N2O molecular tagging velocimetry

NASA Astrophysics Data System (ADS)

ElBaz, A. M.; Pitz, R. W.

2012-03-01

A new seeded velocity measurement technique, N2O molecular tagging velocimetry (MTV), is developed to measure velocity in wind tunnels by photochemically creating an NO tag line. Nitrous oxide "laughing gas" is seeded into the air flow. A 193 nm ArF excimer laser dissociates the N2O to O(1D) that subsequently reacts with N2O to form NO. O2 fluorescence induced by the ArF laser "writes" the original position of the NO line. After a time delay, the shifted NO line is "read" by a 226-nm laser sheet and the velocity is determined by time-of-flight. At standard atmospheric conditions with 4% N2O in air, ˜1000 ppm of NO is photochemically created in an air jet based on experiment and simulation. Chemical kinetic simulations predict 800-1200 ppm of NO for 190-750 K at 1 atm and 850-1000 ppm of NO for 0.25-1 atm at 190 K. Decreasing the gas pressure (or increasing the temperature) increases the NO ppm level. The presence of humid air has no significant effect on NO formation. The very short NO formation time (<10 ns) makes the N2O MTV method amenable to low- and high-speed air flow measurements. The N2O MTV technique is demonstrated in air jet to measure its velocity profile. The N2O MTV method should work in other gas flows as well (e.g., helium) since the NO tag line is created by chemical reaction of N2O with O(1D) from N2O photodissociation and thus does not depend on the bulk gas composition.

Properties of fluorosulfate-based ionic liquids and geometries of (FO2SOH)OSO2F- and (FO2SOH)2O2SOF-.

PubMed

Enomoto, Takeshi; Matsumoto, Kazuhiko; Hagiwara, Rika

2011-12-14

A room temperature ionic liquid (IL) based on the fluorosulfate anion (SO(3)F(-)) has been synthesized by the reaction of 1-ethyl-3-methylimidazolium (EMIm(+)) chloride and fluorosulfuric acid (HOSO(2)F). The viscosity, ionic conductivity, and electrochemical window of EMImSO(3)F at 25 °C are 46.6 mPa s, 10.8 mS cm(-1), and 4.3 V, respectively. According to a solvatochromic measurement using ILs, there is a trend in the donor ability of fluoro- and oxofluoroanions, PF(6)(-) < BF(4)(-) < N(SO(2)CF(3))(2)(-) < SO(3)CF(3)(-) < SO(3)F(-) < PO(2)F(2)(-), which is explained by the atomic charges obtained from quantum mechanical calculations. The 1 : 2 and 1 : 3 stoichiometric reactions of EMImCl and HOSO(2)F give EMIm(FO(2)SOH)OSO(2)F and EMIm(FO(2)SOH)(2)O(2)SOF, respectively. Both the salts are liquid at room temperature without a HOSO(2)F dissociation pressure (< 1 Pa) and have low viscosity and high ionic conductivity (9.2 mPa s and 30.8 mS cm(-1) for EMIm(FO(2)SOH)OSO(2)F and 5.1 mPa s and 43.2 mS cm(-1) for EMIm(FO(2)SOH)(2)O(2)SOF). The vibrational modes and bonding properties of these anionic species are discussed with the aid of quantum mechanical calculations. The (FO(2)SOH)OSO(2)F(-) anion in EMIm(FO(2)SOH)OSO(2)F does not have an inversion centre, which stands in contrast to the one with an inversion centre (e.g. observed in solid Cs(FO(2)SOH)OSO(2)F). The (FO(2)SOH)(2)O(2)SOF(-) anion in EMIm(FO(2)SOH)(2)O(2)SOF is characterized by vibrational spectroscopy under C(s) symmetry.

Fluoride ion donor properties of cis-OsO(2)F(4): synthesis, raman spectroscopic study, and X-ray crystal structure of [OsO(2)F(3)][Sb(2)F(11)].

