stockholm, Sweden; sterdahl, F. [Royal Institute of Technology, Stockholm, Sweden; Larsson, Mats [Stockholm University, Stockholm, Sweden; Thomas, R. D. [Stockholm University, Stockholm, Sweden; Bahati Musafiri, Eric [ORNL; Bannister, Mark E [ORNL; Fogle, Mark R. [Oak Ridge National Laboratory (ORNL); Vane, C Randy [ORNL

2008-02-01

249

Statistical Characterization of the Charge State and Residue Dependence of Low-Energy CID Peptide Dissociation Patterns  

SciTech Connect

Data mining was performed on 28 330 unique peptide tandem mass spectra for which sequences were assigned with high confidence. By dividing the spectra into different sets based on structural features and charge states of the corresponding peptides, chemical interactions involved in promoting specific cleavage patterns in gas-phase peptides were characterized. Pairwise fragmentation maps describing cleavages at all Xxx-Zzz residue combinations for b and y ions reveal that the difference in basicity between Arg and Lys results in different dissociation patterns for singly charged Arg- and Lys-ending tryptic peptides. While one dominant protonation form (proton localized) exists for Arg-ending peptides, a heterogeneous population of different protonated forms or more facile interconversion of protonated forms (proton partially mobile) exists for Lys-ending peptides. Cleavage C-terminal to acidic residues dominates spectra from peptides that have a localized proton and cleavage N-terminal to Pro dominates those that have a mobile or partially mobile proton. When Pro is absent from peptides that have a mobile or partially mobile proton, cleavage at each peptide bond becomes much more prominent. Whether the above patterns can be found in b ions, y ions, or both depends on the location of the proton holder(s). Enhanced cleavages C-terminal to branched aliphatic residues (Ile, Val, Leu) are observed in both b and y ions from peptides that have a mobile proton, as well as in y ions from peptides that have a partially mobile proton; enhanced cleavages N-terminal to these residues are observed in b ions from peptides that have a partially mobile proton. Statistical tools have been designed to visualize the fragmentation maps and measure the similarity between them. The pairwise cleavage patterns observed expand our knowledge of peptide gas-phase fragmentation behaviors and should be useful in algorithm development that employs improved models to predict fragment ion intensities.

Huang, Yingying; Triscari, Joseph M.; Tseng, George C.; Pasa-Tolic, Ljiljana; Lipton, Mary S.; Smith, Richard D.; Wysocki, Vicki H.

2005-09-01

250

Oxygen-oxygen bonds : catalytic redox pathways in energy storage  

E-print Network

Introduction: The present understanding of energy - its many forms, and its governing role in the time evolution of physical systems - underlies many of the most fundamental and unifying principles furnished by scientific ...

Fried, Stephen D. (Stephen David), 1987-

2009-01-01

251

Analyzing angular distributions for two-step dissociation mechanisms in velocity map imaging.  

PubMed

Increasingly, velocity map imaging is becoming the method of choice to study photoinduced molecular dissociation processes. This paper introduces an algorithm to analyze the measured net speed, P(vnet), and angular, ?(vnet), distributions of the products from a two-step dissociation mechanism, where the first step but not the second is induced by absorption of linearly polarized laser light. Typically, this might be the photodissociation of a C-X bond (X = halogen or other atom) to produce an atom and a momentum-matched radical that has enough internal energy to subsequently dissociate (without the absorption of an additional photon). It is this second step, the dissociation of the unstable radicals, that one wishes to study, but the measured net velocity of the final products is the vector sum of the velocity imparted to the radical in the primary photodissociation (which is determined by taking data on the momentum-matched atomic cophotofragment) and the additional velocity vector imparted in the subsequent dissociation of the unstable radical. The algorithm allows one to determine, from the forward-convolution fitting of the net velocity distribution, the distribution of velocity vectors imparted in the second step of the mechanism. One can thus deduce the secondary velocity distribution, characterized by a speed distribution P(v1,2°) and an angular distribution I(?2°), where ?2° is the angle between the dissociating radical's velocity vector and the additional velocity vector imparted to the product detected from the subsequent dissociation of the radical. PMID:23464815

Straus, Daniel B; Butler, Lynne M; Alligood, Bridget W; Butler, Laurie J

2013-08-15

252

Dissociation mechanisms of excited CH3X (X = Cl, Br, and I) formed via high-energy electron transfer using alkali metal targets  

NASA Astrophysics Data System (ADS)

High-energy electron transfer dissociation (HE-ETD) on collisions with alkali metal targets (Cs, K, and Na) was investigated for CH3X+ (X = Cl, Br, and I) ions by a charge inversion mass spectrometry. Relative peak intensities of the negative ions formed via HE-ETD strongly depend on the precursor ions and the target alkali metals. The dependency is explained by the exothermicities of the respective dissociation processes. Peak shapes of the negative ions, especially of the X- ions, which comprise a triangle and a trapezoid, also strongly depend on the precursor ions and the target alkali metals. The trapezoidal part of the I- peak observed with the Na target is more dominant and much broader than that with the Cs target. This dependence on the targets shows an inverse relation between the peak width and the available energy, which corresponds to the exothermicity assuming formation of fragment pair in their ground internal states. From a comparison of the kinetic energy release value calculated from the trapezoidal shape of I- with the available energy of the near-resonant level on the CH3I potential energy curve reported by ab initio calculations, the trapezoidal part is attributed to the dissociation to CH3 + I(2P3/2) via the repulsive 3Q1 state of CH3I, which is not dominant in the photo-dissociation of CH3I. The observation of trapezoid shape of the CH2I- peak with the Cs target indicates spontaneous dissociation via repulsive potential from the 3R2 Rydberg state, although the correlation between the 3R2 Rydberg state and relevant repulsive states has not been reported by any theoretical calculation.

Hayakawa, Shigeo; Tsujinaka, Taiga; Fujihara, Akimasa

2012-11-01

253

An effective Hamiltonian survey of the anharmonic vibrational state space of SCCl2 up to the dissociation energy.  

PubMed

We survey about 3.5 million feature states in the anharmonic state space of SCCl(2) to answer three questions: how sharp is the threshold for intramolecular vibrational energy redistribution (IVR), how do specific resonances and regions of state space contribute to the threshold, and how many undiluted spectral features (or localized eigenstates) persist as energy increases? As quantitative measures we use the dilution factor sigma, Heller's F, and e, which describes how close to the edge of state space a feature lies. We find that an IVR threshold can be identified and lies between 250 and 300 THz. The threshold is softened because different resonances act at different energies in different parts of state space. According to our calculation, about 1 in 10(3) feature states remains undiluted near the dissociation limit of SCCl(2). This fraction matches the number of sharp spectral features observed recently by experiment when symmetry and Franck-Condon factors are taken into account, and it is in agreement with an analytical model that predicts an increasing fraction of undiluted features as molecular size increases. PMID:19355735

Chowdary, Praveen D; Gruebele, Martin

2009-04-01

254

Bridging the Gap between Molecular and Elemental Mass Spectrometry: Higher Energy Collisional Dissociation (HCD) Revealing Elemental Information.  

PubMed

Molecular mass spectrometry has been applied to simultaneously obtain molecular and elemental information from metal-containing species. Energy tuning of the higher-energy collision dissociation (HCD) fragmentation cell allows the controlled production of typical peptide fragments or elemental reporter ions informing about the metallic content of the analyzed species. Different instrumental configurations and fragmentation techniques have been tested, and the efficiency extracting the elemental information has been compared. HCD fragmentation operating at very high energy led to the best results. Platinum, lanthanides, and iodine reporter ions from peptides interacting with cisplatin, peptides labeled with lanthanides-MeCAT-IA, and iodinated peptides, respectively, were obtained. The possibility to produce abundant molecular and elemental ions in the same analysis simplifies the correlation between both signals and open pathways in metallomics studies enabling the specific tracking of metal-containing species. The proposed approach has been successfully applied to in solution standards and complex samples. Moreover, interesting preliminary MALDI-imaging experiments have been performed showing similar metal distribution compared to laser ablation (LA)-ICPMS. PMID:25528895

Esteban-Fernández, Diego; El-Khatib, Ahmed H; Moraleja, Irene; Gómez-Gómez, M Milagros; Linscheid, Michael W

2015-02-01

255

The dissociation of low energy 1,2-propanediol ions: an intriguing mechanism revisited  

NASA Astrophysics Data System (ADS)

The fascinating unimolecular chemistry of ionized 1,2-propanediol, CH3C(H)OHCH2OH[middle dot]+, 1, has been re-examined using computational chemistry (ab initio MO and density functional theories) in conjunction with modern tandem mass spectrometric and 13C labelling experiments. The calculations allow a considerable simplification of a previously proposed complex mechanism (Org. Mass Spectrom., 23 (1988) 355). Again, the central intermediates are proposed to be stable hydrogen bridged ion--dipole complexes, but our present calculations indicate that the key transformation now is the rearrangement CH3C(H)OH+[middle dot][middle dot][middle dot]O(H)-CH2. --> CH3C(H)OH+[middle dot][middle dot][middle dot].OCH3, which can best be viewed as the cation-catalyzed 1,2-hydrogen shift .CH2OH --> CH3O., a rearrangement which does not occur so easily in the unassisted system. Another important process is the electron transfer CH3C(H)=O[middle dot][middle dot][middle dot]CH3OH[middle dot]+ --> O=CH(CH3)[middle dot]+[middle dot][middle dot][middle dot]O(H)CH3 which allows proton transfer to generate CH3OH2+ + CH3C=O.. Other dissociation processes (loss of CH3., H2O, H2O + CH3., H2O + CH4) are interpreted in terms of Bohme's `methyl cation shuttle' (J. Am. Chem. Soc., 118 (1996) 4500) taking place in ion-dipole complexes. The most stable intermediate is the hydrogen bridged ion-dipole complex CH2=CHOH.+[middle dot][middle dot][middle dot]O(H)CH3, which is the reacting configuration for loss of methanol.

Burgers, Peter C.; Fell, Lorne M.; Milliet, Arielle; Rempp, Muriel; Ruttink, Paul J. A.; Terlouw, Johan K.

1997-11-01

256

Experimental determination of energy disposal in the dissociative electron recombinations of CS2(+) and HCS2(+).  

PubMed

Vibronic optical emissions from CS(A1pi --> X1sigma+) and CS(a3pi --> X1sigma+) transitions have been identified from dissociative recombination (DR) of CS2(+) and HCS2(+) plasmas. All of the spectra were taken in flowing afterglow plasmas using an optical monochromator in the UV-visible wavelength region of 180-800 nm. For the CS(A --> X) and CS(a --> X) emissions, the relative vibrational distributions have been calculated for v' < 5 and v' < 3 in both types of plasmas for the CS(A) and CS(a) states, respectively. Both recombining plasmas show a population inversion from the v' = 0 to v' = 1 level of the CS(A) state, similar to other observations of the CS(A) state populations, which were generated using two other energetic processes. The possibility of spectroscopic cascading is addressed, such that transitions from upper level electronic states into the CS(A) and CS(a) states would affect the relative vibrational distribution, and there is no spectroscopic evidence supporting the cascading effect. Additionally, excited-state transitions from neutral sulfur (S(5S(2)0 --> 3P(2)) and S(5S(2)0 --> 3P(1))) and the products of ion-molecule reactions (CS(B1sigma+ --> A1pi), CS(+)(B2sigma+ --> A2pi(i)), and CS2(+) (A2pi(u) --> X2pi(g))) have been observed and are discussed. PMID:18186620

Molek, C D; Plasil, R; McLain, J L; Adams, N G; Babcock, L M

2008-02-01

257

Dissociative recombination of CH4(+).  

PubMed

CH4(+) is an important molecular ion in the astrochemistry of diffuse clouds, dense clouds, cometary comae, and planetary ionospheres. However, the rate of one of the common destruction mechanisms for molecular ions in these regions, dissociative recombination (DR), is somewhat uncertain. Here, we present absolute measurements for the DR of CH4(+) made using the heavy ion storage ring CRYRING in Stockholm, Sweden. From our collision-energy dependent cross-sections, we infer a thermal rate constant of k(Te) = 1.71(±0.02) × 10(–6)(Te/300)(?0.66(±0.02)) cm3 s(–1) over the region of electron temperatures 10 ? Te ? 1000 K. At low collision energies, we have measured the branching fractions of the DR products to be CH4 (0.00 ± 0.00); CH3 + H (0.18 ± 0.03); CH2 + 2H (0.51 ± 0.03); CH2 + H2 (0.06 ± 0.01); CH + H2 + H (0.23 ± 0.01); and CH + 2H2 (0.02 ± 0.01), indicating that two or more C–H bonds are broken in 80% of all collisions. PMID:23651407

Thomas, Richard D; Kashperka, Iryna; Vigren, E; Geppert, Wolf D; Hamberg, Mathias; Larsson, Mats; af Ugglas, Magnus; Zhaunerchyk, Vitali

2013-10-01

258

Chemical bond as a test of density-gradient expansions for kinetic and exchange energies  

SciTech Connect

Errors in kinetic and exchange contributions to the molecular bonding energy are assessed for approximate density functionals by reference to near-exact Hartree-Fock values. From the molecular calculations of Allan et al. and of Lee and Ghosh, it is demonstrated that the density-gradient expansion does not accurately describe the noninteracting kinetic contribution to the bonding energy, even when this expansion is carried to fourth order and applied in its spin-density-functional form to accurate Hartree-Fock densities. In a related study, it is demonstrated that the overbinding of molecules such as N/sub 2/ and F/sub 2/, which occurs in the local-spin-density (LSD) approximation for the exchange-correlation energy, is not attributable to errors in the self-consistent LSD densities. Contrary to expectations based upon the Gunnarsson-Jones nodality argument, it is found that the LSD approximation for the exchange energy can seriously overbind a molecule even when bonding does not create additional nodes in the occupied valence orbitals. LSD and exact values for the exchange contribution to the bonding energy are displayed and discussed for several molecules.

Perdew, J.P.; Levy, M.; Painter, G.S.; Wei, S.; Lagowski, J.B.

1988-01-15

259

Metal carbon bond energies for adsorbed hydrocarbons from calorimetric data  

Microsoft Academic Search

Single crystal adsorption calorimetry (SCAC) is a powerful new method for measuring adsorption and reaction energies. Particularly for hydrocarbons, where little or no information is available from either experiment or theory on well-defined surfaces, this method can provide crucially needed information. Assignment of the measured calorimetric heats to the appropriate surface reaction yields directly reaction heats and heats of formation

Heike Gross; Charles T. Campbell; David A. King

2004-01-01

260

Calorimetric and computational study of thiacyclohexane 1-oxide and thiacyclohexane 1,1-dioxide (thiane sulfoxide and thiane sulfone). Enthalpies of formation and the energy of the S=O bond.  

PubMed

A rotating-bomb combustion calorimeter specifically designed for the study of sulfur-containing compounds [J. Chem. Thermodyn. 1999, 31, 635] has been used for the determination of the enthalpy of formation of thiane sulfone, 4, Delta(f)H(o) m(g) = -394.8 +/- 1.5 kJ x mol(-1). This value stands in stark contrast with the enthalpy of formation reported for thiane itself, Delta(f)H(o) m(g) = -63.5 +/- 1.0 kJ x mol(-1), and gives evidence of the increased electronegativity of the sulfur atom in the sulfonyl group, which leads to significantly stronger C-SO2 bonds. Given the known enthalpy of formation of atomic oxygen in the gas phase, Delta(f)H(o) m(O,g) = +249.18 kJ x mol(-1), and the reported bond dissociation energy for the S=O bond in alkyl sulfones, BDE(S=O) = +470.0 kJ x mol(-1), it was possible to estimate the enthalpy of formation of thiane sulfoxide, 5, a hygroscopic compound not easy to use in experimental calorimetric measurements, Delta(f)H(o) m(5) = -174.0 kJ x mol(-1). The experimental enthalpy of formation of both 4 and 5 were closely reproduced by theoretical calculations at the G2(MP2)+ level, Delta(f)H(o) m(4) = -395.0 kJ x mol(-1) and Delta(f)H(o) m(5) = -178.0 kJ x mol(-1). Finally, calculated G2(MP2)+ values for the bond dissociation energy of the S=O bond in cyclic sulfoxide 5 and sulfone 4 are +363.7 and +466.2 kJ x mol(-1), respectively. PMID:12608789

Roux, María Victoria; Temprado, Manuel; Jiménez, Pilar; Dávalos, Juan Zenón; Notario, Rafael; Guzmán-Mejía, Ramón; Juaristi, Eusebio

2003-03-01

261

Average bond energies between boron and elements of the fourth, fifth, sixth, and seventh groups of the periodic table  

NASA Technical Reports Server (NTRS)

The average bond energies D(gm)(B-Z) for boron-containing molecules have been calculated by the Pauling geometric-mean equation. These calculated bond energies are compared with the average bond energies D(exp)(B-Z) obtained from experimental data. The higher values of D(exp)(B-Z) in comparison with D(gm)(B-Z) when Z is an element in the fifth, sixth, or seventh periodic group may be attributed to resonance stabilization or double-bond character.

Altshuller, Aubrey P

1955-01-01

262

Electronic structure, molecular bonding and potential energy surfaces  

SciTech Connect

By virtue of the universal validity of the generalized Born-Oppenheimer separation, potential energy surfaces (PES`) represent the central conceptual as well as quantitative entities of chemical physics and provide the basis for the understanding of most physicochemical phenomena in many diverse fields. The research in this group deals with the elucidation of general properties of PES` as well as with the quantitative determination of PES` for concrete systems, in particular pertaining to reactions involving carbon, oxygen, nitrogen and hydrogen molecules.

Ruedenberg, K. [Ames Laboratory, IA (United States)

1993-12-01

263

Ionic bond effects on the mean excitation energy for stopping power  

NASA Technical Reports Server (NTRS)

Molecular mean excitation energies for ionic bonded molecules calculated according to the local plasma approximation are compared to the Bragg rule. Adjustments of 15% are calculated for LiF in agreement with experiments while 6% adjustments are predicted for HF and 3% for LiH.

Wilson, J. W.; Chang, C. K.; Kamaratos, E.; Xu, Y. J.

1982-01-01

264

Chemical bond effects on the low energy electronic stopping power: theory  

Microsoft Academic Search

We discuss the applicability of a modified version of the Firsov model to account for the low-energy electronic stopping cross section (Se) due to molecular targets. We employ floating spherical Gaussian orbitals (FSGO), which reproduce major trends in electronic and geometrical structure of molecules. Two advantages of using FSGO are: i) each localized orbital is classified as inner shell, bonding

S. A. Cruz; J. Soullard

1991-01-01

265

Real-Time Evolution of the Valence Electronic Structure in a Dissociating Molecule  

SciTech Connect

Time-resolved valence band photoelectron spectroscopy with a temporal resolution of 135 fs is used to map the entire occupied valence electronic structure of photoexcited gas-phase Br{sub 2} molecules during dissociation. The observed shifting and mixing of valence energy levels defines a transition period where the system appears to be intermediate between atoms and molecules. The surprisingly short bond breaking or dissociation time is determined by monitoring in real time how the photoelectron multiplet structure of the free atom arises from the valence states of the photoexcited molecule.

Wernet, Ph.; Godehusen, K.; Gaudin, J.; Schwarzkopf, O.; Eberhardt, W. [Helmholtz-Zentrum Berlin, Albert-Einstein-Strasse 15, D-12489 Berlin (Germany); Odelius, M. [FYSIKUM, Stockholm University, AlbaNova, S-106 91 Stockholm (Sweden)

2009-07-03

266

High-Energy Collision-Induced Dissociation by MALDI TOF/TOF Causes Charge-Remote Fragmentation of Steroid Sulfates  

NASA Astrophysics Data System (ADS)

A method for structural elucidation of biomolecules dating to the 1980s utilized high-energy collisions (~10 keV, laboratory frame) that induced charge-remote fragmentations (CRF), a class of fragmentations particularly informative for lipids, steroids, surfactants, and peptides. Unfortunately, the capability for high-energy activation has largely disappeared with the demise of magnetic sector instruments. With the latest designs of tandem time-of-flight mass spectrometers (TOF/TOF), however, this capability is now being restored to coincide with the renewed interest in metabolites and lipids, including steroid-sulfates and other steroid metabolites. For these metabolites, structure determinations are required at concentration levels below that appropriate for NMR. To meet this need, we explored CRF with TOF/TOF mass spectrometry for two groups of steroid sulfates, 3-sulfates and 21-sulfates. We demonstrated that the current generation of MALDI TOF/TOF instruments can generate charge-remote fragmentations for these materials. The resulting collision-induced dissociation (CID) spectra are useful for positional isomer differentiation and very often allow the complete structure determination of the steroid. We also propose a new nomenclature that directly indicates the cleavage sites on the steroid ring with carbon numbers.

Yan, Yuetian; Ubukata, Masaaki; Cody, Robert B.; Holy, Timothy E.; Gross, Michael L.

2014-08-01

267

High-energy collision-induced dissociation by MALDI TOF/TOF causes charge-remote fragmentation of steroid sulfates.  

PubMed

A method for structural elucidation of biomolecules dating to the 1980s utilized high-energy collisions (~10 keV, laboratory frame) that induced charge-remote fragmentations (CRF), a class of fragmentations particularly informative for lipids, steroids, surfactants, and peptides. Unfortunately, the capability for high-energy activation has largely disappeared with the demise of magnetic sector instruments. With the latest designs of tandem time-of-flight mass spectrometers (TOF/TOF), however, this capability is now being restored to coincide with the renewed interest in metabolites and lipids, including steroid-sulfates and other steroid metabolites. For these metabolites, structure determinations are required at concentration levels below that appropriate for NMR. To meet this need, we explored CRF with TOF/TOF mass spectrometry for two groups of steroid sulfates, 3-sulfates and 21-sulfates. We demonstrated that the current generation of MALDI TOF/TOF instruments can generate charge-remote fragmentations for these materials. The resulting collision-induced dissociation (CID) spectra are useful for positional isomer differentiation and very often allow the complete structure determination of the steroid. We also propose a new nomenclature that directly indicates the cleavage sites on the steroid ring with carbon numbers. PMID:24781458

Yan, Yuetian; Ubukata, Masaaki; Cody, Robert B; Holy, Timothy E; Gross, Michael L

2014-08-01

268

The H2 dissociation on the BN, AlN, BP and AlP nanotubes: a comparative study.  