PubMed

Hughes, Michael J; Mercier, Hélène P A; Schrobilgen, Gary J

2010-01-04

The salt, [OsO(2)F(3)][Sb(2)F(11)], has been synthesized by dissolution of cis-OsO(2)F(4) in liquid SbF(5), followed by removal of excess SbF(5) at 0 degrees C to yield orange, crystalline [OsO(2)F(3)][Sb(2)F(11)]. The X-ray crystal structure (-173 degrees C) consists of an OsO(2)F(3)(+) cation fluorine bridged to an Sb(2)F(11)(-) anion. The light atoms of OsO(2)F(3)(+) and the bridging fluorine atom form a distorted octahedron around osmium in which the osmium atom is displaced from its center toward an oxygen atom and away from the trans-fluorine bridge atom. As in other transition metal dioxofluorides, the oxygen ligands are cis to one another and the fluorine bridge atom is trans to an oxygen ligand and cis to the remaining oxygen ligand. The Raman spectrum (-150 degrees C) of solid [OsO(2)F(3)][Sb(2)F(11)] was assigned on the basis of the ion pair observed in the low-temperature crystal structure. Under dynamic vacuum, [OsO(2)F(3)][Sb(2)F(11)] loses SbF(5), yielding the known [mu-F(OsO(2)F(3))(2)][Sb(2)F(11)] salt with no evidence for [OsO(2)F(3)][SbF(6)] formation. Attempts to synthesize [OsO(2)F(3)][SbF(6)] by the reaction of [OsO(2)F(3)][Sb(2)F(11)] with an equimolar amount of cis-OsO(2)F(4) or by a 1:1 stoichiometric reaction of cis-OsO(2)F(4) with SbF(5) in anhydrous HF yielded only [mu-F(OsO(2)F(3))(2)][Sb(2)F(11)]. Quantum-chemical calculations at the SVWN and B3LYP levels of theory and natural bond orbital analyses were used to calculate the gas-phase geometries, vibrational frequencies, natural population analysis charges, bond orders, and valencies of OsO(2)F(3)(+), [OsO(2)F(3)][Sb(2)F(11)], [OsO(2)F(3)][SbF(6)], and Sb(2)F(11)(-). The relative thermochemical stabilities of [OsO(2)F(3)][SbF(6)], [OsO(2)F(3)][Sb(2)F(11)], [OsO(2)F(3)][AsF(6)], [mu-F(OsO(2)F(3))(2)][SbF(6)], [mu-F(OsO(2)F(3))(2)][Sb(2)F(11)], and [mu-F(OsO(2)F(3))(2)][AsF(6)] were assessed using the appropriate Born-Haber cycles to account for the preference for [mu-F(OsO(2)F(3))(2

Production of N2O/+/ by reaction of metastable O2/+/ ions with N2

NASA Technical Reports Server (NTRS)

Ajello, J. M.; Rayermann, P.

1975-01-01

Photoionization mass spectrometry examination of the production of N2O(+) was undertaken to determine whether N2(+) or O2(+) ions are responsible for onset of N2O(+). It appears that the N2(+) ion does not contribute significantly to the production of N2O(+) in this experiment. Therefore, it is clear that excited O2(+) is responsible for the formation of N2O(+) near the appearance potential of these ions.

Study of structure and antireflective properties of LaF3/HfO2/SiO2 and LaF3/HfO2/MgF2 trilayers for UV applications

NASA Astrophysics Data System (ADS)

Marszalek, K.; Jaglarz, J.; Sahraoui, B.; Winkowski, P.; Kanak, J.

2015-01-01

The aim of this paper is to study antireflective properties of the tree-layer systems LaF3/HfO2/SiO2 and LaF3/HfO2/MgF2 deposited on heated optical glass substrates. The films were evaporated by the use two deposition techniques. In first method oxide films were prepared by means of e-gun evaporation in vacuum of 5 × 10-5 mbar in the presence of oxygen. The second was used for the deposition of fluoride films. They were obtained by means of thermal source evaporation. Simulation of reflectance was performed for 1M2H1L (Quarter Wavelength Optical Thickness) film stack on an optical quartz glass with the refractive index n = 1.46. The layer thickness was optimized to achieve the lowest light scattering from glass surface covered with dioxide and fluoride films. The values of the interface roughness were determined through atomic force microscopy measurements. The essence of performed calculation was to find minimum reflectance of light in wide ultraviolet region. The spectral dispersion of the refractive index needed for calculations was determined from ellipsometric measurements using the spectroscopic ellipsometer M2000. Additionally, the total reflectance measurements in integrating sphere coupled with Perkin Elmer 900 spectrophotometer were performed. These investigations allowed to determine the influence of such film features like surface and interface roughness on light scattering.

Description and crystal structure of albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O

NASA Astrophysics Data System (ADS)

Mereiter, Kurt

2013-04-01

Albrechtschraufite, MgCa4F2[UO2(CO3)3]2ṡ17-18H2O, triclinic, space group Pī, a = 13.569(2), b = 13.419(2), c = 11.622(2) Å, α = 115.82(1), β = 107.61(1), γ = 92.84(1)° (structural unit cell, not reduced), V = 1774.6(5) Å3, Z = 2, D c = 2.69 g/cm3 (for 17.5 H2O), is a mineral that was found in small amounts with schröckingerite, NaCa3F[UO2(CO3)3](SO4)ṡ10H2O, on a museum specimen of uranium ore from Joachimsthal (Jáchymov), Czech Republic. The mineral forms small grain-like subhedral crystals (≤ 0.2 mm) that resemble in appearance liebigite, Ca2[UO2(CO3)3]ṡ ~ 11H2O. Colour pale yellow-green, luster vitreous, transparent, pale bluish green fluorescence under ultraviolet light. Optical data: Biaxial negative, nX = 1.511(2), nY = 1.550(2), nZ = 1.566(2), 2 V = 65(1)° ( λ = 589 nm), r < v weak. After qualitative tests had shown the presence of Ca, U, Mg, CO2 and H2O, the chemical formula was determined by a crystal structure analysis based on X-ray four-circle diffractometer data. The structure was later on refined with data from a CCD diffractometer to R1 = 0.0206 and wR2 = 0.0429 for 9,236 independent observed reflections. The crystal structure contains two independent [UO2(CO3)3]4- anions of which one is bonded to two Mg and six Ca while the second is bonded to only one Mg and three Ca. Magnesium forms a MgF2(Ocarbonate)3(H2O) octahedron that is linked via the F atoms with three Ca atoms so as to provide each F atom with a flat pyramidal coordination by one Mg and two Ca. Calcium is 7- and 8-coordinate forming CaFO6, CaF2O2(H2O)4, CaFO3(H2O)4 and CaO2(H2O)6 coordination polyhedra. The crystal structure is built up from MgCa3F2[UO2(CO3)3]ṡ8H2O layers parallel to (001) which are linked by Ca[UO2(CO3)3]ṡ5H2O moieties into a framework of the composition MgCa4F2[UO2(CO3)3]ṡ13H2O. Five additional water molecules are located in voids of the framework and show large displacement parameters. One of the water positions is partly vacant, leading to a

Studies of CW lasing action in CO2-CO, N2O-CO, CO2-H2O, and N2O-H2O mixtures pumped by blackbody radiation

NASA Technical Reports Server (NTRS)

Abel, Robert W.; Christiansen, Walter H.; Li, Jian-Guo

1988-01-01

A proof of principle experiment to evaluate the efficacy of CO and H2O in increasing the power output for N2O and CO2 lasing mixtures has been conducted and theoretically analyzed for a blackbody radiation-pumped laser. The results for N2O-CO, CO2-CO, N2O-H2O and CO2-H2O mixtures are presented. Additions of CO to the N2O lasant increased power up to 28 percent for N2O laser mixtures, whereas additions of CO to the CO2 lasant, and the addition of H2O to both the CO2 and N2O lasants, resulted in decreased output power.

Quenching of I(2P1/2) by NO2, N2O4, and N2O.