PubMed

The thermodynamic and kinetic feasibility of H(2) dissociation on the BN, AlN, BP and AlP zigzag nanotubes has been investigated theoretically by calculating the dissociation and activation energies. We determined the BN and AlP tubes to be inert toward H(2) dissociation, both thermodynamically and kinetically. The reactions are endothermic by 5.8 and 3 kcal mol(-1), exhibiting high activation energies of 38.8 and 30.6 kcal mol(-1), respectively. Our results indicated that H(2) dissociation is thermodynamically favorable on both PB and AlN nanotubes. However, in spite of the thermodynamic feasibility of H(2) dissociation on PB types, this process is kinetically unfavorable due to partly high activation energy. Generally, we concluded that among the four studied tubes, the AlN nanotube may be an appropriate model for H(2) dissociation process, from a thermodynamic and kinetic stand point. We also indicated that H(2) dissociation is not homolytic, rather it takes place via a heterolytic bond cleavage. In addition, a comparative study has been performed on the electrical and geometrical properties of the tubes. Our analysis showed that the electrical conductivity of tubes is as follows: BP>AlP>BN>AlN depending on how to combine the electron rich and electron poor atoms. PMID:21979405

Beheshtian, Javad; Soleymanabadi, Hamed; Kamfiroozi, Mohammad; Ahmadi, Ali

2012-06-01

269

Dissociative Identity Disorder  

MedlinePLUS

Dissociative Identity Disorder What is dissociative identity disorder (DID)? Dissociative identity disorder (DID), previously referred to as ... among their possessions. What are the symptoms of DID? Often people living with DID are depressed or ...

270

An energy criterion for determining d orbital contribution to adsorbate bonding to a transition metal: CO\\/Fe 12  

Microsoft Academic Search

Summary A new criterion is presented for determining the contribution of a particular class or group of orbitals to a chemical bond. The new criterion is the diatomic energy contribution of particular orbitals to a bond. In neglect to differential overlap methods the total energy may be decomposed entirely into monoatomic and diatomic terms. The contribution of the electrons ind

George Blyholder; Michael Lawless

1990-01-01

271

Quantum dynamics study of fulvene double bond photoisomerization: The role of intramolecular vibrational energy redistribution and excitation energy  

SciTech Connect

The double bond photoisomerization of fulvene has been studied with quantum dynamics calculations using the multi-configuration time-dependent Hartree method. Fulvene is a test case to develop optical control strategies based on the knowledge of the excited state decay mechanism. The decay takes place on a time scale of several hundred femtoseconds, and the potential energy surface is centered around a conical intersection seam between the ground and excited state. The competition between unreactive decay and photoisomerization depends on the region of the seam accessed during the decay. The dynamics are carried out on a four-dimensional model surface, parametrized from complete active space self-consistent field calculations, that captures the main features of the seam (energy and locus of the seam and associated branching space vectors). Wave packet propagations initiated by single laser pulses of 5-25 fs duration and 1.85-4 eV excitation energy show the principal characteristics of the first 150 fs of the photodynamics. Initially, the excitation energy is transferred to a bond stretching mode that leads the wave packet to the seam, inducing the regeneration of the reactant. The photoisomerization starts after the vibrational energy has flowed from the bond stretching to the torsional mode. In our propagations, intramolecular energy redistribution (IVR) is accelerated for higher excess energies along the bond stretch mode. Thus, the competition between unreactive decay and isomerization depends on the rate of IVR between the bond stretch and torsion coordinates, which in turn depends on the excitation energy. These results set the ground for the development of future optical control strategies.

Blancafort, Lluis [Institut de Quimica Computacional, Department de Quimica, Universitat de Girona, Campus de Montilivi, 17071 Girona (Spain); Gatti, Fabien [CTMM, Institut Charles Gerhardt Montpellier (UMR 5253), CC 1501, Universite Montpellier 2, 34095 Montpellier Cedex 05 (France); Meyer, Hans-Dieter [Theoretische Chemie, Ruprecht-Karls-Universitaet, Im Neuenheimer Feld 229, 69120 Heidelberg (Germany)

2011-10-07

272

Low-energy electron dissociative attachment processes in HgBr2  

Microsoft Academic Search

Br- formation in HgBr2 has been studied by means of two cross-beam electron impact spectrometers, one equipped with a trochoidal electron monochromator and a magnetic mass analyser and the other one equipped with two 127 degrees electrostatic energy filters and a quadrupole mass analyser. It is found that the Br- cross section in the energy range 0-7 eV exhibits two

R. Azria; J. P. Ziesel; R. Abouaf; L. Bouby; M. Tronc

1983-01-01

273

Structure, energy, vibrational spectrum, and Bader's analysis of ?···H hydrogen bonds and H(-?)···H(+?) dihydrogen bonds.  

PubMed

In this paper, the intermolecular structural study asserted by the vibrational analysis in the stretch frequencies of hydrogen bonds (?···H) and dihydrogen bonds (H(-?)···H(+?)) have definitively been revisited by means of calculations carried out by Density Functional Theory (DFT) and topological parameters derived from the classic treatise of the Quantum Theory of Atoms in Molecules (QTAIM). As a matter of fact the ?···H hydrogen bond is formed between the hydrofluoric acid and the C?C bond of the acetylene, but the QTAIM calculations revealed a distortion in this interaction due to the formation of the ternary complex C(2)H(2)···2(HF). Although the ? bonds of ethylene (C(2)H(4)), propylene (C(2)H(3)(CH(3))), and t-butylene (C(2)H(2)(CH(3))(2)) are considered proton acceptors, two hydrogen-bond types--?···H and C···H--can be observed. Over and above the analysis of the ? hydrogen bonds, theoretical arguments also were used to discuss the red-shifts in the stretch frequencies of the binary dihydrogen complexes formed by BeH(2)···HX with X = F, Cl, CN, and CCH. Although a vibrational blue-shift in the stretch frequency of the H-C bond of HCF(3) due to the formation of the BeH(2)···HCF(3) dihydrogen complex was obtained, unmistakable red-shifts were detected in LiH···HCF(3), MgH(2)···HCF(3), and NaH···HCF(3). Moreover, the alkali-halogen bonds were identified in relation to the formation of the trimolecular systems NaH···2(HCF(3)) and NaH···2(HCCl(3)). At last, theoretical calculations and QTAIM molecular integrations were used to study a novel class of dihydrogen-bonded complexes (mC(2)H(5)(+)···nMgH(2) with m = 1 or 2 and n = 1 or 2) based in the insight that MgH(2) can bind with the non-localized hydrogen H(+?) of the ethyl cation (C(2)H(5)(+)). In an overview, QTAIM calculations were applied to evaluate the molecular topography, charge density, as well as to interpret the shifted frequencies either to red or blue caused by the formation of the hydrogen bonds and dihydrogen bonds. PMID:23138158

de Oliveira, Boaz Galdino

2013-01-01

274

Dissociative ionization of biomolecules  

NASA Astrophysics Data System (ADS)

Dissociative ionization (DI) by electron impact plays a role in many different applications, including low-temperature plasma processing, the study of space and astrophysical plasmas, and the study of biological damages by high-energy radiation. In the present study, our goal is to understand the health hazard to humans from exposure to radiation during an extended space flight. DI by secondary electrons can damage the DNA, either directly by causing a DNA lesion, or indirectly by producing radicals and cations that attack the DNA. The theoretical model employed makes use of the fact that electronic motion is much faster than nuclear motion, allowing DI to be treated as a two-step process. The first step is electron-impact ionization resulting in a dissociative state of the molecular ion with the same geometry as the neutral molecule. In the second step the ion relaxes from the initial geometry and undergoes unimolecular dissociation. Thus the DI cross section is given by the product of the ionization cross section and the dissociation probability. For the ionization process we use the improved binary-encounter dipole (iBED) model. For unimolecular dissociation, we use the multiconfigurational self-consistent field (MCSCF) method to determine the minimum energy pathways to possible product channels. This model has been applied to study the DI of H_2O, NH_3, and CH_4, and the results are in good agreement with experiment. The DI from the low-lying channels of benzene has also been studied and the dissociation products are compared with photoionization measurements. The DI of the DNA bases guanine and cytosine are then discussed. Of the four DNA bases, guanine has the largest ionization cross section and cytosine has the smallest. The guanine radical cation is considered to be one of the precursors to the primary, direct-type lesions formed in DNA when it is irradiated. Comparison of DI products of guanine and cytosine will be made to understand the differences in their behavior upon irradiation.

Huo, Winifred

2004-09-01

275

Analysis of low complex region peptides derived from mollusk shell matrix proteins using CID, high-energy collisional dissociation, and electron transfer dissociation on an LTQ-orbitrap: implications for peptide to spectrum match.  

PubMed

Identification of proteins involved in mollusk biomineralization by proteomics approach is gaining importance. These proteins are often characterized by low-complexity regions (LCRs) made of repeating motifs that are constituted by few amino acids (e.g. IGG, DD, KK, and GGG). In this work, we have analyzed the fragmentation of model LCR peptides under different fragmentation regimes (CID, high-energy collisional dissociation [HCD], and electron transfer dissociation [ETD]) and its consequences on peptide to spectrum matches (PSMs) using two search algorithms (Mascot and PEAKS DB). For both search tools, higher number of PSMs was obtained using CID spectra, followed by HCD and ETD. Intense fragment ions present in the lower m/z region of HCD led to lower PSM scores and absence of low mass cut off seems to offer little advantage for the identification of LCR peptides. Generally, doubly charged peptides under ETD conditions did not fragment to yield sequence information rich spectra. The spectral quality is affected by the nature of the repeating motifs in the peptide. The performance of both Mascot and PEAKS DB (de novo based search tool) vary according to the fragment regime employed to acquire MS/MS spectra. PMID:22888092

Marie, Arul; Alves, Sandra; Marie, Benjamin; Dubost, Lionel; Bédouet, Laurent; Berland, Sophie

2012-10-01

276

The dissociation dynamics of low lying triplet states in butane and butene molecules  

NASA Astrophysics Data System (ADS)

Butane, methylpropane, 1-,2-butene and isobutene are studied as a complete set of doubley methylated ethane and ethene molecules in order to probe the dissociation dynamics of their excited states. The butane and butene molecules are formed in electronically highly excited states by neutralization of their respective radical cations in collisions with alkali metal atoms. Processes that lead to dissociations into two fragments are measured with differential translational spectroscopy. it is found that the first triplet state is dominantly populated. Butanes exhibit direct dissociation of a carbon?carbon (C?C) bond via a repulsive state. Intramolecular vibrational energy redistribution (IVR) prior to dissociation is observed for the unsaturated butenes. For the butenes the C?C bond cleavage is even preceded by a hydrogen shift, resulting in molecular losses like methane and ethene. In this paper we stress the relations between the present results and optical excitation and electron scattering experiments. For butane the proposed dissociation via a repulsive triplet state is corroborated in ab initio calculations.

Beijersbergen, Jaap H. M.; de Koster, Chris. G.; van der Zande, Win J.; Kistemaker, Piet G.; Los, Joop

1992-02-01

277

Dissociation Channels of c-C4F8 to CF2 Radical in Reactive Plasma  

NASA Astrophysics Data System (ADS)

It has been generally assumed that octafluorocyclobutane (c-C4F8) is mainly decomposed to CF2 via C2F4 in etching process plasma. However, the detailed mechanism for the dissociations is yet ambiguous. In this paper we have calculated the probable dissociation pathways by using ab initio molecular orbital method. The results show that c-C4F8 is dissociated via the first triplet excited state T1(3A2), the fourth triplet excited state T4(32E) and the fourth singlet excited state S4(12E). One of the degenerate excited states of T4 and S4 is constituted by antibonding combination of two ? bonding orbital of C2F4. T1 state is constituted by antibonding combination of b1u antibonding ? orbital of C2F4. Therefore, in the case of the dissociation via S4 and T4 excited states c-C4F8 may dissociate to two C2F4, and in the case of the dissociation via T1 excited state c-C4F8 may dissociate to four CF2 radicals. It is also found that C3F5+ ion observed as the main peak in c-C4F8 process plasma is produced by electron collision with the slightly larger energy than the ionization threshold value. The main dissociation path of C2F4 is a vertical electron attachment. However, it is also found that dissociation pathways via 1B2g, 3B1u, and 3B2g excited states are very important and should not be ignored.

Hayashi, Toshio; Ishikawa, Kenji; Sekine, Makoto; Hori, Masaru; Kono, Akihiro; Suu, Koukou

2011-03-01

278

Cascade Dissociations of Peptide Cation-Radicals. Part2. Infrared Multiphoton Dissociation and Mechanistic Studies of z-Ions from Pentapeptides  

PubMed Central

Dissociations of z4 ions from pentapeptides AAXAR, where X = H, Y, F, W, and V, produce dominant z2 ions that account for >50% of the fragment ion intensity. The dissociation has been studied in detail by experiment and theory and found to involve several isomerization and bond-breaking steps. Isomerizations in z4 ions proceed by amide transcis rotations followed by radical-induced transfer of a ?-hydrogen atom from the side chain, forming stable C? radical intermediates. These undergo rate-determining cleavage of the C?—CO bond at the X residue followed by loss of the neutral AX fragment, forming x2 intermediates. The latter were detected by energy-resolved resonant excitation collision-activated dissociation (CAD) and infrared multiphoton dissociation (IRMPD) experiments. The x2 intermediates undergo facile loss of HNCO to form z2 fragment ions, as also confirmed by energy-resolved CAD and IRMPD MS4 experiments. The loss of HNCO from the x2 ion from AAHWR is kinetically hampered by the Trp residue that traps the OCNH radical group in a cyclic intermediate. PMID:22669762

Ledvina, Aaron R.; Chung, Thomas W.; Hui, Renjie; Coon, Joshua J.

2013-01-01

279

Cascade dissociations of peptide cation-radicals. Part 2. Infrared multiphoton dissociation and mechanistic studies of z-ions from pentapeptides.  

PubMed

Dissociations of z(4) ions from pentapeptides AAXAR where X=H, Y, F, W, and V produce dominant z(2) ions that account for >50 % of the fragment ion intensity. The dissociation has been studied in detail by experiment and theory and found to involve several isomerization and bond-breaking steps. Isomerizations in z(4) ions proceed by amide trans?cis rotations followed by radical-induced transfer of a ?-hydrogen atom from the side chain, forming stable C(?) radical intermediates. These undergo rate-determining cleavage of the C(?)-CO bond at the X residue followed by loss of the neutral AX fragment, forming x(2) intermediates. The latter were detected by energy-resolved resonant excitation collision-induced dissociation (CID) and infrared multiphoton dissociation (IRMPD) experiments. The x(2) intermediates undergo facile loss of HNCO to form z(2) fragment ions, as also confirmed by energy-resolved CID and IRMPD MS(4) experiments. The loss of HNCO from the x(2) ion from AAHWR is kinetically hampered by the Trp residue that traps the OCNH radical group in a cyclic intermediate. PMID:22669762

Ledvina, Aaron R; Chung, Thomas W; Hui, Renjie; Coon, Joshua J; Ture?ek, Frantisek

2012-08-01

280

Cascade Dissociations of Peptide Cation-Radicals. Part 2. Infrared Multiphoton Dissociation and Mechanistic Studies of z-Ions from Pentapeptides  

NASA Astrophysics Data System (ADS)

Dissociations of z 4 ions from pentapeptides AAXAR where X = H, Y, F, W, and V produce dominant z 2 ions that account for >50 % of the fragment ion intensity. The dissociation has been studied in detail by experiment and theory and found to involve several isomerization and bond-breaking steps. Isomerizations in z 4 ions proceed by amide trans?cis rotations followed by radical-induced transfer of a ?-hydrogen atom from the side chain, forming stable C? radical intermediates. These undergo rate-determining cleavage of the C?-CO bond at the X residue followed by loss of the neutral AX fragment, forming x 2 intermediates. The latter were detected by energy-resolved resonant excitation collision-induced dissociation (CID) and infrared multiphoton dissociation (IRMPD) experiments. The x 2 intermediates undergo facile loss of HNCO to form z 2 fragment ions, as also confirmed by energy-resolved CID and IRMPD MS4 experiments. The loss of HNCO from the x 2 ion from AAHWR is kinetically hampered by the Trp residue that traps the OCNH radical group in a cyclic intermediate.

Ledvina, Aaron R.; Chung, Thomas W.; Hui, Renjie; Coon, Joshua J.; Ture?ek, Frantisek

2012-08-01

281

Dissociation of the effects of preload volume and energy content on subjective appetite and food intake  

Microsoft Academic Search

Previous research suggests that enhancing the volume of a food preload without altering energy content can result in reduced appetite, although the limited evidence means that the conditions under which this effect will occur are not yet clear. In the present study, we used a Universal Eating Monitor (UEM) to record test meal intake constantly, in parallel with appetite ratings,

Richard W. Gray; Stephen J. French; Tristan M. Robinson; Martin R. Yeomans

2002-01-01

282

Binding energies of hydrogen-bonded complexes from extrapolation with localized basis sets  

NASA Astrophysics Data System (ADS)

By incorporating effective basis sets containing diffuse functions only in the interaction region of hydrogen-bonded complexes into the simple extrapolation scheme suitable for such basis sets, an accurate estimation of the MP2 basis set limit hydrogen-bonding energies of formic acid tetramer, formamide tetramer, alanine-water, phenol-water, and guanine-cytosine base pair is made with all estimates falling within 0.1-0.3kcal/mol of the reference basis set limits. The basis sets for extrapolation are composed of the cc-pVDZ and cc-pVDZ plus highest polarization functions from the cc-pVTZ set, or cc-pVDZ and cc-pVTZ set, all of which are augmented by the diffuse functions of the atoms in the interaction region of hydrogen bond. In contrast to the extrapolated estimates by this method, density functional theory binding energies with B3LYP, B971, and TPSS methods yield the differences from the reference values as large as 3.9kcal/mol with much higher computational cost in most cases, signifying the efficacy of the employed extrapolation scheme for study of large hydrogen-bonded complexes.

Lee, Jae Shin

2007-08-01

283

Biradical thermochemistry from collision-induced dissociation threshold energy measurements. Absolute heats of formation of ortho-, meta-, and para-benzyne  

Microsoft Academic Search

The absolute heats of formation of 1,2-, 1,3-, and 1,4-dehydrobenzene (ortho, meta-, and para-benzyne) have been determined from measurements of the threshold energies for collision-induced dissociation (CID) of ortho, meta-, and para-chlorophenyl anions in a flowing afterglow-triple quadrupole apparatus. The 298 K heats of formation for ortho-, meta-, and para-benzyne derived in this manner are 106.6 [+-] 3.0, 122.0 [+-

Paul G. Wenthold; Robert R. Squires

1994-01-01

284

Energy-resolved collision-induced dissociation of Aln+ clusters (n=2-11) in the center of mass energy range from few hundred meV to 10 eV  

NASA Astrophysics Data System (ADS)

Energy-resolved collision-induced dissociation (CID) of Aln+ (n=2-11) in collision with argon is presented for the energy ranges from few hundred meV to 10 eV in the center of mass frame. The experiments were carried out with a recently constructed secondary ion tandem mass spectrometer, that is described in detail. The collision energy dependence is measured for the total and the partial dissociation cross sections, and the dissociation thresholds for the individual processes are estimated. The release of Al+ is found to be the dominating channel for n<8. For n>8, the cross section for the release of Al+ and Al are comparable. The release of more than one neutral atom from the larger clusters (n>6) is found to be in good agreement with sequential atom loss. In the case of the smaller clusters, on the other hand, fission is the energetically favorable process. The closed shell cluster, Al7+ (20 valence electrons), is found to be exceptionally stable and the adiabatic ionization potential of Al7 is found to be lower than that of the monomer. The stability of Al7+ is further reflected in the dissociation dynamics of the next neighbor, Al8+. The high stability of Al7+ as well as the dissociation dynamics of Al8+ are treated in the simple frame of the electronic shell model. Unlike Al7+, Al3+ (with 8 valence electrons) shows no sign of increased stability, and the dissociation dynamics seems to be controlled by the spin selection rules, rather than the energetics. In the present work, general trends and the dissociation dynamics of individual clusters are discussed. Qualitative information on the development of the geometric and electronic structure, with increasing cluster size, is deduced and discussed in terms of a transition from a covalent to a metallic character. Finally, this work is compared to earlier theoretical and experimental approaches to Aln+ clusters.

Ingólfsson, Oddur; Takeo, Harutoshi; Nonose, Shinji

1999-03-01

285

Detection and Characterization of Low Abundance Glycopeptides Via Higher-Energy C-Trap Dissociation and Orbitrap Mass Analysis  

NASA Astrophysics Data System (ADS)

Broad-scale mass spectrometric analyses of glycopeptides are constrained by the considerable complexity inherent to glycoproteomics, and techniques are still being actively developed to address the associated analytical difficulties. Here we apply Orbitrap mass analysis and higher-energy C-trap dissociation (HCD) to facilitate detailed insights into the compositions and heterogeneity of complex mixtures of low abundance glycopeptides. By generating diagnostic oxonium product ions at mass measurement errors of <5 ppm, highly selective glycopeptide precursor ion detections are made at sub-fmol limits of detection: analyses of proteolytic digests of a hen egg glycoprotein mixture detect 88 previously uncharacterized glycopeptides from 666 precursor ions selected for MS/MS, with only one false positive due to co-fragmentation of a non-glycosylated peptide with a glycopeptide. We also demonstrate that by (1) identifying multiple series of glycoforms using high mass accuracy single stage MS spectra, and (2) performing product ion scans at optimized HCD collision energies, the identification of peptide + N-acetylhexosamine (HexNAc) ions (Y1 ions) can be readily achieved at <5 ppm mass measurement errors. These data allow base peptide sequences and glycan compositional information to be attained with high confidence, even for glycopeptides that produce weak precursor ion signals and/or low quality MS/MS spectra. The glycopeptides characterized from low fmol abundances using these methods allow two previously unreported glycosylation sites on the Gallus gallus protein ovoglycoprotein (amino acids 82 and 90) to be confirmed; considerable glycan heterogeneities at amino acid 90 of ovoglycoprotein, and amino acids 34 and 77 of Gallus gallus ovomucoid are also revealed.

Hart-Smith, Gene; Raftery, Mark J.

2012-01-01

286

An experimental study of SO3 dissociation as a mechanism for converting and transporting solar energy  

NASA Technical Reports Server (NTRS)

The high temperature catalytic dissocation of SO3 is an important chemical process being considered in the development and application of solar-thermal energy conversion, transport, and storage systems. A facility for evaluating chemical converter-heat exchangers at temperatures to 1000 C with high flow rates of gaseous SO3 feedstock has been assembled and operated on the NMSU campus. Several quartz and metal reactors containing different catalyst configurations have been tested. Descriptions of the test facility and of the reactors are given along with a presentation and discussion of experimental results.

Mccrary, J. H.; Mccrary, G. E.; Chubb, T. A.; Won, Y. S.

1981-01-01

287

Dissociative Recombination without a Curve Crossing  

NASA Technical Reports Server (NTRS)

Ab initio calculations show that a curve crossing is not always needed for a high dissociative- recombination cross section. For HeH(+), in which no neutral states cross the ion potential curve, dissociative recombination is driven by the nuclear kinetic-energy operator on adiabatic potential curves. The kinetic-energy derivative operator allows for capture into repulsive curves that are outside of the classical turning points for the nuclear motion. The dominant dissociative route is the C (2)Sigma(+) state leading to H(n = 2) atoms. An analogous mechanism is proposed for the dissociative recombination of H3(+).

Guberman, Steven L.

1994-01-01

288

The effects of collision energy, vibrational mode, and vibrational angular momentum on energy transfer and dissociation in NO2  

E-print Network

The effects of collision energy, vibrational mode, and vibrational angular momentum on energy effects of NO2 + vibrational excitation that extend over the entire collision energy range, implying dynamics trajectories for NO2 + +Kr reproduce both the collision energy and vibrational state effects

Anderson, Scott L.

289

Electronic structure, stacking energy, partial charge, and hydrogen bonding in four periodic B-DNA models  

NASA Astrophysics Data System (ADS)

We present a theoretical study of the electronic structure of four periodic B-DNA models labeled (AT)10,(GC)10, (AT)5(GC)5, and (AT-GC)5 where A denotes adenine, T denotes thymine, G denotes guanine, and C denotes cytosine. Each model has ten base pairs with Na counterions to neutralize the negative phosphate group in the backbone. The (AT)5(GC)5 and (AT-GC)5 models contain two and five AT-GC bilayers, respectively. When compared against the average of the two pure models, we estimate the AT-GC bilayer interaction energy to be 19.015 Kcal/mol, which is comparable to the hydrogen bonding energy between base pairs obtained from the literature. Our investigation shows that the stacking of base pairs plays a vital role in the electronic structure, relative stability, bonding, and distribution of partial charges in the DNA models. All four models show a highest occupied molecular orbital (HOMO) to lowest unoccupied molecular orbital (LUMO) gap ranging from 2.14 to 3.12 eV with HOMO states residing on the PO4 + Na functional group and LUMO states originating from the bases. Our calculation implies that the electrical conductance of a DNA molecule should increase with increased base-pair mixing. Interatomic bonding effects in these models are investigated in detail by analyzing the distributions of the calculated bond order values for every pair of atoms in the four models including hydrogen bonding. The counterions significantly affect the gap width, the conductivity, and the distribution of partial charge on the DNA backbone. We also evaluate quantitatively the surface partial charge density on each functional group of the DNA models.

Poudel, Lokendra; Rulis, Paul; Liang, Lei; Ching, W. Y.

2014-08-01

290

Students' reasoning about "high-energy bonds" and ATP: A vision of interdisciplinary education  

NASA Astrophysics Data System (ADS)

As interdisciplinary courses are developed, instructors and researchers have to grapple with questions of how students should make connections across disciplines. We explore the issue of interdisciplinary reconciliation (IDR): how students reconcile seemingly contradictory ideas from different disciplines. While IDR has elements in common with other frameworks for the reconciliation of ideas across contexts, it differs in that each disciplinary idea is considered canonically correct within its own discipline. The setting for the research is an introductory physics course for biology majors that seeks to build greater interdisciplinary coherence and therefore includes biologically relevant topics such as adenosine triphosphate (ATP) and chemical bond energy. In our case-study data, students grapple with the apparent contradiction between the energy released when the phosphate bond in ATP is broken and the idea that an energy input is required to break a bond. We see students justifying context-dependent modeling choices, showing nuance in articulating how system choices may be related to disciplinary problems of interest. This represents a desired end point of IDR, in which students can build coherent connections between concepts from different disciplines while understanding each concept in its own disciplinary context. Our case study also illustrates elements of the instructional environment that play roles in the process of IDR.

Dreyfus, Benjamin W.; Sawtelle, Vashti; Turpen, Chandra; Gouvea, Julia; Redish, Edward F.

2014-06-01

291

Low and high-energy collision-induced dissociation of pyridinoline and deoxypyridinoline ions using Fourier transform ion cyclotron resonance electrospray and liquid secondary-ion magnetic sector mass spectrometry  

Microsoft Academic Search

The trifunctional collagen cross-link molecules pyridinoline and deoxypyridinoline have been structurally characterised by (1) low-energy collision-induced dissociation (CID) (ECOM [approximate] 15 eV) using Fourier transform ion cyclotron resonance electrospray ionisation mass spectrometry (FT-ICR-ESI-MS), and (2) high-energy collision-induced dissociation (ECOM [approximate] 400 eV) using liquid secondary-ion mass spectrometry (LSIMS) on a four-sector mass spectrometer. Both ESI and LSIMS ionisation readily produce

Tracey L. Rafferty; Richard T. Gallagher; Peter J. Derrick; Albert J. R. Heck; A. Duncan; Simon P. Robins

1997-01-01

292

Low and high-energy collision-induced dissociation of pyridinoline and deoxypyridinoline ions using Fourier transform ion cyclotron resonance electrospray and liquid secondary-ion magnetic sector mass spectrometry  

Microsoft Academic Search

The trifunctional collagen cross-link molecules pyridinoline and deoxypyridinoline have been structurally characterised by (1) low-energy collision-induced dissociation (CID) (ECOM ? 15 eV) using Fourier transform ion cyclotron resonance electrospray ionisation mass spectrometry (FT-ICR-ESI-MS), and (2) high-energy collision-induced dissociation (ECOM ? 400 eV) using liquid secondary-ion mass spectrometry (LSIMS) on a four-sector mass spectrometer. Both ESI and LSIMS ionisation readily produce

Tracey L. Rafferty; Richard T. Gallagher; Peter J. Derrick; Albert J. R. Heck; A. Duncan; Simon P. Robins

1997-01-01

293

Influence of Buried Hydrogen-Bonding Groups within Monolayer Films on Gas-Surface Energy Exchange and Accommodation  

NASA Astrophysics Data System (ADS)

Self-assembled monolayers (SAMs) of carbonyl-containing alkanethiols on gold are employed to explore the influence of hydrogen-bonding interactions on gas-surface energy exchange and accommodation. H-bonding, COOH-terminated SAMs are found to produce more impulsive scattering and less thermal accommodation than non-H-bonding, COOCH3-terminated monolayers. For carbamate-functionalized SAMs of the form Au/S(CH2)16OCONH(CH2)n-1CH3, impulsive scattering decreases and accommodation increases as the H-bonding group is positioned farther below the terminal CH3.

Ferguson, M. K.; Lohr, J. R.; Day, B. S.; Morris, J. R.

2004-02-01

294

Energy of dissociation of lipid bilayer from the membrane skeleton of red blood cells.  

PubMed Central

The association between the lipid bilayer and the membrane skeleton is important to cell function. In red blood cells, defects in this association can lead to various forms of hemolytic anemia. Although proteins involved in this association have been well characterized biochemically, the physical strength of this association is only beginning to be studied. Formation of a small cylindrical strand of membrane material (tether) from the membrane involves separation of the lipid bilayer from the membrane skeleton. By measuring the force required to form a tether, and knowing the contribution to the force due to the deformation of a lipid bilayer, it is possible to calculate the additional contribution to the work of tether formation due to the separation of membrane skeleton from the lipid bilayer. In the present study, we measured the tethering force during tether formation using a microcantilever (a thin, flexible glass fiber) as a force transducer. Numerical calculations of the red cell contour were performed to examine how the shape of the contour affects the calculation of tether radius, and subsequently separation work per unit area W(sk) and bending stiffness k(c). At high aspiration pressure and small external force, the red cell contour can be accurately modeled as a sphere, but at low aspiration pressure and large external force, the contour deviates from a sphere and may affect the calculation. Based on an energy balance and numerical calculations of the cell contour, values of the membrane bending stiffness k(c) = 2.0 x 10(-19) Nm and the separation work per unit area W(sk) = 0.06 mJ/m2 were obtained. Images FIGURE 1 FIGURE 2 FIGURE 3 FIGURE 8 PMID:9168042

Hwang, W C; Waugh, R E

1997-01-01

295

Dissociation of {sup 10}C nuclei in a track nuclear emulsion at an energy of 1.2 GeV per nucleon  

SciTech Connect

The charge topology in the fragmentation of {sup 10}C nuclei in a track nuclear emulsion at an energy of 1.2 GeV per nucleon is studied. In the coherent dissociation of {sup 10}C nuclei, about 82% of events are associated with the channel {sup 10}C {yields} 2{alpha}+ 2p. The angular distributions and correlations of product fragments are presented for this channel. It is found that among {sup 10}C {yields} 2{alpha}+ 2p events, about 30% are associated with the process in which dissociation through the ground state of the unstable {sup 9}Be{sub g.s.} nucleus is followed by {sup 8}Be{sub g.s.} + p decays.

Mamatkulov, K. Z.; Kattabekov, R. R. [Joint Institute for Nuclear Research (Russian Federation)] [Joint Institute for Nuclear Research (Russian Federation); Alikulov, S. S. [A. Kodirii Jizzakh State Pedagogical Institute (Uzbekistan)] [A. Kodirii Jizzakh State Pedagogical Institute (Uzbekistan); Artemenkov, D. A. [Joint Institute for Nuclear Research (Russian Federation)] [Joint Institute for Nuclear Research (Russian Federation); Bekmirzaev, R. N. [A. Kodirii Jizzakh State Pedagogical Institute (Uzbekistan)] [A. Kodirii Jizzakh State Pedagogical Institute (Uzbekistan); Bradnova, V.; Zarubin, P. I., E-mail: zarubin@lhe.jinr.ru; Zarubina, I. G.; Kondratieva, N. V.; Kornegrutsa, N. K.; Krivenkov, D. O.; Malakhov, A. I. [Joint Institute for Nuclear Research (Russian Federation)] [Joint Institute for Nuclear Research (Russian Federation); Olimov, K. [Uzbek Academy of Sciences, Institute for Physics and Technology (Uzbekistan)] [Uzbek Academy of Sciences, Institute for Physics and Technology (Uzbekistan); Peresadko, N. G.; Polukhina, N. G. [Russian Academy of Sciences, Lebedev Physical Institute (Russian Federation)] [Russian Academy of Sciences, Lebedev Physical Institute (Russian Federation); Rukoyatkin, P. A.; Rusakova, V. V.; Stanoeva, R. [Joint Institute for Nuclear Research (Russian Federation)] [Joint Institute for Nuclear Research (Russian Federation); Kharlamov, S. P. [Russian Academy of Sciences, Lebedev Physical Institute (Russian Federation)] [Russian Academy of Sciences, Lebedev Physical Institute (Russian Federation)

2013-10-15

296

Computational study of the dissociation of oxalic acid in water clusters  

NASA Astrophysics Data System (ADS)

The ionic dissociation of the oxalic acid in water was examined by performing a theoretical study of the different properties of clusters formed by the acid with up to five water molecules. Geometry optimization and frequency calculations were done at density functional theory level with the B3LYP functional using the 6-31+G* basis set. The influence of water in the acid dissociation was characterized by analyzing several cluster properties including energies, stretching frequencies and lengths of the O-H bonds involved in the hydrogen bond lattice. The relative stability of the different conformers for the oxalic acid is altered by the formation of clusters with water. Thus, the most stable conformation of oxalic acid becomes the second most stable for clusters with two water molecules; moreover, this conformer loses stability in relation to other configurations as the size of the cluster increases. The addition of water molecules to the cluster lengthens the O-H bond involved in the hydrogen bonds and simultaneously decreases the O⋯H intermolecular distances. This process results in the formation of ion-pairs for a cluster with five water molecules. The O-H bond stretching frequency undergoes a marked redshift as a consequence of the weakening of the O-H bond. However, the drop in the size of the frequency is gradual and no abrupt gap appears.

Hermida-Ramón, Jose M.; Cabaleiro-Lago, Enrique M.; Rodríguez-Otero, Jesús

2004-07-01

297

Free energy decomposition analysis of bonding and nonbonding interactions in solution  

NASA Astrophysics Data System (ADS)

A free energy decomposition analysis algorithm for bonding and nonbonding interactions in various solvated environments, named energy decomposition analysis-polarizable continuum model (EDA-PCM), is implemented based on the localized molecular orbital-energy decomposition analysis (LMO-EDA) method, which is recently developed for interaction analysis in gas phase [P. F. Su and H. Li, J. Chem. Phys. 130, 074109 (2009)], 10.1063/1.3077917. For single determinant wave functions, the EDA-PCM method divides the interaction energy into electrostatic, exchange, repulsion, polarization, desolvation, and dispersion terms. In the EDA-PCM scheme, the homogeneous solvated environment can be treated by the integral equation formulation of PCM (IEFPCM) or conductor-like polarizable continuum model (CPCM) method, while the heterogeneous solvated environment is handled by the Het-CPCM method. The EDA-PCM is able to obtain physically meaningful interaction analysis in different dielectric environments along the whole potential energy surfaces. Test calculations by MP2 and DFT functionals with homogeneous and heterogeneous solvation, involving hydrogen bonding, vdW interaction, metal-ligand binding, cation-?, and ionic interaction, show the robustness and adaptability of the EDA-PCM method. The computational results stress the importance of solvation effects to the intermolecular interactions in solvated environments.

Su, Peifeng; Liu, Hui; Wu, Wei

2012-07-01

298

Intermolecular hydrogen bond energies in crystals evaluated using electron density properties: DFT computations with periodic boundary conditions.  

PubMed

The hydrogen bond (H-bond) energies are evaluated for 18 molecular crystals with 28 moderate and strong O-H···O bonds using the approaches based on the electron density properties, which are derived from the B3LYP/6-311G** calculations with periodic boundary conditions. The approaches considered explore linear relationships between the local electronic kinetic G(b) and potential V(b) densities at the H···O bond critical point and the H-bond energy E(HB). Comparison of the computed E(HB) values with the experimental data and enthalpies evaluated using the empirical correlation of spectral and thermodynamic parameters (Iogansen, Spectrochim. Acta Part A 1999, 55, 1585) enables to estimate the accuracy and applicability limits of the approaches used. The V(b)-E(HB) approach overestimates the energy of moderate H-bonds (E(HB) < 60 kJ/mol) by ~20% and gives unreliably high energies for crystals with strong H-bonds. On the other hand, the G(b)-E(HB) approach affords reliable results for the crystals under consideration. The linear relationship between G(b) and E(HB) is basis set superposition error (BSSE) free and allows to estimate the H-bond energy without computing it by means of the supramolecular approach. Therefore, for the evaluation of H-bond energies in molecular crystals, the G(b) value can be recommended to be obtained from both density functional theory (DFT) computations with periodic boundary conditions and precise X-ray diffraction experiments. PMID:22786749

Vener, M V; Egorova, A N; Churakov, A V; Tsirelson, V G

2012-11-01

299

High-energy collision-activated and electron-transfer dissociation of gas-phase complexes of tryptophan with Na+, K+, and Ca2+  

NASA Astrophysics Data System (ADS)

The structure and reactivity of gas-phase complexes of tryptophan (Trp) with Na+, K+, and Ca2+ were examined by high-energy collision-activated dissociation (CAD) and electron transfer dissociation (ETD) using alkali metal targets. In the CAD spectra of M+Trp (M = Na and K), neutral Trp loss was the primary dissociation pathway, and the product ion of collision-induced intracomplex electron transfer from the indole ? ring of Trp to the alkali metal ion was observed, indicating a charge-solvated structure in which Trp is non-zwitterionic. The NH3 loss observed in the CAD spectrum of Ca2+Trp2 is ascribed to a CZ (mixed charge-solvated/zwitterionic)-type structure, in which one Trp is non-zwitterionic and the other Trp adopts a zwitterionic structure with an NH3+ moiety. The H atom and NH3 losses observed in the ETD spectrum of Ca2+Trp2 indicate the formation of a hypervalent radical in the complex, R-NH3, via electron transfer from the alkali metal target to the NH3+ group of the CZ-type structure. Ca2+ attachment to Trp cluster induces the zwitterionic structure of Trp in the gas phase, and an electron transfer to the zwitterionic Trp forms the hypervalent radical as a reaction intermediate.

Fujihara, Akimasa; Sha, Yuki; Matsuo, Sou; Toyoda, Michisato; Hayakawa, Shigeo

2014-10-01

300

Dissociation and dissociative ionization of H2+ using the time-dependent surface flux method  

E-print Network

The time-dependent surface flux method developed for the description of electronic spectra [L. Tao and A. Scrinzi, New J. Phys. 14, 013021 (2012); A. Scrinzi, New J. Phys. 14, 085008 (2012)] is extended to treat dissociation and dissociative ionization processes of H2+ interacting with strong laser pulses. By dividing the simulation volume into proper spatial regions associated with the individual reaction channels and monitoring the probability flux, the joint energy spectrum for the dissociative ionization process and the energy spectrum for dissociation is obtained. The methodology is illustrated by solving the time-dependent Schr\\"{o}dinger equation (TDSE) for a collinear one-dimensional model of H2+ with electronic and nuclear motions treated exactly and validated by comparison with published results for dissociative ionization. The results for dissociation are qualitatively explained by analysis based on dressed diabatic Floquet potential energy curves, and the method is used to investigate the breakdow...

Yue, Lun

2014-01-01

301

Bond Orientational Order, Molecular Motion, and Free Energy of High-Density DNA Mesophases  

NASA Astrophysics Data System (ADS)

By equilibrating condensed DNA arrays against reservoirs of known osmotic stress and examining them with several structural probes, it has been possible to achieve a detailed thermodynamic and structural characterization of the change between two distinct regions on the liquid-crystalline phase diagram: (i) a higher density hexagonally packed region with long-range bond orientational order in the plane perpendicular to the average molecular direction and (ii) a lower density cholesteric region with fluid-like positional order. X-ray scattering on highly ordered DNA arrays at high density and with the helical axis oriented parallel to the incoming beam showed a sixfold azimuthal modulation of the first-order diffraction peak that reflects the macroscopic bond-orientational order. Transition to the less-dense cholesteric phase through osmotically controlled swelling shows the loss of this bond orientational order, which had been expected from the change in optical birefringence patterns and which is consistent with a rapid onset of molecular positional disorder. This change in order was previously inferred from intermolecular force measurements and is now confirmed by 31P NMR. Controlled reversible swelling and compaction under osmotic stress, spanning a range of densities between ? 120 mg/ml to ? 600 mg/ml, allow measurement of the free-energy changes throughout each phase and at the phase transition, essential information for theories of liquid-crystalline states.

Podgornik, R.; Strey, H. H.; Gawrisch, K.; Rau, D. C.; Rupprecht, A.; Parsegian, V. A.

1996-04-01

302

Comparison of DFT with Traditional Methods for the Calculation of Vibrational Frequencies and Bond Energies  

NASA Technical Reports Server (NTRS)

The vibrational frequencies of MO2 are computed at many levels of theory, including HF, B3LYP, BP86, CASSCF, MP2, and CCSD(T). The computed results are compared with the available experimental results. Most of the methods fail for at least one state of the systems considered. The accuracy of the results and the origin of the observed failures are discussed. The B3LYP bond energies are compared with traditional methods for a variety of systems, ranging from FeCOn+ to SiCln and its positive ions. The cases where B3LYP differs from the traditional methods are discussed.

Bauschlicher, Charles W.; Arnold, James O. (Technical Monitor)

1997-01-01

303

Electronic structure, charge transfer and bonding in intermetallics using EELS and density functional theory[Electron Energy Loss Spectroscopy  

SciTech Connect

Electron energy loss spectroscopy and density functional theory have been used to show that there is a covalent component to the bonding in NiAl, CoAl and FeAl, between the transition metal atom and Al. There is no charge transfer and no ionic component to the bonding in NiAl and probably not in CoAl and FeAl. The bonding is non-stoichiometric NiAl is studied. Preliminary results are given for a {Sigma}{sub 3} boundary in NiAl.

Humphreys, C.J.; Botton, G.A.; Pankhurst, D.A.; Keast, V.J.; Temmerman, W.M.

1999-07-01

304

Binding Energies of the Proton-Bound Amino Acid Dimers Gly·Gly, Ala·Ala, Gly·Ala, and Lys·Lys Measured by Blackbody Infrared Radiative Dissociation  

PubMed Central

Arrhenius activation energies in the zero-pressure limit for dissociation of gas-phase proton-bound homodimers of N,N-dimethylacetamide (N,N-DMA), glycine, alanine, and lysine and the heterodimer alanine·glycine were measured using blackbody infrared radiative dissociation (BIRD). In combination with master equation modeling of the kinetic data, binding energies of these dimers were determined. A value of 1.25 ± 0.05 eV is obtained for N,N-DMA and is in excellent agreement with that reported in the literature. The value obtained from the truncated Boltzmann model is significantly higher, indicating that the assumptions of this model do not apply to these ions. This is due to the competitive rates of photon emission and dissociation for these relatively large ions. The binding energies of the amino acid dimers are ~1.15 ± 0.05 eV and are indistinguishable despite the difference in their gas-phase basicity and structure. The threshold dissociation energies can be accurately modeled using a range of dissociation parameters and absorption/emission rates. However, the absolute values of the dissociation rates depend more strongly on the absorption/emission rates. For N,N-DMA and glycine, an accurate fit was obtained using frequencies and transition dipole moments calculated at the ab initio RHF/2-31G* and MP2/2-31G* level, respectively. In order to obtain a similar accuracy using values obtained from AM1 semiempirical calculations, it was necessary to multiply the transition dipole moments by a factor of 3. These results demonstrate that in combination with master equation modeling, BIRD can be used to obtain accurate threshold dissociation energies of relatively small ions of biological interest. PMID:17235378

Price, William D.; Schnier, Paul D.

2005-01-01

305

ELECTRON INDUCED DISSOCIATION OF GLYCOSAMINOGLYCAN TETRASACCHARIDES  

PubMed Central

Electron detachment dissociation (EDD) Fourier transform mass spectrometry has recently been shown to be a powerful tool for examining the structural features of sulfated glycosaminoglycans (GAGs). The characteristics of GAG fragmentation by EDD include abundant cross-ring fragmentation primarily on hexuronic acid residues, cleavage of all glycosidic bonds, and the formation of even- and odd-electron product ions. GAG dissociation by EDD has been proposed to occur through the formation of an excited species that can undergo direct decomposition, or eject an electron which then undergoes dissociation. In this work, we perform electron induced dissociation (EID) on singly-charged GAGs to identify products that form via direct decomposition by eliminating the pathway of electron detachment. EID of GAG tetrasaccharides produces cleavage of all glycosidic bonds and abundant cross-ring fragmentation primarily on hexuronic acid residues, producing fragmentation similar to EDD of the same molecules, but distinctly different from the products of infrared multiphoton dissociation or collisionally activated decomposition. These results suggest that observed abundant fragmentation of hexuronic acid residues occurs due to their increased lability when they undergo electronic excitation. EID fragmentation of GAG tetrasaccharides results in both even- and odd-electron products. EID of heparan sulfate tetrasaccharide epimers produces identical fragmentation, in contrast to EDD, in which the epimers can be distinguished by their fragment ions. These data suggest that for EDD, electron detachment play a significant role in distinguishing glucuronic acid from iduronic acid. PMID:18657442

Wolff, Jeremy J.; Laremore, Tatiana N.; Aslam, Hammad; Linhardt, Robert J.; Amster, I. Jonathan

2008-01-01

306

Dissociative Electron Attachment to Hydrocarbons. A Laboratory Study  

NASA Astrophysics Data System (ADS)

Laboratory studies of PAHs continue to be essential if we are to interpret the wealth and variety of processes contributing to star formation. In the realm of gas-phase kinetics reactions involving negative ions are being studied to help modellers understand the role of these species in interstellar chemistry. Observations have shown that PAHs molecules are abundant and ubiquitous in the interstellar medium of galaxies, play an important role in its physical and chemical characteristics and form a key link between small hydrocarbon species and large carbonaceous grains. There is therefore considerable interest in the mechanisms by which these molecules and their anions may form. One method is electron induced chemistry within the icy mantles on the surface of dust grains. In particular it has been recently shown that functional group dependence exists in electron attachment processes giving rise to site selective fragmentation of molecules at the C-H, O-H and N-H bonds at energies well beyond the threshold for the breaking of any of these bonds allowing novel forms of chemistry that have little or no activation barriers, such as are necessary in the ISM. In this poster we present the results of recent studies on dissociative electron attachment (DEA) to PAHs using an improved version of a Velocity Map Imaging (VMI) spectrometer comprised of a magnetically collimated and low energy pulsed electron gun, a Faraday cup, an effusive molecular beam, a pulsed field ion extraction, a time of flight analyzer and a two-dimensional position sensitive detector consisting of microchannel plate and a phosphor screen. The VMI spectrometer measures the kinetic energy and angular distribution of the fragment anions produced in the dissociative electron attachment process. Kinetic energy measurements provide information on the internal energies of the fragment anions and determine the dissociation limits of the parent negative ion resonant states responsible for the dissociative electron attachment process. Angular distribution measurements provide information about the symmetry of these negative ion resonant states. We shall present the details, results and conclusions of these measurements during the conference for some illustrative hydrocarbons.

Szymanska, E.; Mason, N. J.

2011-05-01

307

An alternative energy–size relationship to that proposed by Bond for the design and optimisation of grinding circuits  

Microsoft Academic Search

Despite reservations of a number of researchers concerning the applicability of Bond's equation for relating specific energy to the size reduction of rocks, his approach has become an industry standard.Data from a large number of pilot and full-scale autogenous (AG), semi-autogenous (SAG) and ball mill circuits are used to show that Bond's equation does not hold over the particle size

Stephen Morrell

2004-01-01

308

Evaluating interaction energies of weakly bonded systems using the Buckingham-Hirshfeld method  

SciTech Connect

We present the finalized Buckingham-Hirshfeld method (BHD-DFT) for the evaluation of interaction energies of non-bonded dimers with Density Functional Theory (DFT). In the method, dispersion energies are evaluated from static multipole polarizabilities, obtained on-the-fly from Coupled Perturbed Kohn-Sham calculations and partitioned into diatomic contributions using the iterative Hirshfeld partitioning method. The dispersion energy expression is distributed over four atoms and has therefore a higher delocalized character compared to the standard pairwise expressions. Additionally, full multipolar polarizability tensors are used as opposed to effective polarizabilities, allowing to retain the anisotropic character at no additional computational cost. A density dependent damping function for the BLYP, PBE, BP86, B3LYP, and PBE0 functionals has been implemented, containing two global parameters which were fitted to interaction energies and geometries of a selected number of dimers using a bi-variate RMS fit. The method is benchmarked against the S22 and S66 data sets for equilibrium geometries and the S22x5 and S66x8 data sets for interaction energies around the equilibrium geometry. Best results are achieved using the B3LYP functional with mean average deviation values of 0.30 and 0.24 kcal/mol for the S22 and S66 data sets, respectively. This situates the BHD-DFT method among the best performing dispersion inclusive DFT methods. Effect of counterpoise correction on DFT energies is discussed.

Krishtal, A. [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin Schrödinger Straße 52, D-67663 Kaiserslautern (Germany)] [Fachbereich Chemie, Technische Universität Kaiserslautern, Erwin Schrödinger Straße 52, D-67663 Kaiserslautern (Germany); Van Alsenoy, C. [Department of Chemistry, University of Antwerp, Universiteitsplein 1, B2610 Antwerp (Belgium)] [Department of Chemistry, University of Antwerp, Universiteitsplein 1, B2610 Antwerp (Belgium); Geerlings, P. [Algemene Chemie, Vrije Universiteit Brussel, Pleinlaan 2, B-1050 Brussels (Belgium)] [Algemene Chemie, Vrije Universiteit Brussel, Pleinlaan 2, B-1050 Brussels (Belgium)

2014-05-14

309

Surprising Quenching of the Spin-Orbit Interaction Significantly Diminishes H2O···X [X = F, Cl, Br, I] Dissociation Energies.  

PubMed

The H2O···X complexes, with X = F, Cl, Br, and I, show considerable viability with nonspin-orbit De(D0) dissociation energy values of 3.73(2.42), 3.60(2.68), 3.54(2.72), and 3.36(2.77) kcal mol(-1) for X = F, Cl, Br, and I, respectively, obtained at the CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory using relativistic pseudopotentials (PPs) for Br and I. Spin-orbit (SO) corrections, computed with the Breit-Pauli operator in the interacting states approach at the all-electron MRCI+Q/aug-cc-pwCVTZ(-PP) level, are found to depend sensitively and unpredictably on the O···X separations. 96% (F), 87% (Cl), 54% (Br), and 30% (I) quenching of the SO corrections significantly reduces the dissociation energies of the H2O···X complexes, resulting in De(D0) values of 3.38(2.06), 2.86(1.94), 1.64(0.83), and 1.23(0.64) kcal mol(-1) for X = F, Cl, Br, and I, respectively. PMID:25133702

Czakó, Gábor; Császár, Attila G; Schaefer, Henry F

2014-12-26

310

Effect of excitation energy on dentine bond strength and composite properties.  

PubMed

A number of available dentine adhesives and dental composites require light activation for polymerization. There are many variables which affect the light absorbing properties (e.g. bond strength) of these materials. The purpose of this study was to determine the influence of excitation energy (EE) on the dentine shear bond strength (SBS) of two lengths (2.1 mm and 3.25 mm) of light-cured (or dual-cured) dentine adhesives/dental composites. Diametral tensile (DTS) and compressive (CS) strengths of the same composites were also studied as a function of EE. Three resin composites with their respective adhesives (Marathon One/Tenure, Z100/Scotchbond Multi-Purpose and Herculite XRV/Optibond) were used. Five commercial curing lights were used to produce spectra of 100-650 mW cm-2. The data were analysed using ANOVA and the Tukey LSD test. No significant correlation was observed at the P > 0.05 level between EE and SBS in the shorter specimens. The SBS of Optibond is independent of EE and composite length. The SBS data were also analysed with Weibull statistics. The characteristic strengths calculated varied between 14 and 27 MPa. For the composites tested, mean values of DTS varied between 33 and 54 MPa and CS varied between 167 and 414 MPa. The DTS and CS of Z100 were significantly greater than those of the other materials. Intensities > or = 250 mW cm-2 produced equivalent mechanical properties within all composite materials and equivalent bond strengths in systems which included dentine, adhesive and composite resin. PMID:8027461

Lee, S Y; Greener, E H

1994-06-01

311

Wavepacket theory of collisional dissociation in molecules  

SciTech Connect

An explicit integration scheme is used to solve the time dependent Schroedinger equation for wavepackets which model collisions in the collinear H + H/sub 2/ system. A realistic LEPS-type potential energy surface is used. Collision energies considered are above the dissociation threshold and probabilities for collision induced dissociation are reported. Also quantum mechanical state-to-state transition probabilities are generated. These results are compared to extensive classical trajectory calculations performed on this same system. The time evolution of the wavepacket densities is studied to understand the dynamics of the collinear collisional dissociation process.

Kulander, K.

1980-01-01

312

Monte Carlo configuration interaction with perturbation corrections for dissociation energies of first row diatomic molecules: C{sub 2}, N{sub 2}, O{sub 2}, CO, and NO  

SciTech Connect

Dissociation energies for the diatomic molecules C{sub 2}, N{sub 2}, O{sub 2}, CO, and NO are estimated using the Monte Carlo configuration interaction (MCCI) and augmented by a second order perturbation theory correction. The calculations are performed using the correlation consistent polarized valence “triple zeta” atomic orbital basis and resulting dissociation energies are compared to coupled cluster calculations including up to triple excitations (CCSDT) and Full Configuration Interaction Quantum Monte Carlo (FCIQMC) estimates. It is found that the MCCI method readily describes the correct behavior for dissociation for the diatomics even when capturing only a relatively small fraction (?80%) of the correlation energy. At this level only a small number of configurations, typically O(10{sup 3}) from a FCI space of dimension O(10{sup 14}), are required to describe dissociation. Including the perturbation correction to the MCCI estimates, the difference in dissociation energies with respect to CCSDT ranges between 1.2 and 3.1 kcal/mol, and the difference when comparing to FCIQMC estimates narrows to between 0.5 and 1.9 kcal/mol. Discussions on MCCI's ability to recover static and dynamic correlations and on the form of correlations in the electronic configuration space are presented.

Kelly, Thomas P.; Greer, James C., E-mail: jim.greer@tyndall.ie [Tyndall National Institute, University College Cork, Dyke Parade, Lee Maltings, Cork (Ireland); Perera, Ajith; Bartlett, Rodney J. [Quantum Theory Project, 2234 New Physics Building 92, PO Box 118435, University of Florida at Gainesville, Gainesville, Florida 32611-8435 (United States)] [Quantum Theory Project, 2234 New Physics Building 92, PO Box 118435, University of Florida at Gainesville, Gainesville, Florida 32611-8435 (United States)

2014-02-28

313

Effect of aging on surface chemical bonds of PTFE irradiated by low energy Ti ion  

NASA Astrophysics Data System (ADS)

Polytetrafluoroethylene (PTFE) was irradiated by low energy titanium ion in a metal vapor vacuum arc (MEVVA) implanter. The samples were irradiated with 80 keV Ti ion with fluences from 5×10 15 to 5×10 17 Ti/cm 2, respectively. Transportation of Ion in Matters (TRIM) code was employed to simulate Ti ion irradiation. The as-irradiated samples were investigated by ESCA, SEM and wettability. As increasing ion fluence, various chemical bonds and irradiation-damaged surfaces were observed. The water droplet contact angel of PTFE samples increased gradually with ion fluence. All the as-irradiated PTFE samples were aged in air for 1 year. After aging the surface-restructuring behavior was observed on the surfaces of the samples irradiated with ion fluence equal to or less than 5×10 16 Ti/cm 2, which resulted in decrease of the droplet contact angle of these samples. The surface roughness change of the aged samples, which were measured by atomic force microscopy (AFM), was consistent with the droplet contact angle change. The experimental results revealed that Ti ion fluence closely affected the surface chemical bond, morphology and wettability, as well as the aging stability of the as-irradiated PTFE samples.

Zhang, Jizhong; Zhang, Xiaoji; Zhou, Hongyu

2003-01-01

314

Combining ab initio quantum mechanics with a dipole-field model to describe acid dissociation reactions in water: first-principles free energy and entropy calculations.  

PubMed

We introduce a novel approach to compute dissociation free energy and entropy values in simulations that employ a density functional theory description of the acidic moiety and of the solvent. The approach consists of utilizing an alchemical transformation of a weak acid A-COOH into the strong acid B-COOH, which makes it practical to employ alchemical free energy perturbation methods in the context of ab initio molecular dynamics simulations. The present alchemical transformation circumvents the need to tackle changes in the total number of electrons and atoms by replacing the chemical residue responsible for the change in acidity with an easily tunable external effective potential. Our investigation demonstrates that (1) a simple but effective class of external potentials that control acidity changes in the acetic/trifluoroacetic acid series can be achieved by replacing the methyl and trifluoromethyl substituents by screened dipoles. Using this dipole-field/quantum-mechanics (DF/QM) approach one can predict gas-phase geometries, proton dissociation energies, total dipole moments, and water binding energies in good agreement with full-QM values. (2) The resulting alchemical perturbation calculations are stable and well converged and allow one to compute absolute pK(a) values whose accuracy is limited primarily by the exchange-correlation functional employed: H-COOH=2.5+/-0.6 (full-QM calculation), 3.7 (exp); F(3)C-COOH=0.4+/-0.6 (DF/QM calculation), 0.5 (exp); H(3)C-COOH=3.1+/-0.7 (DF/QM calculation), 4.7 (exp); 3) Our DF/QM model predicts that the difference in acidity between H-COOH and H(3)C-COOH is dominated by solvent entropy effects, in excellent agreement with experimental observations. The calculated difference between the dissociation energies of these acids is DeltaDelta(d)U=0.0+/-0.26 kcal/mol while the experimental value is 0.0+/-0.1 kcal/mol. PMID:20170220

Maurer, Patrick; Iftimie, Radu

2010-02-21

315

Dissociation of dicarboxylate and disulfonate dianions  

NASA Astrophysics Data System (ADS)

Collision-induced dissociation (CID), along with infrared multiple photon dissociation/detachment (IRMPD) techniques, is utilized to study a series of doubly substituted aromatic dianions containing sulfonate and carboxylate functionalities (1,2- and 1,3-benzenedisulfonate, 1,5-naphthalenedisulfonate, 2,6-naphthalenedisulfonate, 4-sulfobenzoate, 2,6-naphthalenedicarboxylate, and terephthalate dianions). The molecules were chosen because of the electronegativity of the CO2 and SO3 moieties along with their varied spatial separation in order to investigate the effect of the repulsive Coulomb barrier (RCB) on the dianions' respective dissociation pathways. Density functional theory calculations of the structures, electron detachment and dissociation energies, as well as vibrational frequencies are performed. Calculated infrared active vibrational frequencies are largely in agreement with the IRMPD spectra which provide support for interpretations based upon computed energies. Calculated and experimental results show that fragmentation dominates over electron detachment as the lowest energy dissociation pathway for these systems and the nature of this dissociation is dictated by properties of the substituent group. CID and IRMPD of dianions with two sulfonate groups (SO3-) resulted in a single dissociation channel leading to observation of SO3- and its anion conjugate pair, whereas the carboxylate (CO2-) containing dianions dissociated via loss of one or both CO2 molecules and an electron. The SO3- collisional dissociation exhibited a clear energetic threshold toward ionic fragmentation with an isomeric dependence that is in reasonable agreement with a simple electrostatic model of the RCB, as well as with published reports on electron photodetachment. The loss of one or both CO2 units and an electron from CID of the carboxylate dianions appeared with no threshold (dissociation occurs with no collision gas), implying these dianions to be metastable toward the dissociation pathway. However, calculations show these ions to be energetically stable toward dissociation as well as electron detachment. More importantly, in the case of the 2,6-naphthalenedicarboxylate dianion, experiments performed at the FELIX Fourier-transform ion cyclotron resonance facility and the ELISA electrostatic storage ring, where ions are collisionally cooled prior to analysis, showed this ion to be stable (? >1.5 s). We conclude that the carboxylate (CO2-) containing dianions formed in the present CID experiment are electronically stable but vibrationally metastable due to internal energy imparted in the harsh electrospray conditions. The delocalized nature of the excess electrons associated with the carboxylate containing dianions may lead to circumvention of the RCB by dissociating via neutral fragmentation followed by (or accompanied by) electron detachment.

Ard, Shaun; Mirsaleh-Kohan, Nasrin; Steill, Jeffrey D.; Oomens, Jos; Nielsen, Steen Brøndsted; Compton, R. N.

2010-03-01

316

Excited Carriers Relaxation and Hydrogen Dissociation on Hydrogenated Graphene: A Theory  

NASA Astrophysics Data System (ADS)

Using ab initio molecular dynamics coupled with time-dependent density functional theory (TDDFT), we show that the energy transfer of photo-excited carriers into atomic kinetic energy on hydrogenated graphene depends sensitively on the surface H coverage. Here, the energy transfer rate plays a crucial role in the determination of the H dissociation dynamics from graphene. In the low density ``isolated'' hydrogen atom limit, the energy transfer is significantly suppressed 80 fs after the excitation. Thus, it is difficult to dissociate hydrogen due to the faster energy dissipation from H into carbon backbone, despite that initially the H kinetic energy had increased to around 1.5 eV and the C-H bondlength had starched to 2.4 å. In sharp contrast, at the high-density graphane limit, an efficient energy transfer channel is established when the C-H bondlength exceeds 1.4 å. A fraction of the H readily dissociates within 15 fs. This is because ionized H forms a charged layer that expels, and as such accelerates the H ions with higher initial thermal velocities flying away. Our study thus reveals the importance of performing TDDFT calculations for excited carrier dynamics as from the widely adopted ground-state or constrained DFT dynamics one would expect the C-H bonds in graphane to be significantly stronger, due to full surface passivation, than that of isolated H.

Bang, Junhyeok; Sun, Y. Y.; West, D.; Zhang, S. B.; Meng, S.; Wang, Z. G.; Gao, F.

2012-02-01

317

A simple non-empirical procedure for spin-component-scaled MP2 methods applied to the calculation of the dissociation energy curve of noncovalently-interacting systems.  

PubMed

We present a simple and non-empirical method to determine optimal scaling coefficients, within the (spin-component)-scaled MP2 approach, for calculating intermolecular potential energies of noncovalently-interacting systems. The method is based on an observed proportionality between (spin-component) MP2 and CCSD(T) energies for a wide range of intermolecular distances and allows us to compute with high accuracy a large portion of the dissociation curve at the cost of a single CCSD(T) calculation. The accuracy of the present procedure is assessed for a series of noncovalently-interacting test systems: the obtained results reproduce CCSD(T) quality in all cases and definitely outperform conventional MP2, CCSD and SCS-MP2 results. The difficult case of the beryllium dimer is also considered. PMID:23942763

Grabowski, Ireneusz; Fabiano, Eduardo; Della Sala, Fabio

2013-10-01

318

[Dissociative symptoms and sleep].  

PubMed

There is a widespread view among psychiatrists that dissociative experiences such as depersonalisation, derealisation, absorption, and psychogenic amnesia have a traumatic etiology. This view is subjected to a critical evaluation. We also discuss an alternative interpretation namely that dissociative experiences are caused by a labile sleep-wake rhythm. We evaluated this alternative view in two exploratory studies. In study 1 we looked at the relationship between the Dissociative Experience Scale (DES) and the Iowa Sleep Experiences Survey (ISES) and in study 2, we checked this relationship when the response bias was controlled for. Dissociative experiences (measured with the DES) correlated with the ISES. The correlation between DES and ISES remained completely intact even when we controlledfor response bias. Our findings show that dissociative symptoms are associated with typical sleep experiences such as nightmares and strange dreams. The association is not the by-product of the positive response bias which generally characterises persons with dissociative symptoms. PMID:16956084

Giesbrecht, T; Merckelbach, H

2006-01-01

319

Dissociation and Dissociative Identity Disorder: Treatment Guidelines and Cautions  

Microsoft Academic Search

?? ? Interest in dissociation and dissociative disorders has waxed and waned from the time of Janet’s (1889) landmark writings to contemporary attempts to understand dissociative phenomena in light of competing explanatory models and increasingly sophisticated experimental methods. From the eclipse of dissociation theory by early psychoanalytic theory, to the attack on dissociation by experimentalists later in the century (Rosenberg,

Steven Jay Lynn; Oliver Fassler; Joshua A. Knox; Scott O. Lilienfeld

320

Density function theory study of the adsorption and dissociation of carbon monoxide on tungsten nanoparticles.  

PubMed

The adsorption and dissociation properties of carbon monoxide (CO) molecule on tungsten W(n) (n = 10-15) nanoparticles have been investigated by density-functional theory (DFT) calculations. The lowest-energy structures for W(n) (n = 10-15) nanoparticles are found by the basin-hopping method and big-bang method with the modified tight-binding many-body potential. We calculated the corresponding adsorption energies, C-O bond lengths and dissociation barriers for adsorption of CO on nanoparticles. The electronic properties of CO on nanoparticles are studied by the analysis of density of state and charge density. The characteristic of CO on W(n) nanoparticles are also compared with that of W bulk. PMID:23646573

Weng, Meng-Hsiung; Ju, Shin-Pon; Chen, Hsin-Tsung; Chen, Hui-Lung; Lu, Jian-Ming; Lin, Ken-Huang; Lin, Jenn-Sen; Hsieh, Jin-Yuan; Yang, Hsi-Wen

2013-02-01

321

Support effects on the dissociation of hydrogen over gold clusters on ZnO(101) surface: Theoretical insights  

NASA Astrophysics Data System (ADS)

We perform density functional studies of the support effects on the gold-catalyzed dissociation of H2 using the model clusters (Au10 and Au13) on ZnO(101) surface and find that H2 prefers to adsorb on the bottom layer of Au clusters on the ZnO surface. The interaction energies of H2 are exponentially correlated with the H-H and H-Au bond parameters. The dissociation of H2 easily occurs on the bottom layer with the energy barriers no more than 0.44 eV. The support effects on the dissociation barriers are greatly dependent on the H-H bond distance in the transition state (TS), i.e., the early TSs with small barriers have larger support effects than the late TSs with large barriers. We find that the charge transfer from the gold clusters to the oxide support creates the localized charging states of the interface gold with the high feasibility for H2 activation and dissociation.

Li, Zhe; Li, Yongxiu; Li, Jinlin

2012-12-01

322

Internal Energy Dependence of the H + Allene/H + Propyne Product Branching from the Unimolecular Dissociation of 2-Propenyl Radicals  

E-print Network

-H bond fission product channels via tunable vacuum-UV photoionization of the products. Dispersing the neutral products by arrival time at the detector allows us to measure the branching between isomeric photoionization as a function of their neutral flight time, allowing us to measure the change in product branching

Butler, Laurie J.

323

Influence of Light Intensity on Surface Free Energy and Dentin Bond Strength of Core Build-up Resins.  

PubMed

SUMMARY Objective : We examined the influence of light intensity on surface free energy characteristics and dentin bond strength of dual-cure direct core build-up resin systems. Methods : Two commercially available dual-cure direct core build-up resin systems, Clearfil DC Core Automix with Clearfil Bond SE One and UniFil Core EM with Self-Etching Bond, were studied. Bovine mandibular incisors were mounted in acrylic resin and the facial dentin surfaces were wet ground on 600-grit silicon carbide paper. Adhesives were applied to dentin surfaces and cured with light intensities of 0 (no irradiation), 200, 400, and 600 mW/cm(2). The surface free energy of the adhesives (five samples per group) was determined by measuring the contact angles of three test liquids placed on the cured adhesives. To determine the strength of the dentin bond, the core build-up resin pastes were condensed into the mold on the adhesive-treated dentin surfaces according to the methods described for the surface free energy measurement. The resin pastes were cured with the same light intensities as those used for the adhesives. Ten specimens per group were stored in water maintained at 37°C for 24 hours, after which they were shear tested at a crosshead speed of 1.0 mm/minute in a universal testing machine. Two-way analysis of variance (ANOVA) and a Tukey-Kramer test were performed, with the significance level set at 0.05. Results : The surface free energies of the adhesive-treated dentin surfaces decreased with an increase in the light intensity of the curing unit. Two-way ANOVA revealed that the type of core build-up system and the light intensity significantly influence the bond strength, although there was no significant interaction between the two factors. The highest bond strengths were achieved when the resin pastes were cured with the strongest light intensity for all the core build-up systems. When polymerized with a light intensity of 200 mW/cm(2) or less, significantly lower bond strengths were observed. Conclusions : The data suggest that the dentin bond strength of core build-up systems are still affected by the light intensity of the curing unit, which is based on the surface free energy of the adhesives. On the basis of the results and limitations of the test conditions used in this study, it appears that a light intensity of >400 mW/cm(2) may be required for achieving the optimal dentin bond strength. PMID:24809538

Shimizu, Y; Tsujimoto, A; Furuichi, T; Suzuki, T; Tsubota, K; Miyazaki, M; Platt, Ja

2015-01-01

324

Tripartite efflux pumps: energy is required for dissociation, but not assembly or opening of the outer membrane channel of the pump  

PubMed Central

The MtrCDE multidrug pump, from Neisseria gonorrhoeae, is assembled from the inner and outer membrane proteins MtrD and MtrE, which are connected by the periplasmic membrane fusion protein MtrC. Although it is clear that MtrD delivers drugs to the channel of MtrE, it remains unclear how drug delivery and channel opening are connected. We used a vancomycin sensitivity assay to test for opening of the MtrE channel. Cells expressing MtrE or MtrE-E434K were insensitive to vancomycin; but became moderately and highly sensitive to vancomycin respectively, when coexpressed with MtrC, suggesting that the MtrE channel opening requires MtrC binding and is energy-independent. Cells expressing wild-type MtrD, in an MtrCE background, were vancomycin-insensitive, but moderately sensitive in an MtrCE-E434K background. The mutation of residues involved in proton translocation inactivated MtrD and abolished drug efflux, rendered both MtrE and MtrE-E434K vancomycin-insensitive; imply that the pump–component interactions are preserved, and that the complex is stable in the absence of proton flux, thus sealing the open end of MtrE. Following the energy-dependent dissociation of the tripartite complex, the MtrE channel is able to reseal, while MtrE-E434K is unable to do so, resulting in the vancomycin-sensitive phenotype. Thus, our findings suggest that opening of the OMP via interaction with the MFP is energy-independent, while both drug export and complex dissociation require active proton flux. PMID:23565750

Janganan, Thamarai K; Bavro, Vassiliy N; Zhang, Li; Borges-Walmsley, Maria Inês; Walmsley, Adrian R

2013-01-01

325

The catalytic adsorption and dissociation of carbon dioxide on a double icosahedral Ru19 nanocluster - A theoretical study  

NASA Astrophysics Data System (ADS)

Using density-functional theory, we investigated the adsorption and dissociation of CO2 on Ru19 clusters of nm size. According to our results, the CO2 molecule adsorbed on the rhombus-center region of a double icosahedral Ru19 nanocluster has the largest adsorption energy, -1.48 eV, and the greatest elongation of C-O bond. Dissociating the first C-O bond of a CO2 molecule we got a reaction barrier of 0.78 eV, smaller than that of adsorbed on otherwise octahedral and low-symmetry Ru19 cluster structures. To understand the electronic properties, we calculated the electron localization functions and local densities of states, and the result was explicable.

Li, Han-Jung; Yeh, Chen-Hao; Ho, Jia-Jen

2013-10-01

326

Products of Dissociative Recombination in the Ionosphere  

NASA Technical Reports Server (NTRS)

SRI International undertook a novel experimental measurement of the product states formed by dissociative ro-combination (DR) of C2(+), NO(+), and N2(+) as a function of both electron energy and reactant ion vibrational level. For these measurements we used a recently developed experimental technique for measuring dissociation product distributions that allows both the branching ratios to be accurately determined and the electronic and ro-vibrational state composition of the reactant ions to be specified. DR is the dominant electron loss mechanism in all regions of the ionosphere. In this process, electron attachment to the molecular ion produces an unstable neutral molecule that rapidly dissociates.

Cosby, Philip

1996-01-01

327

Dissociative electron attachment to DNA.  

PubMed

Electron-stimulated desorption of anions from thin films of linear and supercoiled DNA is investigated in the range 3-20 eV. Resonant structures are observed with maxima at 9.4+/-0.3, 9.2+/-0.3, and 9.2+/-0.3 eV, respectively, in the yield dependence of H-, O-, and OH- on the incident electron energy. Their formation is attributed to dissociative electron attachment. PMID:12785930

Pan, X; Cloutier, P; Hunting, D; Sanche, L

2003-05-23

328

Identification of c-Type Heme-Containing Peptides Using Non-Activated Immobilized Metal Affinity Cchromatography Resin Enrichment and Higher-Energy Collisional Dissociation  

SciTech Connect

c-type cytochromes play essential roles in many biological activities of both prokaryotic and eukaryotic cells, including electron transfer, enzyme catalysis and induction of apoptosis. We report a novel enrichment strategy for identifying c-type heme-containing peptides that uses non-activated IMAC resin. The strategy demonstrated at least seven-fold enrichment for heme-containing peptides digested from a cytochrome c protein standard, and quantitative linear performance was also assessed for heme-containing peptide enrichment. Heme-containing peptides extracted from the periplasmic fraction of Shewanella oneidensis MR-1 were further identified using higher-energy collisional dissociation tandem mass spectrometry. The results demonstrated the applicability of this enrichment strategy to identify c-type heme-containing peptides from a highly complex biological sample, and at the same time, confirmed the periplasmic localization of heme-containing proteins during suboxic respiration activities of S. oneidensis MR-1.

Zhang, Haizhen; Yang, Feng; Qian, Weijun; Brown, Roslyn N.; Wang, Yuexi; Merkley, Eric D.; Park, Jea H.; Monroe, Matthew E.; Purvine, Samuel O.; Moore, Ronald J.; Shi, Liang; Fredrickson, Jim K.; Pasa-Tolic, Ljiljana; Smith, Richard D.; Lipton, Mary S.

2011-10-01

329

Isotope dependent, temperature regulated, energy repartitioning in a low-barrier, short-strong hydrogen bonded cluster  

E-print Network

Isotope dependent, temperature regulated, energy repartitioning in a low-barrier, short/deuterium isotope effects, in a fundamental organic hydrogen bonded system using multiple experimental infrared the isotopically labeled systems arises from an analysis of the simulated cluster spectroscopy and leads

Iyengar, Srinivasan S.

330

Solvent dependent competition between fluorescence resonance energy transfer and through bond energy transfer in rhodamine appended hexaphenylbenzene derivatives for sensing of Hg(2+) ions.  

PubMed

Hexaphenylbenzene (HPB) derivatives 5 and 7 having rhodamine B moieties have been designed and synthesized, and have been shown to display solvent dependent. Fluorescence resonance energy transfer (FRET) and through bond energy transfer (TBET) in the presence of Hg(2+) ions among the various cations (Cu(2+), Pb(2+), Zn(2+), Ni(2+), Cd(2+), Ag(+), Ba(2+), Mg(2+), K(+), Na(+), and Li(+)) have been tested. Derivative 5 displays quite high through bond energy transfer efficiency in the presence of Hg(2+) ions in methanol whereas derivative 7 exhibits better FRET efficiency in the presence of Hg(2+) ions in THF and CH(3)CN than derivative 5. PMID:23385981

Bhalla, Vandana; Vij, Varun; Tejpal, Ruchi; Singh, Gopal; Kumar, Manoj

2013-04-01

331

Dissociative recombination of the acetaldehyde cation, CH(3)CHO(+).  

PubMed

The dissociative recombination of the acetaldehyde cation, CH(3)CHO(+), has been investigated at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. The dependence of the absolute cross section of the reaction on the relative kinetic energy has been determined and a thermal rate coefficient of k(T) = (1.5 ± 0.2) × 10(-6) (T/300)(-0.70±0.02) cm(3) s(-1) has been deduced, which is valid for electron temperatures between ?10 and 1000 K. The branching fractions of the reaction were studied at ?0 eV relative kinetic energy and we found that breaking one of the bonds between two of the heavy atoms occurs in 72 ± 2% of the reactions. In the remaining events the three heavy atoms stay in the same product fragment. While the branching fractions are fairly similar to the results from an earlier investigation into the dissociative recombination of the fully deuterated acetaldehyde cation, CD(3)CDO(+), the thermal rate coefficient is somewhat larger for CH(3)CHO(+). Astrochemical implications of the results are discussed. PMID:20714489

Vigren, Erik; Hamberg, Mathias; Zhaunerchyk, Vitali; Kaminska, Magdalena; Thomas, Richard D; Trippel, Sebastian; Zhang, Mingwu; Kashperka, Iryna; Ugglas, Magnus Af; Walsh, Catherine; Wester, Roland; Semaniak, Jacek; Larsson, Mats; Geppert, Wolf D

2010-10-01

332

Dissociative adsorption of CH?X (X = Br and Cl) on a silicon(100) surface revisited by density functional theory.  

PubMed

During the dissociative adsorption on a solid surface, the substrate usually participates in a passive manner to accommodate fragments produced upon the cleavage of the internal bond(s) of a (transient) molecular adsorbate. This simple picture, however, neglects the flexibility of surface atoms. Here, we report a Density Functional Theory study to revisit our early studies of the dissociative adsorption of CH3X (X = Br and Cl) on Si(100). We have identified a new reaction pathway, which involves a flip of a silicon dimer; this new pathway agrees better with experiments. For our main exemplar of CH3Br, insights have been gained using a simple model that involves a three-atom reactive center, Br-C-Si. When the silicon dimer flips, the interaction between C and Si in the Br-C-Si center is enhanced, evident in the increased energy-split of the frontier orbitals. We also examine how the dissociation dynamics of CH3Br is altered on a heterodimer (Si-Al, Si-P, and Si-Ge) in a Si(100) surface. In each case, we conclude, on the basis of computed reaction pathways, that no heterodimer flipping is involved before the system transverses the transition state to dissociative adsorption. PMID:25381532

Wang, Chen-Guang; Huang, Kai; Ji, Wei

2014-11-01

333

Benchmark binding energies of ammonium and alkyl-ammonium ions interacting with water. Are ammonium-water hydrogen bonds strong?  

NASA Astrophysics Data System (ADS)

Alkyl-ammonium ion/water interactions are investigated using high level quantum computations, yielding thermodynamics data in good agreement with gas-phase experiments. Alkylation and hydration lead to weaken the NHsbnd O hydrogen bonds. Upon complete hydration by four water molecules, their main features are close to those of the OHsbnd O bond in the isolated water dimer. Energy decomposition analyses indicate that hydration of alkyl-ammonium ions are mainly due to electrostatic/polarization effects, as for hard monoatomic cations, but with a larger effect of dispersion.

Vallet, Valérie; Masella, Michel

2015-01-01

334

Bonding in silicates: Investigation of the Si L 2,3 edge by parallel electron energy-loss spectroscopy  

Microsoft Academic Search

The Si L2,3 core-loss edge can be used to probe the crystal chemistry around Si, providing information on the s- and d-like partial density of unoccupied states of the Si-O bonds. We present Si L 2,3 edges from 59 silicates, glasses, and amorphous materials acquired by parallel electron energy-loss spectroscopy (PEELS) with a transmission electron microscope (TEM) at an energy

LAURENCE A. J. GARVIE; PETER R. BUSECK

1999-01-01

335

The Effect of Carbon Monoxide Co-Adsorption on Ni-Catalysed Water Dissociation  

PubMed Central

The effect of carbon monoxide (CO) co-adsorption on the dissociation of water on the Ni(111) surface has been studied using density functional theory. The structures of the adsorbed water molecule and of the transition state are changed by the presence of the CO molecule. The water O–H bond that is closest to the CO is lengthened compared to the structure in the absence of the CO, and the breaking O–H bond in the transition state structure has a larger imaginary frequency in the presence of CO. In addition, the distances between the Ni surface and H2O reactant and OH and H products decrease in the presence of the CO. The changes in structures and vibrational frequencies lead to a reaction energy that is 0.17 eV less exothermic in the presence of the CO, and an activation barrier that is 0.12 eV larger in the presence of the CO. At 463 K the water dissociation rate constant is an order of magnitude smaller in the presence of the CO. This reveals that far fewer water molecules will dissociate in the presence of CO under reaction conditions that are typical for the water-gas-shift reaction. PMID:24287907

Mohsenzadeh, Abas; Borjesson, Anders; Wang, Jeng-Han; Richards, Tobias; Bolton, Kim

2013-01-01

336

Further Theoretical Evidence for Hydrogen-Assisted CO Dissociation on Ru(0001)  

SciTech Connect

Extensive calculations based on spin-polarized density functional theory were carried out to examine how CH{sub x} are formed from the dissociation of CO on Ru(0001) in the presence of hydrogen. Common pathways, such as the direct CO dissociation and H-assisted route leading to HCO or COH, including alternative routes that involve the formation of HCOH and CH{sub 2}O, were examined. The reaction energy and barrier for each elementary step were calculated. The calculations show that the carbide mechanism is not the main reaction pathway for the conversion of CO on Ru(0001). Complementary microkinetic simulations utilizing results from first-principles quantum mechanical calculations indicate that a branch starting from the hydrogenation of CO to HCOH (via COH intermediate) and subsequent C–O bond cleavage is more plausible.

Alfonso, Dominic R.

2013-10-10

337

Adsorption and dissociation of molecular oxygen on ?-Pu (020) surface: A density functional study  

NASA Astrophysics Data System (ADS)

Molecular and dissociative oxygen adsorption on the (020) surface of ?-Pu have been studied using the full-potential linearized augmented-plane-wave plus local orbitals (FP-LAPW+lo) basis method. Four adsorption sites and three approaches of O2 molecule have been considered. Adsorption energies have been optimized according to the distance of the adsorbates from the Pu surface as well as the oxygen dimer bond length. Dissociative adsorption is found for two horizontal approaches (O2 is parallel to the surface and parallel/perpendicular to a lattice vector) and to be more energetically favorable at the scalar and "fully" relativistic (NSOC vs. SOC) levels of theory. Hor2 approach on the top site was the preferred adsorption site among all cases studied here. Molecular adsorption occurs at the Vert (O2 is vertical to the surface) approach. The work functions, net spin magnetic moments, and charge transfer are also calculated.

Wang, Jianguang; Ray, Asok

2011-03-01

338

Ultrafast dissociation pathways of diphenylmethyl chloride to generate reactive carbo cations  

NASA Astrophysics Data System (ADS)

The primary processes in the formation of electrophilic precursor ions are studied on a microscopic scale by quantum chemical and quantum dynamical methods. For the competing reaction channels of heterolysis and homolysis in the photochemically induced dissociation of diphenylmethyl chloride, ab initio data for the ground and excited electronic states are evaluated in the gas phase. Here, the simultaneous formation of ionic and radicalic products can solely be attributed to the existence of conical intersections which are localized and characterized for the first time. The interaction of different electronic states also leads to the initial charge transfer from the phenyl ?-system to the ?-bond of the leaving group which is essential for the fast dissociation and is explained by orbital analysis. Quantum dynamical calculations in one and two dimensions suggest that in gas phase the ion pair constitutes the main product despite its higher potential energy. Possible changes in polar solvents, where the ionic fragments are stabilized below the radical channel, are discussed.

Fingerhut, Benjamin P.; Geppert, Dorothee; de Vivie-Riedle, Regina

2008-01-01

339

Coordination-resolved local bond contraction and electron binding-energy entrapment of Si atomic clusters and solid skins  

SciTech Connect

Consistency between x-ray photoelectron spectroscopy measurements and density-function theory calculations confirms our bond order-length-strength notation-incorporated tight-binding theory predictions on the quantum entrapment of Si solid skin and atomic clusters. It has been revealed that bond-order deficiency shortens and strengthens the Si-Si bond, which results in the local densification and quantum entrapment of the core and valence electrons. Unifying Si clusters and Si(001) and (111) skins, this mechanism has led to quantification of the 2p binding energy of 96.089?eV for an isolated Si atom, and their bulk shifts of 2.461?eV. Findings evidence the significance of atomic undercoordination that is of great importance to device performance.

Bo, Maolin; Huang, Yongli; Zhang, Ting [Key Laboratory of Low-Dimensional Materials and Application Technologies, Xiangtan University, Hunan 411105 (China); Wang, Yan, E-mail: ywang8@hnust.edu.cn, E-mail: ecqsun@ntu.edu.sg [Key Laboratory of Low-Dimensional Materials and Application Technologies, Xiangtan University, Hunan 411105 (China); School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); Zhang, Xi [School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Li, Can [Center for Coordination Bond Engineering, School of Materials Science and Engineering, China Jiliang University, Hangzhou 330018 (China); Sun, Chang Q., E-mail: ywang8@hnust.edu.cn, E-mail: ecqsun@ntu.edu.sg [Key Laboratory of Low-Dimensional Materials and Application Technologies, Xiangtan University, Hunan 411105 (China); School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Center for Coordination Bond Engineering, School of Materials Science and Engineering, China Jiliang University, Hangzhou 330018 (China)

2014-04-14

340

Bonding silicones with epoxies  

SciTech Connect

It is shown that silicones, both room temperature vulcanizing (RTV) and millable rubber (press cured) can be successfully bonded to other materials using plasma treatment and epoxy adhesives. The plasma treatment using dry air atmosphere increases the surface energy of the silicone and thus provides a lower water contact angle. This phenomenon allows the epoxy adhesive to wet the silicone surface and ultimately bond. Bond strengths are sufficiently high to result in failures in the silicone materials rather than the adhesive bond.

Tira, J.S.

1980-01-01

341

Dissociative Identity Disorder  

PubMed Central

A brief description of the controversies surrounding the diagnosis of dissociative identity disorder is presented, followed by a discussion of the proposed similarities and differences between dissociative identity disorder and borderline personality disorder. The phenomenon of autohypnosis in the context of early childhood sexual trauma and disordered attachment is discussed, as is the meaning of alters or alternate personalities. The author describes recent neurosciences research that may relate the symptoms of dissociative identity disorder to demonstrable disordered attention and memory processes. A clinical description of a typical patient presentation is included, plus some recommendations for approaches to treatment. PMID:19724751

2009-01-01

342

Total energies and bonding for crystallographic structures in titanium-carbon and tungsten-carbon systems  

NASA Astrophysics Data System (ADS)

A full-potential linearized muffin-tin orbital calculation is presented of titanium-carbon systems in a variety of crystallographic forms. The calculated electronic structure, total energies, and equilibrium lattice constants are determined for the ground-state NaCl structure of TiC and for prototype superlattice structures, and these results are discussed in terms of the nature of bonding found in TiC. Similar calculations are also given for WC in two of these crystalline forms, and the differing ground-state structure and equilibrium lattice constants in these two carbide materials are related to the behavior of those metallic d states which are occupied in WC and unoccupied in TiC. The behavior of these one-electron states, which stabilize WC in a simple hexagonal form, is similar to the calculated behavior of associated states in the prototype superlattice Ti-C structures, and these states are found to play a similar role in determining the structural characteristics in these systems. Some of the properties and probable stability of the various crystalline forms are also discussed in terms of our results.

Price, David L.; Cooper, Bernard R.

1989-03-01

343

On the existence and characteristics of ?-beryllium bonds.  

PubMed

The existence of ?-beryllium bonds explains the stability of the complexes between ethylene and acetylene and BeX2 (X = H, F, and Cl) derivatives. These linkers involve a significant charge transfer from the ?(CC) bonding orbitals into the empty p orbitals of Be and to a much smaller degree into the ?(BeH)* antibonding orbitals. The significant deformation of the BeX2 moiety and the slight deformation of the unsaturated hydrocarbon result in distortion energies as high as the dissociation energy of the complex. The ?-beryllium bonds are about four times stronger than conventional ?-hydrogen bonds and even stronger than the strongest ?-hydrogen bond reported to date in the literature. The topology of their electron density is characterized as being very flat in the bonding region between the ?-system and Be, which leads to topologically unstable structures close to catastrophe points. Among the functionals considered in our study M06 is the one that leads to values in better agreement with CCSD(T)/aug-cc-pVTZ calculations used as a reference. B3LYP underestimates some interactions, whereas M06-2X overestimates all of them. MP2 also yields good agreement with the CCSD(T) method. PMID:25026560

Villanueva, Estefanía Fernández; Mó, Otilia; Yáñez, Manuel

2014-09-01

344

Bent Bonds and Multiple Bonds.  

ERIC Educational Resources Information Center

Considers carbon-carbon multiple bonds in terms of Pauling's bent bond model, which allows direct calculation of double and triple bonds from the length of a CC single bond. Lengths of these multiple bonds are estimated from direct measurements on "bent-bond" models constructed of plastic tubing and standard kits. (CS)

Robinson, Edward A.; Gillespie, Ronald J.

1980-01-01

345

Financing Public Sector Projects with Clean Renewable Energy Bonds; Fact Sheet Series on Financing Renewable Energy Projects, National Renewable Energy Laboratory (NREL)  

SciTech Connect

Clean renewable energy bonds (CREBs) present a low-cost opportunity for public entities to issue bonds to finance renewable energy projects. The federal government lowers the cost of debt by providing a tax credit to the bondholder in lieu of interest payments from the issuer. Because CREBs are theoretically interest free, they may be more attractive than traditional tax-exempt municipal bonds. In February 2009, Congress appropriated a total of $2.4 billion for the "New CREBs" program. No more than one-third of the budget may be allocated to each of the eligible entities: governmental bodies, electric cooperatives, and public power providers. Applications for this round of "New CREBs" were due to the Internal Revenue Service (IRS) on August 4, 2009. There is no indication Congress will extend the CREBs program; thus going forward, only projects that are approved under the 2009 round will be able to issue CREBs. This factsheet explains the CREBs mechanism and provides guidance on procedures related to issuing CREBs.

Kreycik, C.; Couglin, J.

2009-12-01

346

Initiation stage of alkene metathesis: Insights from natural bond orbital and charge decomposition analyses  

NASA Astrophysics Data System (ADS)

The Rusbnd PR3 bonds of 1-2(a-b)-PC, Rudbnd CHPh bonds of 1a-b, 2-Inact/Act and 1a-b, 2-RCB were analyzed by charge decomposition (CDA) and natural bond orbital (NBO). We have found that the dissociation step of the Rusbnd PR3 bond is driven by charge transfer, while the RCB by polarization effects. Furthermore, the ?(Cipso)-?*(Rudbnd C) interaction was associated with delocalization effects in the benzylidene ring. Likewise, the nature of the rotameric changes in the carbene was studied through the resonance stabilization energy (ENLW). 2 presented a lower ?ENLW (Inactive ? Active) than 1a-b, which confirms that the delocalization effects are related to a low carbene rotameric energy.

Paredes-Gil, Katherine; Jaque, Pablo

2015-01-01

347

Phosphodiester and N-glycosidic bond cleavage in DNA induced by 4-15 eV electrons  

NASA Astrophysics Data System (ADS)

Thin molecular films of the short single strand of DNA, GCAT, were bombarded under vacuum by electrons with energies between 4 and 15 eV. Ex vacuo analysis by high-pressure liquid chromatography of the samples exposed to the electron beam revealed the formation of a multitude of products. Among these, 12 fragments of GCAT were identified by comparison with reference compounds and their yields were measured as a function of electron energy. For all energies, scission of the backbone gave nonmodified fragments containing a terminal phosphate, with negligible amounts of fragments without the phosphate group. This indicates that phosphodiester bond cleavage by 4-15 eV electrons involves cleavage of the C-O bond rather than the P-O bond. The yield functions exhibit maxima at 6 and 10-12 eV, which are interpreted as due to the formation of transient anions leading to fragmentation. Below 15 eV, these resonances dominate bond dissociation processes. All four nonmodified bases are released from the tetramer, by cleavage of the N-glycosidic bond, which occurs principally via the formation of core-excited resonances located around 6 and 10 eV. The formation of the other nonmodified products leading to cleavage of the phosphodiester bond is suggested to occur principally via two different mechanisms: (1) the formation of a core-excited resonance on the phosphate unit followed by dissociation of the transient anion and (2) dissociation of the CO bond of the phosphate group formed by resonance electron transfer from the bases. In each case, phosphodiester bond cleavage leads chiefly to the formation of stable phosphate anions and sugar radicals with minimal amounts of alkoxyl anions and phosphoryl radicals.

Zheng, Yi; Cloutier, Pierre; Hunting, Darel J.; Wagner, J. Richard; Sanche, Léon

2006-02-01

348

Influence of oxygen inhibition on the surface free energy and enamel bond strength of self-etch adhesives.  

PubMed

We compared the surface free energies and enamel bond strengths of single-step self-etch adhesives with and without an oxygen-inhibited layer. The adhesives were applied to the enamel surfaces of bovine incisors, light irradiated, and the oxygen-inhibited layer was either retained or removed with ethanol. The surface free energies and their components (?(S)(LW), ?(S)(+), and ?(S)(-)) were determined by measuring the contact angles of three test liquids placed on the cured adhesives. The enamel bond strengths of specimens with and without the oxygen-inhibited layer were measured. For all surfaces, the value of the estimated surface tension component ?(S)(LW) was relatively constant. The value of the ?(S)(+) component increased slightly when the oxygen-inhibited layer was removed, whereas that of the ?(S)(-) component decreased significantly. The enamel bond strengths of the self-etch adhesives were significantly lower in the specimens without an oxygen-inhibited layer. The oxygen-inhibited layer therefore appeared to promote higher enamel bond strength. PMID:22277602

Oyama, Koji; Tsujimoto, Akimasa; Otsuka, Eiichiro; Shimizu, Yusuke; Shiratsuchi, Koji; Tsubota, Keishi; Takamizawa, Toshiki; Miyazaki, Masashi

2012-02-01

349

Excited singlet (S1) state interactions of calixarenes with chloroalkanes: A combination of concerted and stepwise dissociative electron transfer mechanism  

NASA Astrophysics Data System (ADS)

Both steady-state and time-resolved studies in acetonitrile (ACN) solutions show that the excited singlet (S1) states of calixarenes (CX) undergo quenching by chloroalkanes (CA). It has been revealed by characterizing the Cl ions in the photolyzed CX-CA systems in ACN solutions that the quenching occurs due to dissociative electron transfer (DET) mechanism, whereby a C-Cl bond of the CAs undergoes dissociation on acceptance of an electron from excited CX. The bimolecular quenching constants (kq) in the present systems were correlated with the free energy changes for the concerted DET reactions based on a suitable DET theory. Such a correlation results in the recovery of an intramolecular reorganization energy, which is substantially lower to account for the C-Cl bond dissociation energy of the CAs. Comparing present results with those of an another donor-acceptor system (e.g., biphenyldiol-CA systems) where a concerted DET mechanism is applicable, it is inferred that in CX-CA systems both concerted and stepwise DET mechanisms operate simultaneously. It is proposed that the interaction of excited CXs with encaged CAs follows the stepwise mechanism whereas that with the out of cage CAs follows the concerted mechanism.

Mohanty, J.; Pal, H.; Nayak, S. K.; Chattopadhyay, S.; Sapre, A. V.

2002-12-01

350

State-resolved probes of methane dissociation dynamics  

NASA Astrophysics Data System (ADS)

A new generation of experimental techniques quantifies the gas-surface reactivity of polyatomic reactants prepared in a single quantum state. These experiments eliminate internal state averaging and permit reactivity measurements on molecules with well-defined internal and translational energy. Varying the identity of the selected vibrational and rotational state and the molecule’s translational energy reveals how energy in specific energetic coordinates promotes reaction. When applied to methane’s dissociative chemisorption, which is rate-limiting in the industrial steam reforming reaction, these experiments reveal the molecular basis for activation, and they provide detailed insight into energy flow dynamics prior to reaction. This review will focus on experiments that quantify the reactivity of methane prepared in select rovibrational quantum states via optical excitation in a supersonic molecular beam. An overview will provide context, and a survey of experimental methods will emphasize features unique to these experiments. A presentation and discussion of state-resolved beam-surface scattering studies of methane activation on Ni(1 1 1), Ni(1 0 0), and Pt(1 1 1) will highlight the mechanistic and dynamical insights that such studies can provide. For example, while C-H stretching excitation best promotes transition state access on Ni(1 1 1) and Ni(1 0 0), bending excitation also activates dissociation, suggesting that many different energetic coordinates contribute to reactivity. Among those states studied, non-statistical behavior, including vibrational mode-specific and even bond-selective chemistry, is widespread, which indicates that the assumptions underlying statistical rate theories do not apply to this reaction. We examine the relevant timescales for energy exchange and reaction to provide a plausible explanation for the observation of non-statistical behavior. Finally, we suggest how these methods, and the results they have produced, might guide future work in the field.

Juurlink, L. B. F.; Killelea, D. R.; Utz, A. L.

2009-04-01

351

Inferring modules of functionally interacting proteins using the Bond Energy Algorithm  

PubMed Central

Background Non-homology based methods such as phylogenetic profiles are effective for predicting functional relationships between proteins with no considerable sequence or structure similarity. Those methods rely heavily on traditional similarity metrics defined on pairs of phylogenetic patterns. Proteins do not exclusively interact in pairs as the final biological function of a protein in the cellular context is often hold by a group of proteins. In order to accurately infer modules of functionally interacting proteins, the consideration of not only direct but also indirect relationships is required. In this paper, we used the Bond Energy Algorithm (BEA) to predict functionally related groups of proteins. With BEA we create clusters of phylogenetic profiles based on the associations of the surrounding elements of the analyzed data using a metric that considers linked relationships among elements in the data set. Results Using phylogenetic profiles obtained from the Cluster of Orthologous Groups of Proteins (COG) database, we conducted a series of clustering experiments using BEA to predict (upper level) relationships between profiles. We evaluated our results by comparing with COG's functional categories, And even more, with the experimentally determined functional relationships between proteins provided by the DIP and ECOCYC databases. Our results demonstrate that BEA is capable of predicting meaningful modules of functionally related proteins. BEA outperforms traditionally used clustering methods, such as k-means and hierarchical clustering by predicting functional relationships between proteins with higher accuracy. Conclusion This study shows that the linked relationships of phylogenetic profiles obtained by BEA is useful for detecting functional associations between profiles and extending functional modules not found by traditional methods. BEA is capable of detecting relationship among phylogenetic patterns by linking them through a common element shared in a group. Additionally, we discuss how the proposed method may become more powerful if other criteria to classify different levels of protein functional interactions, as gene neighborhood or protein fusion information, is provided. PMID:18559112

Watanabe, Ryosuke LA; Morett, Enrique; Vallejo, Edgar E

2008-01-01

352

Evaluation of Die-Attach Bonding Using High-Frequency Ultrasonic Energy for High-Temperature Application  

NASA Astrophysics Data System (ADS)

Room-temperature die-attach bonding using ultrasonic energy was evaluated on Cu/In and Cu/Sn-3Ag metal stacks. The In and Sn-3Ag layers have much lower melting temperatures than the base material (Cu) and can be melted through the heat generated during ultrasonic bonding, forming intermetallic compounds (IMCs). Samples were bonded using different ultrasonic powers, bonding times, and forces and subsequently aged at 300°C for 500 h. After aging, die shear testing was performed and the fracture surfaces were inspected by scanning electron microscopy. Results showed that the shear strength of Cu/In joints reached an upper plateau after 100 h of thermal aging and remained stable with aging time, whereas that of the Cu/Sn-3Ag joints decreased with increasing aging time. ?-Cu7In4 and (Cu,Au)11In9 IMCs were observed at the Cu/In joint, while Cu3Sn and (Ag,Cu)3Sn IMCs were found at the Cu/Sn-3Ag joint after reliability testing. As Cu-based IMCs have high melting temperatures, they are highly suitable for use in high-temperature electronics, but can be formed at room temperature using an ultrasonic approach.

Lee, Jong-Bum; Aw, Jie-Li; Rhee, Min-Woo

2014-09-01

353

A B3LYP and MP2(full) theoretical investigation into the strength of the C-NO(2) bond upon the formation of the intermolecular hydrogen-bonding interaction between HF and the nitro group of nitrotriazole or its methyl derivatives.  

PubMed

The changes of bond dissociation energy (BDE) in the C-NO(2) bond and nitro group charge upon the formation of the intermolecular hydrogen-bonding interaction between HF and the nitro group of 14 kinds of nitrotriazoles or methyl derivatives were investigated using the B3LYP and MP2(full) methods with the 6-311++G**, 6-311++G(2df,2p) and aug-cc-pVTZ basis sets. The strength of the C-NO(2) bond was enhanced and the charge of nitro group turned more negative in complex in comparison with those in isolated nitrotriazole molecule. The increment of the C-NO(2) bond dissociation energies correlated well with the intermolecular H-bonding interaction energies. Electron density shifts analyses showed that the electron density shifted toward the C-NO(2) bond upon complex formation, leading to the strengthened C-NO(2) bond and the possibly reduced explosive sensitivity. PMID:22955424

Li, Bao-Hui; Shi, Wen-Jing; Ren, Fu-de; Wang, Yong

2013-02-01

354

A comparative study of Dissociative Ionization of N2 and CO  

NASA Astrophysics Data System (ADS)

A comparative study on the properties of charge symmetric dissociation (CSD) and charge asymmetric dissociation (CAD) of doubly ionized N2 and CO is performed. Kinetic energy release (KER) distributions resulting from the dissociation of doubly charged molecular ions are explained on the basis of calculated potential energy curves.

Pandey, Amrendra; Bapat, B.; Shamsundar, K. R.

2014-04-01

355

Chemically bonded ceramic materials for use in thermal energy storage devices  

SciTech Connect

Calcium aluminate cement and sodium polyphosphate bonded refractory concretes, i.e., ''castables'', based on North Carolina olivine aggregates were developed for use in electric ''off peak'' or ''night'' storage heaters. The calcium aluminate cement bonded concretes exhibited no deterioration after 50 thermal cycles in a 15 kW room size storage heater. These cement bonded castables are limited to use below 1200/sup 0/C when using the ''high iron (oxide)'' cements. The phosphate bonded concretes exhibited limited thermal shock damage after 50 thermal cycles, but this damage might be acceptable in storage core zones where temperatures exceed 1200/sup 0/C due to the high refractoriness of the phosphate bonded compositions. Additions of high specific gravity minerals such as magnetite increased the bulk density of the concrete to equal that of conventionally fired (sintered) olivine brick. The performance of the storage heater with castable core components was similar to the heater's performance with a core constructed of conventionally fired brick. Concrete sections were cast directly about the heater's resistive elements without any deterioration of the concrete or effect on the heater's performance. These results demonstrate that simple concrete casting and curing steps can be employed to produce storage heater cores and that significant cost savings can be realized by using olivine concretes in storage devices as compared to the use of conventionally fired brick.

Brosnan, D.A.

1985-08-01

356

Novel C?-C? bond cleavages of tryptophan-containing peptide radical cations.  

PubMed

In this study, we observed unprecedented cleavages of the C(?)-C(?) bonds of tryptophan residue side chains in a series of hydrogen-deficient tryptophan-containing peptide radical cations (M(•+)) during low-energy collision-induced dissociation (CID). We used CID experiments and theoretical density functional theory (DFT) calculations to study the mechanism of this bond cleavage, which forms [M - 116](+) ions. The formation of an ?-carbon radical intermediate at the tryptophan residue for the subsequent C(?)-C(?) bond cleavage is analogous to that occurring at leucine residues, producing the same product ions; this hypothesis was supported by the identical product ion spectra of [LGGGH - 43](+) and [WGGGH - 116](+), obtained from the CID of [LGGGH](•+) and [WGGGH](•+), respectively. Elimination of the neutral 116-Da radical requires inevitable dehydrogenation of the indole nitrogen atom, leaving the radical centered formally on the indole nitrogen atom ([Ind](•)-2), in agreement with the CID data for [WGGGH](•+) and [W(1-CH3)GGGH](•+); replacing the tryptophan residue with a 1-methyltryptophan residue results in a change of the base peak from that arising from a neutral radical loss (116 Da) to that arising from a molecule loss (131 Da), both originating from C(?)-C(?) bond cleavage. Hydrogen atom transfer or proton transfer to the ?-carbon atom of the tryptophan residue weakens the C(?)-C(?) bond and, therefore, decreases the dissociation energy barrier dramatically. PMID:22135037

Song, Tao; Hao, Qiang; Law, Chun-Hin; Siu, Chi-Kit; Chu, Ivan K

2012-02-01

357

Dissociative photoionization of methyl chloride studied with threshold photoelectron-photoion coincidence velocity imaging  

NASA Astrophysics Data System (ADS)

Utilizing threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging, dissociation of state-selected CH3Cl+ ions was investigated in the excitation energy range of 11.0-18.5 eV. TPEPICO time-of-flight mass spectra and three-dimensional time-sliced velocity images of CH3+ dissociated from CH3Cl+(A2A1 and B2E) ions were recorded. CH3+ was kept as the most dominant fragment ion in the present energy range, while the branching ratio of CH2Cl+ fragment was very low. For dissociation of CH3Cl+(A2A1) ions, a series of homocentric rings was clearly observed in the CH3+ image, which was assigned as the excitation of umbrella vibration of CH3+ ions. Moreover, a dependence of anisotropic parameters on the vibrational states of CH3+(11A') provided a direct experimental evidence of a shallow potential well along the C-Cl bond rupture. For CH3Cl+(B2E) ions, total kinetic energy released distribution for CH3+ fragmentation showed a near Maxwell-Boltzmann profile, indicating that the Cl-loss pathway from the B2E state was statistical predissociation. With the aid of calculated Cl-loss potential energy curves of CH3Cl+, CH3+ formation from CH3Cl+(A2A1) ions was a rapid direct fragmentation, while CH3Cl+(B2E) ions statistically dissociated to CH3+ + Cl via internal conversion to the high vibrational states of X2E.

Tang, Xiaofeng; Zhou, Xiaoguo; Wu, Manman; Liu, Shilin; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi

2012-01-01

358

Dissociative photoionization of methyl chloride studied with threshold photoelectron-photoion coincidence velocity imaging.  

PubMed

Utilizing threshold photoelectron-photoion coincidence (TPEPICO) velocity imaging, dissociation of state-selected CH(3)Cl(+) ions was investigated in the excitation energy range of 11.0-18.5 eV. TPEPICO time-of-flight mass spectra and three-dimensional time-sliced velocity images of CH(3)(+) dissociated from CH(3)Cl(+)(A(2)A(1) and B(2)E) ions were recorded. CH(3)(+) was kept as the most dominant fragment ion in the present energy range, while the branching ratio of CH(2)Cl(+) fragment was very low. For dissociation of CH(3)Cl(+)(A(2)A(1)) ions, a series of homocentric rings was clearly observed in the CH(3)(+) image, which was assigned as the excitation of umbrella vibration of CH(3)(+) ions. Moreover, a dependence of anisotropic parameters on the vibrational states of CH(3)(+)(1(1)A') provided a direct experimental evidence of a shallow potential well along the C-Cl bond rupture. For CH(3)Cl(+)(B(2)E) ions, total kinetic energy released distribution for CH(3)(+) fragmentation showed a near Maxwell-Boltzmann profile, indicating that the Cl-loss pathway from the B(2)E state was statistical predissociation. With the aid of calculated Cl-loss potential energy curves of CH(3)Cl(+), CH(3)(+) formation from CH(3)Cl(+)(A(2)A(1)) ions was a rapid direct fragmentation, while CH(3)Cl(+)(B(2)E) ions statistically dissociated to CH(3)(+) + Cl via internal conversion to the high vibrational states of X(2)E. PMID:22280757

Tang, Xiaofeng; Zhou, Xiaoguo; Wu, Manman; Liu, Shilin; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi

2012-01-21

359

Dissociation dynamics and thermochemistry of tin species, (CH3)4Sn and (CH3)6Sn2, by threshold photoelectron-photoion coincidence spectroscopy.  

PubMed

The dissociative photoionization of tetramethyltin (Me?Sn) and hexamethylditin (Me?Sn?) has been investigated by threshold photoelectron-photoion coincidence (TPEPICO). Ions are energy-selected, and their 0 K dissociation onsets are measured by monitoring the mass spectra as a function of ion internal energy. Me?Sn(+) dissociates rapidly by methyl loss, with a 0 K onset of E? = 9.382 ± 0.020 eV. The hexamethylditin ion dissociates slowly on the time scale of the experiment (i.e., during the 40 ?s flight time to the detector) so that dissociation rate constants are measured as a function of the ion energy. RRKM and the simplified statistical adiabatic channel model (SSACM) are used to extrapolate the measured rate constants for methyl and Me?Sn(•) loss to their 0 K dissociation onsets, which were found to be 8.986 ± 0.050 and 9.153 ± 0.075 eV, respectively. Updated values for the heats of formation of the neutral Me?Sn and Me?Sn? are used to derive the following 298.15 K gas-phase standard heats of formation, in kJ·mol?¹: ?(f)H(m)(o)(Me?Sn(+),g) = 746.3 ± 2.9; ?(f)H(m)(o)(Me?Sn?(+),g) = 705.1 ± 7.5; ?(f)H(m)(o)(Me?Sn(•),g) = 116.6 ± 9.7; ?(f)H(m)(o)(Me?Sn,g) = 123.0 ± 16.5; ?(f)H(m)(o)(MeSn(+),g) = 877.8 ± 16.4. These energetic values also lead to the following 298.15 K bond dissociation enthalpies, in kJ·mol?¹: BDE(Me?Sn-Me) = 284.1 ± 9.9; BDE(Me?Sn-SnMe?) = 252.6 ± 14.8. PMID:21182297

Dávalos, Juan Z; Herrero, Rebeca; Shuman, Nicholas S; Baer, Tomas

2011-02-01

360

Analysis of behavior of sodiated sugar hemiacetals under low-energy collision-induced dissociation conditions and application to investigating mutarotation and mechanism of a glycosidase  

PubMed Central

Analysis of anomericity is one of the most important issues in the structure elucidation of carbohydrates. Mass spectrometry (MS)-based methods are of particular interest and important to address the issue related to resolving anomericity of monosaccharide units in a glycan. However, direct analysis of hemiacetals has not been possible by MS because of the nonavailability of information regarding the gas-phase behavior of such ion species. We addressed this issue by using stage-discriminated energy-resolved mass spectrometry (ERMS) at the stages of MSn and MSn+1 and showed that such analysis can be made. This was achieved by proving that individual anomers can be identified and that the equilibrium of sodium adducted ion species of ?- and ?-anomers can be negated in the gas phase under collision-induced dissociation (CID) conditions. On the basis of these results, we could 1) observe the mutarotation of lactose and 2) speculate the hydrolysis mechanism of endo-glycosylceramidase by using mass spectrometry. PMID:19521058

Kanie, Osamu; Kurimoto, Ayako; Kanie, Yoshimi; Daikoku, Shusaku; Ohtake, Atsuko; Suzuki, Katsuhiko

2009-01-01

361

Analysis of behavior of sodiated sugar hemiacetals under low-energy collision-induced dissociation conditions and application to investigating mutarotation and mechanism of a glycosidase.  

PubMed

Analysis of anomericity is one of the most important issues in the structure elucidation of carbohydrates. Mass spectrometry (MS)-based methods are of particular interest and important to address the issue related to resolving anomericity of monosaccharide units in a glycan. However, direct analysis of hemiacetals has not been possible by MS because of the nonavailability of information regarding the gas-phase behavior of such ion species. We addressed this issue by using stage-discriminated energy-resolved mass spectrometry (ERMS) at the stages of MS(n) and MS(n+1) and showed that such analysis can be made. This was achieved by proving that individual anomers can be identified and that the equilibrium of sodium adducted ion species of alpha- and beta-anomers can be negated in the gas phase under collision-induced dissociation (CID) conditions. On the basis of these results, we could 1) observe the mutarotation of lactose and 2) speculate the hydrolysis mechanism of endo-glycosylceramidase by using mass spectrometry. PMID:19521058

Kanie, Osamu; Kurimoto, Ayako; Kanie, Yoshimi; Daikoku, Shusaku; Ohtake, Atsuko; Suzuki, Katsuhiko

2009-01-01

362

Tubulin bond energies and microtubule biomechanics determined from nanoindentation in silico  

E-print Network

Microtubules, the primary components of the chromosome segregation machinery, are stabilized by longitudinal and lateral non-covalent bonds between the tubulin subunits. However, the thermodynamics of these bonds and the microtubule physico-chemical properties are poorly understood. Here, we explore the biomechanics of microtubule polymers using multiscale computational modeling and nanoindentations in silico of a contiguous microtubule fragment. A close match between the simulated and experimental force-deformation spectra enabled us to correlate the microtubule biomechanics with dynamic structural transitions at the nanoscale. Our mechanical testing revealed that the compressed MT behaves as a system of rigid elements interconnected through a network of lateral and longitudinal elastic bonds. The initial regime of continuous elastic deformation of the microtubule is followed by the transition regime, during which the microtubule lattice undergoes discrete structural changes, which include first the reversib...

Kononova, Olga; Theisen, Kelly E; Marx, Kenneth A; Dima, Ruxandra I; Ataullakhanov, Fazly I; Grishchuk, Ekaterina L; Barsegov, Valeri

2015-01-01

363

Intracavity system design for IR multiphoton dissociation  

NASA Astrophysics Data System (ADS)

An intracavity system for the infrared multiple photon dissociation (IRMPD) of molecules with high dissociation energy threshold has been designed and implemented. The system design based on a TEA CO2 laser with a cavity folded in V-shape included the analysis of its stability varying the cavity dimensions as well as the analysis of the positions of the beam waists and of the beam size at them. The intracavity energy as a function of the total sample pressure has been measured and the laser-operation threshold has been determined. Intracavity IRMPD has been compared to traditional IRMPD performed in an irradiation geometry in which the radiation is focused into a photoreactor placed outside the laser cavity. Dissociation volumes in intracavity irradiation have resulted an order of magnitude larger than those obtained in experiments performed with the photoreactor outside the laser cavity.

Freytes, V. M.; Codnia, J.; Azcárate, M. L.

2011-06-01

364

Using Qualified Energy Conservation Bonds (QECBs) to Fund a Residential Energy Efficiency Loan Program: Case Study on Saint Louis County, MO  

SciTech Connect

Qualified Energy Conservation Bonds (QECBs) are federally-subsidized debt instruments that enable state, tribal, and local government issuers to borrow money to fund a range of qualified energy conservation projects. QECBs offer issuers very attractive borrowing rates and long terms, and can fund low-interest energy efficiency loans for home and commercial property owners. Saint Louis County, MO recently issued over $10 million of QECBs to finance the Saint Louis County SAVES residential energy efficiency loan program. The county's experience negotiating QECB regulations and restrictions can inform future issuers.

Zimring, Mark

2011-06-23

365

Polarization induced water molecule dissociation below the first-order electronic-phase transition temperature  

E-print Network

Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O$-$H covalent bonds within a single water molecule adsorbed on MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the...

Arulsamy, Andrew Das; Elersic, Kristina; Modic, Martina; Subramani, Uma Shankar

2011-01-01

366

Polarization induced water molecule dissociation below the first-order electronic-phase transition temperature.  

PubMed

Hydrogen produced from the photocatalytic splitting of water is one of the reliable alternatives to replace the polluting fossil and the radioactive nuclear fuels. Here, we provide unequivocal evidence for the existence of blue- and red-shifting O-H covalent bonds within a single water molecule adsorbed on the MgO surface as a result of asymmetric displacement polarizabilities. The adsorbed H-O-H on MgO gives rise to one weaker H-O bond, while the other O-H covalent bond from the same adsorbed water molecule compensates this effect with a stronger bond. The weaker bond (nearest to the surface), the interlayer tunneling electrons and the silver substrate are shown to be the causes for the smallest dissociative activation energy on the MgO monolayer. The origin that is responsible to initiate the splitting mechanism is proven to be due to the changes in the polarizability of an adsorbed water molecule, which are further supported by the temperature-dependent static dielectric constant measurements for water below the first-order electronic-phase transition temperature. PMID:21776515

Das Arulsamy, Andrew; Kregar, Zlatko; Elerši?, Kristina; Modic, Martina; Subramani, Uma Shankar

2011-09-01

367

Aircraft surface coatings study: Energy efficient transport program. [sprayed and adhesive bonded coatings for drag reduction  

NASA Technical Reports Server (NTRS)

Surface coating materials for application on transport type aircraft to reduce drag, were investigated. The investigation included two basic types of materials: spray on coatings and adhesively bonded films. A cost/benefits analysis was performed, and recommendations were made for future work toward the application of this technology.

1979-01-01

368

Dissociation and psychosis in dissociative identity disorder and schizophrenia.  

PubMed

Dissociative symptoms, first-rank symptoms of schizophrenia, and delusions were assessed in 40 schizophrenia patients and 40 dissociative identity disorder (DID) patients with the Multidimensional Inventory of Dissociation (MID). Schizophrenia patients were diagnosed with the Structured Clinical Interview for the DSM-IV Axis I Disorders; DID patients were diagnosed with the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised. DID patients obtained significantly (a) higher dissociation scores; (b) higher passive-influence scores (first-rank symptoms); and (c) higher scores on scales that measure child voices, angry voices, persecutory voices, voices arguing, and voices commenting. Schizophrenia patients obtained significantly higher delusion scores than did DID patients. What is odd is that the dissociation scores of schizophrenia patients were unrelated to their reports of childhood maltreatment. Multiple regression analyses indicated that 81% of the variance in DID patients' dissociation scores was predicted by the MID's Ego-Alien Experiences Scale, whereas 92% of the variance in schizophrenia patients' dissociation scores was predicted by the MID's Voices Scale. We propose that schizophrenia patients' responses to the MID do not index the same pathology as do the responses of DID patients. We argue that neither phenomenological definitions of dissociation nor the current generation of dissociation instruments (which are uniformly phenomenological in nature) can distinguish between the dissociative phenomena of DID and what we suspect are just the dissociation-like phenomena of schizophrenia. PMID:22651674

Laddis, Andreas; Dell, Paul F

2012-01-01

369

The dissociation of 13CH and 12CH 2 molecules in He and N 2 at beam energies of 80-250 keV and possible implications for radiocarbon mass spectrometry  

NASA Astrophysics Data System (ADS)

Isotopic ratios of 14C at natural levels can be efficiently measured with accelerator mass spectrometry (AMS). In compact AMS systems, 13CH and 12CH 2 molecular interferences are destroyed in collisions with the stripper gas, a process which can be described by dissociation cross sections. These dissociation cross sections determine the gas areal density required for sufficient attenuation of the interfering molecular beams, and are therefore key parameters in the effort to further reduce the terminal voltage and thus the size of the AMS system. We measured the dissociation cross sections of 13CH and 12CH 2 in N 2 and He in the energy range of 80-250 keV. In N 2, cross sections were constant for energies above 100 keV with average values per molecule of (8.1 ± 0.4) × 10 -16 cm 2 for 13CH and (9.5 ± 0.5) × 10 -16 cm 2 for 12CH 2. In He, cross sections were constant over the full measured range of 80-150 keV with average values of (4.2 ± 0.3) × 10 - 16 cm 2 and (4.8 ± 0.4) × 10 -16 cm 2, respectively. A considerable reduction of the terminal voltage from the currently used 200 kV while using N 2 for 13CH and 12CH 2 molecule dissociation is not possible: the required N 2 areal densities of ˜1.4 ?g/cm 2, consequential angular straggling and a decreasing 1+ charge state fraction would reduce the ion beam transmission too much. This is not the case for He: sufficient molecule dissociation can be obtained with gas densities of ˜0.4 ?g/cm 2, for which angular straggling is relatively small. In addition, the 1+ charge state fraction still increases at lower stripping energies. Thus, the usage of He for stripping and molecule dissociation might allow the development of even smaller 14C-AMS systems than available today.

Schulze-König, T.; Seiler, M.; Suter, M.; Wacker, L.; Synal, H.-A.

2011-01-01

370

Dissociative electron attachment to methylacetylene and dimethylacetylene: Symmetry versus proximity  

NASA Astrophysics Data System (ADS)

We have measured absolute dissociative electron attachment (DEA) cross sections in methylacetylene (propyne, C3H4) and dimethylacetylene (but-2-yne, C4H6). The main feature in the low-energy DEA spectrum is a ?* shape resonance giving rise to fragments at 3.4 eV in C3H4 and 4.0 eV in C4H6. The process C3H4+e? C3H3-+H proceeds via abstraction of the acetylenic hydrogen which is mediated by effective vibronic coupling. The abstraction of methyl group hydrogen, which does not require symmetry lowering of the transient negative ion, was not observed; the spatial separation of the bond from the resonance decreases the cross section dramatically. The presence of the methyl group further influences the DEA cross sections via change of the resonance's position and via blocking one or both of the DEA active sites in acetylene. No cleavage of the C-methyl bond has been observed, and reasons for this effect are discussed. Additionally, several higher-lying resonances (6 to 15 eV) leading to production of an H- fragment were observed and assigned.

Jane?ková, R.; May, O.; Fedor, J.

2012-11-01

371

Dissociative Electron Attachment to HCCCN  

NASA Astrophysics Data System (ADS)

Experiments on dissociative electron attachment (DEA) to HCCCN below 12 eV have led predominantly to formation of CCCN^-, CN^-, HCC^- and CC^- negative ions. It has been concluded that these fragments result mainly from the decay of ?*-shape resonant state upon electron attachment that involves distortion of the symmetry of the linear neutral molecule. In order to study the dynamics of dissociation in these channels, we subdivided the molecule into three fragments (H), (CC) and (CN); therefore, four internal coordinates consisting in the distances between the center of masses of (H) and (CC) fragments, (CC) and (CN) fragments, the (H)-(CC) angle and the (CC)-(CN) angle are included in the calculation. We have performed electron scattering calculations using Complex Kohn Variational method to determine the resonance energies and autoionization width for various geometries of the system and construct the complex potential energy surfaces relevant to the metastable HCCCN^-* ion. The nuclear dynamics is treated using the Multiconfiguration Time-Dependent Hartree (MCTDH) formalism and the flux of the propagating wavepacket is used to compute the DEA cross section relevant to 4 channels in question. The results are then compared to the available findings.

Chourou, Slim; Orel, Ann

2009-05-01

372

Dissociative Electron Attachment to HCCCN  

NASA Astrophysics Data System (ADS)

Experiments on dissociative electron attachment (DEA) to HCCCN below 12 eV have led predominantly to formation of CCCN^-, CN^-, HCC^- and CC^- negative ions. It has been concluded that these fragments result mainly from the decay of ?*- shape resonant state upon electron attachment that involves distortion of the symmetry of the linear neutral molecule. In order to study the dynamics of dissociation in these channels, we subdivided the molecule into three fragments (H), (CC) and (CN); therefore, three internal coordinates consisting in the distances between the center of masses (H) and (CC) fragments, (CC) and (CN) fragments and the (H)-(CC)-(CN) angle are included in the calculation. We have performed electron scattering calculations using Complex Kohn Variational method to determine the resonance energies and autoionization width for various geometries of the system and construct the complex potential energy surfaces relevant to the metastable HCCCN^-* ion. The nuclear dynamics is treated using the Multiconfiguration Time-Dependent Hartree (MCTDH) formalism and the flux of the propagating wavepacket is used to compute the DEA cross section relevant to 4 channels in question. The results are then compared to the available findings.

Chourou, S. T.; Orel, A. E.

2008-05-01

373

Spontaneous Exciton Dissociation in Carbon Nanotubes  

NASA Astrophysics Data System (ADS)

Simultaneous photoluminescence and photocurrent measurements on individual single-walled carbon nanotubes reveal spontaneous dissociation of excitons into free electron-hole pairs. The correlation of luminescence intensity and photocurrent shows that a significant fraction of excitons are dissociating before recombination. Furthermore, the combination of optical and electrical signals also allows for extraction of the absorption cross section and the oscillator strength. Our observations explain the reasons why photoconductivity measurements in single-walled carbon nanotubes are straightforward despite the large exciton binding energies.

Kumamoto, Y.; Yoshida, M.; Ishii, A.; Yokoyama, A.; Shimada, T.; Kato, Y. K.

2014-03-01

374

Dissociative Amnesia Related to Pregnancy  

Microsoft Academic Search

Dissociative amnesia, formerly called psychogenic amnesia, involve disruptions or breakdowns of memory, consciousness or awareness, identity and\\/or perception - mental functions that normally operate smoothly. Dissociative amnesia is not the same as simple amnesia, which involves a loss of information from the memory, usually as the result of disease or injury to the brain. With dissociative amnesia, the memories still

Hema Tharoor; Ashutosh Chauhan; Anoop Mathew; Podila Satya

375

Dissociative Style and Directed Forgetting  

Microsoft Academic Search

Dissociative style may correspond to an enhanced ability to avoid conscious recollection of traumatic experiences, which may, however, remain dormant in nonconscious memory. This hypothesis was tested in two “directed-forgetting” experiments with affectively neutral words (experiment 1) and sex and threat words (experiment 2) employing students high and low in dissociative style, and dissociative patients. Conscious and nonconscious memory were

Bernet M. Elzinga; Edwin de Beurs; Joseph A. Sergeant; Richard Van Dyck; R. Hans Phaf

2000-01-01

376

Three dimensions of dissociative amnesia.  

PubMed

Principal axis factor analysis with promax rotation extracted 3 factors from the 42 memory and amnesia items of the Multidimensional Inventory of Dissociation (MID) database (N = 2,569): Discovering Dissociated Actions, Lapses of Recent Memory and Skills, and Gaps in Remote Memory. The 3 factors' shared variance ranged from 36% to 64%. Construed as scales, the 3 factor scales had Cronbach's alpha coefficients of .96, .94, and .93, respectively. The scales correlated strongly with mean Dissociative Experiences Scale scores, mean MID scores, and total scores on the Structured Clinical Interview for DSM-IV Dissociative Disorders-Revised (SCID-D-R). What is interesting is that the 3 amnesia factors exhibited a range of correlations with SCID-D-R Amnesia scores (.52, .63, and .70, respectively), suggesting that the SCID-D-R Amnesia score emphasizes gaps in remote memory over amnesias related to dissociative identity disorder. The 3 amnesia factor scales exhibited a clinically meaningful pattern of significant differences among dissociative identity disorder, dissociative disorder not otherwise specified-1, dissociative amnesia, depersonalization disorder, and nonclinical participants. The 3 amnesia factors may have greater clinical utility for frontline clinicians than (a) amnesia as discussed in the context of the Diagnostic and Statistical Manual of Mental Disorders, Fourth Edition, nosology of the dissociative disorders or (b) P. Janet's (1893/1977 ) 4-fold classification of dissociative amnesia. The author recommends systematic study of the phenomenological differences within specific dissociative symptoms and their differential relationship to specific dissociative disorders. PMID:23282045

Dell, Paul F

2013-01-01

377

A Fracture Resisting Molecular Interaction in Trabecular Bone: Sacrificial Bonds and Hidden Length Dissipate Energy as Mineralized Fibrils Separate  

NASA Astrophysics Data System (ADS)

A molecular energy dissipation mechanism in the form of sacrificial bonds and hidden length was previously found in bone constituent molecules of which the efficiency increased with the presence of Ca^2+ ions in the experimental solution. Here we present evidence for how this sacrificial bond-hidden length mechanism contributes to the mechanical properties of the bone composite. From investigations into the nanoscale arrangement of the bone constituents in combination with pico-Newton adhesion force measurements between mineralized collagen fibrils, based on single molecule force spectroscopy, we find evidence that bone consists of mineralized collagen fibrils and a non fibrillar organic matrix which acts as a ``glue'' that holds the mineralized fibrils together. We propose that this ``glue'' resists the separation of mineralized collagen fibrils. Like in the case of the sacrificial bonds in single molecules, the effectiveness of this ``glue'' increases with the presence of Ca^2+ ions. We further investigate how this molecular scale strengthening mechanism increases the fracture toughness of the macroscopic material.

Fantner, Georg E.

2005-03-01

378

Ion-induced dissociation dynamics of acetylene  

NASA Astrophysics Data System (ADS)

We report on the results of dissociation dynamics of multiple charged acetylene molecules formed in collision with 1.2 MeV Ar8+ projectiles. Using the coincidence map, we can separate out the different dissociation pathways between carbon and hydrogen ionic fragments as well as complete two-body breakup events. From the measured slopes of the coincidence islands for carbon atomic fragments and theoretical values determined from the charge and momentum distribution of the correlated particles, we observe a diatomlike behavior of the C-C charged complex during dissociation of multiply charged C2H2 . We conclude that this behavior in breakup dynamics is a signature of sequentiality in dissociation of this multiply charged molecular species. The shape and orientation of the islands give further information about the momentum balance in the fragmentation process of two- or many-body dissociation pathways. Kinetic energy release of different breakup channels are reported here and compared with values calculated from the pure Coulomb explosion model.

de, Sankar; Rajput, Jyoti; Roy, A.; Ghosh, P. N.; Safvan, C. P.

2008-02-01

379

Surface energy and chemical characteristics of interfaces of adhesively bonded aluminium joints  

Microsoft Academic Search

The deleterious effects of water on the physico-chemical aspects of the durability of adhesively bonded aluminium joints has been investigated. Emphasis was placed on analytical techniques that lead to the better understanding of changes induced at the metal\\/epoxy interface by the presence of water. Analytical techniques such as contact angle measurements, X-ray photoelectron spectroscopy and X-ray diffraction were practical in

G. Kim; F. Ajersch

1994-01-01

380

Anomalous J/? suppression and charmonium dissociation cross sections  

NASA Astrophysics Data System (ADS)

We study J/? suppression in Pb+Pb collisions at CERN-SPS energies in hadronic matter with energy- and temperature-dependent charmonium dissociation cross sections calculated in the quark-interchange model of Barnes and Swanson. The charmonium dissociation cross sections depend sensitively on energy and increase significantly as temperature increases. We find that the variation of J/? survival probability from peripheral to central collisions can be explained as induced by hadronic matter absorption in central collisions.

Xu, Xiao-Ming; Wong, Cheuk-Yin; Barnes, T.

2003-01-01

381

Characterization of drug-product-related impurities and variants of a therapeutic monoclonal antibody by higher energy C-trap dissociation mass spectrometry.  

PubMed

Mass spectrometry (MS) characterization of recombinant monoclonal antibody (mAb) drugs and their degraded and/or post-translationally modified counterparts, drug-product-related impurities and variants, is critical for successful development of biotherapeutics. Specifically in this study, drug-product-related impurities of an anti-Clostridium difficile IgG1 mAb drug substance were profiled by cation-exchange liquid chromatography (CEX) followed by the CEX peaks being fraction-collected for MS characterization. A reversed-phase liquid chromatography/mass spectrometry (LC/MS) methodology was developed on a Thermo Q-Exactive orbitrap mass spectrometer for (1) accurate mass measurements of the mAb, its CEX fractionated impurities, and their respective heavy chains and light chains and (2) middle-down LC/MS/MS of the light chains and the heavy chains using higher energy C-trap dissociation (HCD). The accurate mass measurements and the HCD middle-down MS/MS experiments identify that major impurities and variants of the anti-C. difficile mAb are degradation species of the heavy chains at residue Asn101 as well as at the hinge region amino acids, including Cys222, Lys224, His226, and Thr227, with levels ranging from 0.3% to 6.2% of the total drug substance. Additional impurities were identified as light chain C-terminal truncation at Gly93 and oxidized heavy chains at Met40, Met93, and Met430. Our impurity characterization results demonstrate that the middle-down MS method allows direct and accurate identification of drug-product-related impurities of therapeutic mAbs. It is particularly useful for those low-level impurities and variants that are not suitable for further fractionation and characterization by bottom-up MS. PMID:25513708

Wang, Deyun; Wynne, Colin; Gu, Flora; Becker, Chris; Zhao, Jia; Mueller, Hans-Martin; Li, Huijuan; Shameem, Mohammed; Liu, Yan-Hui

2015-01-20

382

Direct assessment of quantum nuclear effects on hydrogen bond strength by constrained-centroid ab initio path integral molecular dynamics.  

PubMed

The impact of quantum nuclear effects on hydrogen (H-) bond strength has been inferred in earlier work from bond lengths obtained from path integral molecular dynamics (PIMD) simulations. To obtain a direct quantitative assessment of such effects, we use constrained-centroid PIMD simulations to calculate the free energy changes upon breaking the H-bonds in dimers of HF and water. Comparing ab initio simulations performed using PIMD and classical nucleus molecular dynamics (MD), we find smaller dissociation free energies with the PIMD method. Specifically, at 50 K, the H-bond in (HF)(2) is about 30% weaker when quantum nuclear effects are included, while that in (H(2)O)(2) is about 15% weaker. In a complementary set of simulations, we compare unconstrained PIMD and classical nucleus MD simulations to assess the influence of quantum nuclei on the structures of these systems. We find increased heavy atom distances, indicating weakening of the H-bond consistent with that observed by direct calculation of the free energies of dissociation. PMID:21054031

Walker, Brent; Michaelides, Angelos

2010-11-01

383

Direct assessment of quantum nuclear effects on hydrogen bond strength by constrained-centroid ab initio path integral molecular dynamics  

NASA Astrophysics Data System (ADS)

The impact of quantum nuclear effects on hydrogen (H-) bond strength has been inferred in earlier work from bond lengths obtained from path integral molecular dynamics (PIMD) simulations. To obtain a direct quantitative assessment of such effects, we use constrained-centroid PIMD simulations to calculate the free energy changes upon breaking the H-bonds in dimers of HF and water. Comparing ab initio simulations performed using PIMD and classical nucleus molecular dynamics (MD), we find smaller dissociation free energies with the PIMD method. Specifically, at 50 K, the H-bond in (HF)2 is about 30% weaker when quantum nuclear effects are included, while that in (H2O)2 is about 15% weaker. In a complementary set of simulations, we compare unconstrained PIMD and classical nucleus MD simulations to assess the influence of quantum nuclei on the structures of these systems. We find increased heavy atom distances, indicating weakening of the H-bond consistent with that observed by direct calculation of the free energies of dissociation.

Walker, Brent; Michaelides, Angelos

2010-11-01

384

Reactive molecular dynamic simulations of hydrocarbon dissociations on Ni(111) surfaces  

NASA Astrophysics Data System (ADS)

Empirical potential parameters for H, C and Ni elements have been developed for the ReaxFF force field in order to study the decomposition of small hydrocarbon molecules on nickel using molecular dynamics simulations. These parameters were optimized using the geometrical and energetic information obtained from density functional (DFT) calculations on a subset of hydrogen and methane reactions with nickel (111) surfaces. The resulting force field was then used to obtain a molecular perspective of the dynamics of the methane dissociative adsorption on Ni(111) as well as two other small alkane molecules, ethane and n-butane. NVT simulations of dissociative adsorption of methane over a range of temperatures enabled the estimation of the sticking coefficient for the adsorption as well as the activation energy of the first C-H bond breaking. The rate constants of each elementary step (both forward and reverse) of CHx dissociation on Ni(111) were obtained by monitoring the surface species and a microkinetic model was constructed as a result. Qualitative analyses of the simulations of ethane and n-butane decompositions on Ni(111) demonstrate that such reactive MD technique can also be used to obtain useful information on complex reaction networks.

Liu, Bin; Lusk, Mark T.; Ely, James F.

2012-03-01

385

Photoinduced processes in hydrogen bonded system: photodissociation of imidazole clusters.  

PubMed

The photodissociation of imidazole in hydrogen bonded clusters has been studied at photodissociation wavelengths 243 and 193 nm. Imidazole clusters of different mean cluster sizes n approximately 3 and 6 have been produced in expansions with He and Ar carrier gases, and the mean cluster sizes were determined by mass spectrometric and crossed beam scattering experiments. Simultaneously, the (C(3)N(2)H(4))(n) clusters were studied by ab initio calculations for n up to 4 molecules, confirming the hydrogen bond N-H...N motif in the clusters. The measured H-fragment kinetic energy distribution spectra exhibit a bimodal character similar to the KEDs found for the bare molecule. (1) At 243 nm the fast H-atoms originate from the direct dissociation process on the repulsive pi sigma* state, and the slow component results from the dynamics populating the vibrationally hot ground state via an S(1)/S(0) conical intersection. In the clusters the contribution of the slow component increases with the cluster size. The slow component is also dominant at the shorter wavelength of 193 nm, where the dynamics starts with the excitation of pi pi* state. It is shown that the slow component in our experiment is a product of subsequent two-photon absorption. We have proposed different mechanisms how the observed enhanced internal conversion can be rationalized. The increased stability with respect to the H-fragment dissociation in clusters can be caused either by hydrogen transfer in the N-H...N bond or by closing the pi sigma* dissociation channel as in the case of pyrrole clusters. PMID:19572685

Poterya, Viktoriya; Profant, Václav; Fárník, Michal; Sistík, Lukás; Slavícek, Petr; Buck, Udo

2009-12-31

386

Teachers' Domain: Covalent Bonding  

NSDL National Science Digital Library

This Flash interactive tutorial explores covalent bonding, a type of chemical bond that involves sharing of electrons. Learners investigate the attractive and repulsive forces that act on atomic particles and how the sharing of electrons can keep atoms together. See how two hydrogen atoms interact with each other to create a covalent bond. Learn about patterns in the periodic table and how electrostatic potential energy determines the bond length. Teachers' Domain is a growing collection of more than 1,000 free educational resources compiled by researchers and experienced teachers to promote the use of digital resources in the classroom.

2011-08-16

387

Equilibrium and rate constants, and reaction mechanism of the HF dissociation in the HF(H2O)7 cluster by ab initio rare event simulations.  

PubMed

We perform restrained hybrid Monte Carlo (MC) simulations to compute the equilibrium constant of the dissociation reaction of HF in HF(H2O)7. We find that the HF is a stronger acid in the cluster than in the bulk, and its acidity is higher at lower T. The latter phenomenon has a vibrational entropic origin, resulting from a counterintuitive balance of intra- and intermolecular terms. We find also a temperature dependence of the reactions mechanism. At low T (?225 K) the dissociation reaction follows a concerted path, with the H atoms belonging to the relevant hydrogen bond chain moving synchronously. At higher T (300 K), the first two hydrogen atoms move together, forming an intermediate metastable state having the structure of an eigen ion (H9O4(+)), and then the third hydrogen migrates completing the reaction. We also compute the dissociation rate constant, kRP. At very low T (?75 K) kRP depends strongly on the temperature, whereas it gets almost constant at higher T’s. With respect to the bulk, the HF dissociation in the HF(H2O)7 is about 1 order of magnitude faster. This is due to a lower free energy barrier for the dissociation in the cluster. PMID:24256119

Elena, Alin Marin; Meloni, Simone; Ciccotti, Giovanni

2013-12-12

388

A first principle study for the adsorption and absorption of carbon atom and the CO dissociation on Ir(100) surface  

SciTech Connect

We employ density functional theory to examine the adsorption and absorption of carbon atom as well as the dissociation of carbon monoxide on Ir(100) surface. We find that carbon atoms bind strongly with Ir(100) surface and prefer the high coordination hollow site for all coverages. In the case of 0.75?ML coverage of carbon, we obtain a bridging metal structure due to the balance between Ir–C and Ir–Ir interactions. In the subsurface region, the carbon atom prefers the octahedral site of Ir(100) surface. We find large diffusion barrier for carbon atom into Ir(100) surface (2.70 eV) due to the strong bonding between carbon atom and Ir(100) surface, whereas we find a very small segregation barrier (0.22 eV) from subsurface to the surface. The minimum energy path and energy barrier for the dissociation of CO on Ir(100) surface are obtained by using climbing image nudge elastic band. The energy barrier of CO dissociation on Ir(100) surface is found to be 3.01 eV, which is appreciably larger than the association energy (1.61 eV) of this molecule.

Erikat, I. A., E-mail: ihsanas@yahoo.com [Department of Physics, Jerash University, Jerash-26150 (Jordan); Hamad, B. A. [Department of Physics, The University of Jordan, Amman-11942 (Jordan)] [Department of Physics, The University of Jordan, Amman-11942 (Jordan)

2013-11-07

389

Dissociation of strong acid revisited: X-ray photoelectron spectroscopy and molecular dynamics simulations of HNO3 in water  

SciTech Connect

Molecular-level insight into the dissociation of nitric acid in water is obtained from photoelectron X-ray spectroscopy and first-principles molecular dynamics (MD) simulations. Our combined studies reveal surprisingly abrupt changes in solvation configurations of undissociated nitric acid at approximately 4 M concentration. Experimentally, this is inferred from N1s binding energy shifts of HNO3(aq) as a function of concentration, and is associated with variations in the local electronic structure of the nitrogen atom. It also shows up as a discontinuity in the degree of dissociation as a function of concentration, determined here from the N1s photoelectron signal intensity, which can be separately quantified for undissociated HNO3(aq) and dissociated NO3-(aq). Intermolecular interactions within the nitric acid solution are discussed on the basis of MD simulations, which reveal that molecular HNO3 interacts remarkably weakly with solvating water molecules at low concentration; around 4 M there is a turnover to a more structured solvation shell, accompanied by an increase in hydrogen bonding between HNO3 and water. We suggest that the driving force behind the more structured solvent configuration of HNO3 is the overlap of nitric acid solvent shells that sets in around 4 M concentration. This work was supported by the US Department of Energy Basic Energy Sciences' Chemical Sciences, Geosciences & Biosciences Division. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

Lewis, Tanza; Winter, Berndt; Stern, Abraham C.; Baer, Marcel D.; Mundy, Christopher J.; Tobias, Douglas J.; Hemminger, J. C.

2011-08-04

390

Dynamical study of the dissociation and elimination channels in the decomposition of methyl nitrite  

NASA Astrophysics Data System (ADS)

The dynamics of the two unimolecular reactions that initiate the thermal decomposition of methyl nitrite were investigated by classical trajectories and statistical variational efficient microcanonical sampling-transition state theory. These two channels are (I) O-N bond dissociation to produce CH3O and NO and (II) concerted elimination through a four-center transition state to form CH2O and HNO. In order to perform both types of calculations, a potential energy function was developed, which reproduces reasonably well the energies, geometries, and frequencies selected from the literature. Microcanonical rate coefficients and branching ratios were obtained by each method at total energies ranging from 100 to 240 kcal/mol. The computed branching ratios indicated that reaction I is markedly faster than reaction II, which agrees with the experimental observations. It was found that for energies up to 160 kcal/mol the dynamics of reaction I is intrinsically Rice-Ramsperger-Kassel-Marcus (RRKM), but for the highest energies the behavior becomes intrinsically non-RRKM. The classical trajectories showed that the elimination process takes place via a regular dynamics during the last moments before reaction, which is clear evidence for nonstatistical behavior. Analysis of the trajectory rates computed for the deuterated species revealed that the dissociation process exhibits an inverse secondary isotope effect.

Martínez-Núñez, Emilio; Vázquez, Saulo A.

1998-11-01

391

Dissociative electron attachment to abasic DNA.  

PubMed

Thin films of the short single DNA strand, GCAT, in which one of the bases has been removed were bombarded with 3 to 15 eV electrons. The yield functions of the H(-), O(-) and OH(-) ions desorbed from these films exhibit a broad peak near 9 eV, which is attributed to dissociative electron attachment to the basic molecules. Whereas removal of any one of the bases considerably decreases N-glycosidic and backbone C-O bond scission, the creation of basic sites does not appreciably modify bond rupture leading to anion electron stimulated desorption. These seemingly contradictory results make it possible to propose a detailed mechanism leading to the transfer of electrons in the range 5-13 eV within DNA. PMID:17396184

Ptasi?ska, Sylwia; Sanche, Léon

2007-04-14

392

Consecutive ion activation for top down mass spectrometry: improved protein sequencing by nozzle-skimmer dissociation.  

PubMed

Mass spectra produced by nozzle-skimmer dissociation (NSD) have been little used in the past for structural characterization. NSD cannot be used on mass-separated ions (MS/MS), and for electrosprayed protein ions, previous NSD spectra showed backbone cleavages similar to those from energetic methods such as collisionally activated dissociation (CAD) or infrared multiphoton dissociation (IRMPD). However, our experimental configuration with Fourier transform (FT) MS makes possible three consecutive steps of NSD ion activation: thermal in the entrance capillary and collisional in both the nozzle-skimmer (N-S) region and the region after the skimmer before the quadrupole entrance lens (S-Q). In the high-pressure N-S region of adjustable path length, ions undergo high-frequency, low-energy collisions to rupture weak noncovalent or covalent bonds, with these "denatured" products then subjected to high-energy collisions in the low-pressure S-Q region to cleave strong backbone bonds. These NSD spectra, plus those from variable capillary thermal activation, of 8+ to 11+ ubiquitin ions electrosprayed from denatured solution show backbone cleavages between 74 of 75 amino acid pairs, vs 66 for CAD and 50 for IRMPD in the FTMS cell. Thermal activation by the inlet capillary of the newly desolvated 6+, 7+ ubiquitin ions from electrospraying the native conformer increases the NSD yield from 8% at 56 degrees C to 96% at 76 degrees C, but with little change in product branching ratios; this capillary heating has no effect on CAD or IRMPD of these ions collected in the FTMS cell. Ion desolvation with its concomitant H-bond strengthening appears to produce a transiently stable conformer whose formation can be prevented by capillary heating. The far more complex and stable noncovalent tertiary structures of large protein ions in the gas phase have made MS/MS difficult; initial inhibition of tertiary structure formation with immediate NSD ("prefolding dissociation") appears promising for the top down characterization of a 200-kDa protein. PMID:16159106

Zhai, Huili; Han, Xuemei; Breuker, Kathrin; McLafferty, Fred W

2005-09-15

393

Comparison of zero-point energy constrained and quantum anharmonic Rice-Ramsperger-Kassel-Marcus and phase space theory rate constants for Al3 dissociation  

NASA Astrophysics Data System (ADS)

The ZPE constrained trajectory model is found to retain the ergodicity and intrinsic Rice-Ramsperger-Kassel-Marcus (RRKM) behavior observed previously [J. Chem. Phys. 101, 8535 (1994)] in unconstrained trajectories of Al3 decomposition. Microcanonical unimolecular rate constants for Al3 decomposition are calculated from the ZPE constrained trajectories and compared with the predictions of the vibrator and flexible transition state models of RRKM theory, phase space theory, and the orbiting transition state model of phase space theory (OTS/PST). Quantum anharmonic Al3 vibrational densities of state, determined by a semiclassical approach, are used to calculate these statistical rate constants. Anharmonicity increases the density of states threefold for total energies 1-2 kcal/mol above the classical product asymptotic limit, but has a negligible effect on the Al2---Al transition state sum of states. The ZPE constrained trajectory unimolecular rate constants are in poor agreement with the quantum anharmonic OTS/PST and flexible RRKM rate constants. This is because the ZPE constraint is too restrictive and some of the ZPE constrained trajectories are temporarily trapped in the ZPE forbidden region of phase space. The ZPE constrained trajectory rate constants are smaller than their purely classical counterparts, since Al2 is not formed without its ZPE and thus the effective dissociation threshold is larger for the ZPE constrained trajectories. ZPE constrained sums and densities are calculated by including the ZPE constraint when solving the classical phase integral. RRKM rate constants calculated from these ZPE constrained sums and densities are in much better agreement with the quantum anharmonic OTS/PST and flexible RRKM rate constants, than are those calculated from the ZPE constrained trajectories. The difference between the ZPE constrained RRKM and quantum flexible RRKM rate constants becomes small and much less than the anharmonic correction, for energies slightly in excess of the Al2+Al classical asymptotic limit. This is because the number of real frequencies in the instantaneous normal mode analysis decreases as the total energy is increased, which makes the ZPE constrained RRKM rate constant more accurate. Product energy partitioning from the ZPE constrained trajectories is in good agreement with the predictions of quantum phase space theories, except that the product diatom is formed too rotationally excited. The ZPE constraint scheme retains a spurious frequency and zero-point energy for the Al2---Al bending motion at large separations, which increases the Al2 product rotational energy. The work reported here supports the proposal that a ZPE constraint model, based on an instantaneous normal mode analysis, may be a valid approach for including zero-point energy effects in trajectory simulations of ergodic anharmonic coupled systems. However, additional work needs to be done to remove some of the numerical problems with the current ZPE constraint model and to make the model less restrictive.

Peslherbe, Gilles H.; Hase, William L.

1996-06-01

394

Development of chemically bonded ceramic materials for use in thermal-energy-storage devices  

SciTech Connect

The objective of this program is to develop phosphate and calcium aluminate cement bonded ceramic materials based on North Carolina olivine which are capable of serving as the heat storage media in electric furnaces using the off peak power heating concept. These compositions will be castable refractories formed without the conventional step of powder pressing and cured at temperatures below 315/sup 0/C which eliminates the conventional ceramic firing step which requires temperatures in the range of 1370 to 1480/sup 0/C for olivine bricks. New binder technologies have been developed for use with NC olivines whereby phosphate bonded materials may be produced with cured densities of 2.20 g/cm/sup 3/ (138 lb/ft/sup 3/) which can withstand heating rates of 140/sup 0/C/hr to 1200/sup 0/C without appreciable thermal shock damage. Calcium aluminate cement bonded compositions with densities of 2.30 g/cm/sup 3/ also appear capable of similar heating rates. Experiments with gap-graded castable compositions show further improvements in bulk density and are expected to improve thermal shock properties of the various compositions. Additions of iron oxide rich minerals to the compositions have produced cured densities of 2.58 g/cm/sup 3/ which is similar to the density of commercial fired olivine bricks. These iron oxide rich compositions may have higher volumetric heat capacities than fired olivine bricks. Tasks for FY83 include: continued optimization of compositions; determination of thermal properties; and a component test program using commercial storage heaters.

Brosnan, D.A.

1982-01-01

395

Assembly of HCN hydrogen bonding chains in the gas phase. Binding energies and structures of phenylacetylenerad +(HCN)n clusters, n = 1-4  

NASA Astrophysics Data System (ADS)

The stepwise binding energies (?Hon-1,n) of 1-4 HCN molecules to the phenylacetylene radical cation (C8H6rad +) are determined by equilibrium thermochemical measurements. The binding energy (10.5 ± 1 kcal/mol) of the C8H6rad + (HCN) complex is dominated by the ionic hydrogen bonding interaction (ph-Ctbnd CH?+⋯NCH). For higher clusters, the attachment of HCN molecules occurs through two comparable interactions involving the association of HCN molecules (ph-Ctbnd CH?+⋯NCH⋯NCH⋯) to form a linear hydrogen bonding chain or the interaction with the ring hydrogen atoms through hydrogen bonding (>CH?+⋯NCH) and bifurcated charge-dipole structures. An interesting pattern of the assembly of linear hydrogen bonded chains is observed and could result in the formation of molecular wires of nanometer length scale.

Hamid, Ahmed M.; Soliman, Abdel-Rahman; Samy El-Shall, M.

2012-08-01

396

Activation of methane by size-selected iron cluster cations, Fen+ (n=2-15): Cluster-CHx (x=0-3) bond energies and reaction mechanisms  

NASA Astrophysics Data System (ADS)

The kinetic energy dependences of the reactions of Fen+ (n=2-15) with CD4 are studied in a guided ion beam tandem mass spectrometer over the energy range of 0-10 eV. All reactions exhibit thresholds and two main products, FenD+ and FenCD2+, are formed. These primary products decompose at higher energies to form secondary and higher order products, FenCD+, FenC+, Fen-1D+, Fen-1CD2+, Fen-1CD+, and Fen-1C+. The cross-section magnitudes for the dehydrogenation products, FenCD2+, are observed to vary considerably as a function of cluster size; subsequent dehydrogenation to form FenC+ becomes more facile for larger clusters. Thresholds for the various primary and secondary reactions are analyzed and bond energies for iron cluster cation bonds to C, CD, CD2, and CD3 are determined. As a function of cluster size, these bond energies rapidly reach relatively constant values, which are argued to lie close to bulk phase values. The relative magnitudes in these bond energies are consistent with simple bond order considerations. On the basis of this thermochemistry, we find that there are barriers to the primary dehydrogenation reactions for all the clusters, except n=3 and 4. Evidence that this barrier for n?5 corresponds to the chemisorption step is discussed.

Liyanage, Rohana; Zhang, Xiao-Guang; Armentrout, P. B.

2001-12-01

397

Vibrationally promoted dissociation of water on Ni(111).  

PubMed

Water dissociation on transition-metal catalysts is an important step in steam reforming and the water-gas shift reaction. To probe the effect of translational and vibrational activation on this important heterogeneous reaction, we performed state-resolved gas/surface reactivity measurements for the dissociative chemisorption of D2O on Ni(111), using molecular beam techniques. The reaction occurs via a direct pathway, because both the translational and vibrational energies promote the dissociation. The experimentally measured initial sticking probabilities were used to calibrate a first-principles potential energy surface based on density functional theory. Quantum dynamical calculations on the scaled potential energy surface reproduced the experimental results semiquantitatively. The larger increase of the dissociation probability by vibrational excitation than by translation per unit of energy is consistent with a late barrier along the O-D stretch reaction coordinate. PMID:24786076

Hundt, P Morten; Jiang, Bin; van Reijzen, Maarten E; Guo, Hua; Beck, Rainer D

2014-05-01

398

ELECTRON DETACHMENT DISSOCIATION OF DERMATAN SULFATE OLIGOSACCHARIDES  

PubMed Central

The structural characterization of glycosaminoglycans (GAG) oligosaccharides has been a longstanding challenge in the field of mass spectrometry. In this work, we present the application of electron detachment dissociation (EDD) Fourier transform mass spectrometry to the analysis of dermatan sulfate (DS) oligosaccharides up to 10 residues in length. The EDD mass spectra of DS oligosaccharides were compared to their infrared multiphoton dissociation (IRMPD) mass spectra. EDD produces more abundant fragmentation than IRMPD with far less loss of SO3 from labile sulfate modifications. EDD cleaves all glycosidic bonds, yielding both conventional glycosidic bond fragmentation as well as satellite peaks resulting from the additional loss of 1 or 2 hydrogen atoms. EDD also yields more cross-ring fragmentation than IRMPD. For EDD, abundant cross-ring fragmentation in the form of A- and X-ions is observed, with 1,5Xn cleavages occurring for all IdoA residues and many of the GalNAc4S residues, except at the reducing and nonreducing ends. In contrast, IRMPD produces only A-type cross-ring fragmentation for long oligosaccharides (dp6 – dp10). As all the structurally informative fragment ions observed by IRMPD appear as a subset of the peaks found in the EDD mass spectrum, EDD shows great potential for the characterization of GAG oligosaccharides using a single tandem mass spectrometry experiment. PMID:18055211

Wolff, Jeremy J.; Laremore, Tatiana N.; Busch, Alexander M.; Linhardt, Robert J.; Amster, I. Jonathan

2009-01-01

399

Above-threshold dissociative ionization in the intermediate intensity regime.  

PubMed

The problem of dissociative ionization at intermediate intensities ( 10(10)-10(12) W cm(-2)) was studied using the example of I2 and the technique of velocity map imaging. Several new phenomena were observed, including a continuous distribution of recoil energies peaked at zero-kinetic energy, a set of constant dissociative ionic states, and strong anisotropy of the fragment velocity distribution that is diminished by intermediate resonances. PMID:11289900

Unny, S; Du, Y; Zhu, L; Gordon, R J; Sugita, A; Kawasaki, M; Matsumi, Y; Seideman, T

2001-03-12

400

Theoretical studies of dissociative recombination  

NASA Technical Reports Server (NTRS)

The calculation of dissociative recombination rates and cross sections over a wide temperature range by theoretical quantum chemical techniques is described. Model calculations on electron capture by diatomic ions are reported which illustrate the dependence of the rates and cross sections on electron energy, electron temperature, and vibrational temperature for three model crossings of neutral and ionic potential curves. It is shown that cross sections for recombination to the lowest vibrational level of the ion can vary by several orders of magnitude depending upon the position of the neutral and ionic potential curve crossing within the turning points of the v = 1 vibrational level. A new approach for calculating electron capture widths is reported. Ab initio calculations are described for recombination of O2(+) leading to excited O atoms.

Guberman, S. L.

1985-01-01