PubMed

Kabir, Md Humayun; Azyazov, Valeriy N; Heaven, Michael C

2007-10-11

Quenching of excited iodine atoms (I(5p5, 2P1/2)) by nitrogen oxides are processes of relevance to discharge-driven oxygen iodine lasers. Rate constants at ambient and elevated temperatures (293-380 K) for quenching of I(2P1/2) atoms by NO2, N2O4, and N2O have been measured using time-resolved I(2P1/2) --> I(2P3/2) 1315 nm emission. The excited atoms were generated by pulsed laser photodissociation of CF3I at 248 nm. The rate constants for I(2P1/2) quenching by NO2 and N2O were found to be independent of temperature over the range examined with average values of (2.9 +/- 0.3) x 10(-15) and (1.4 +/- 0.1) x 10(-15) cm3 s(-1), respectively. The rate constant for quenching of I(2P1/2) by N2O4 was found to be (3.5 +/- 0.5) x 10(-13) cm3 s(-1) at ambient temperature.

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O.

PubMed

Wang, Xiao-Gang; Carrington, Tucker

2015-07-14

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

NASA Astrophysics Data System (ADS)

Wang, Xiao-Gang; Carrington, Tucker

2015-07-01

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

Silicon nitride and silicon etching by CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams

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

Kaler, Sanbir S.; Lou, Qiaowei; Donnelly, Vincent M., E-mail: vmdonnelly@uh.edu

2016-07-15

Silicon nitride (SiN, where Si:N ≠ 1:1) films low pressure-chemical vapor deposited on Si substrates, Si films on Ge on Si substrates, and p-Si samples were exposed to plasma beams emanating from CH{sub 3}F/O{sub 2} or CH{sub 3}F/CO{sub 2} inductively coupled plasmas. Conditions within the plasma beam source were maintained at power of 300 W (1.9 W/cm{sup 3}), pressure of 10 mTorr, and total gas flow rate of 10 sccm. X-ray photoelectron spectroscopy was used to determine the thicknesses of Si/Ge in addition to hydrofluorocarbon polymer films formed at low %O{sub 2} or %CO{sub 2} addition on p-Si and SiN. Polymer film thickness decreasedmore » sharply as a function of increasing %O{sub 2} or %CO{sub 2} addition and dropped to monolayer thickness above the transition point (∼48% O{sub 2} or ∼75% CO{sub 2}) at which the polymer etchants (O and F) number densities in the plasma increased abruptly. The C(1s) spectra for the polymer films deposited on p-Si substrates appeared similar to those on SiN. Spectroscopic ellipsometry was used to measure the thickness of SiN films etched using the CH{sub 3}F/O{sub 2} and CH{sub 3}F/CO{sub 2} plasma beams. SiN etching rates peaked near 50% O{sub 2} addition and 73% CO{sub 2} addition. Faster etching rates were measured in CH{sub 3}F/CO{sub 2} than CH{sub 3}F/O{sub 2} plasmas above 70% O{sub 2} or CO{sub 2} addition. The etching of Si stopped after a loss of ∼3 nm, regardless of beam exposure time and %O{sub 2} or %CO{sub 2} addition, apparently due to plasma assisted oxidation of Si. An additional GeO{sub x}F{sub y} peak was observed at 32.5 eV in the Ge(3d) region, suggesting deep penetration of F into Si, under the conditions investigated.« less

Synthesis and characterization of new fluoride-containing manganese vanadates A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F

NASA Astrophysics Data System (ADS)

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.; McMillen, Colin D.; Ovidiu Garlea, V.; Willett, Daniel; Chumanov, George; Kolis, Joseph W.

2016-09-01

Large single crystals of A2Mn2V2O7F2 (A=Rb, Cs) and Mn2VO4F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO4F2 building blocks. The A2Mn2V2O7F2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb2Mn2V2O7F2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs2Mn2V2O7F2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains of edge-sharing MnO4F2 units running along the a-axis, and interconnected through V2O7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn2+ indicated that Cs2Mn2V2O7F2 is antiferromagnetic with a Neél temperature, TN=~3 K and a Weiss constant, θ, of -11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V-O vibrational modes in Cs2Mn2V2O7F2. Mn2(VO4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn2+. These interpenetrating chains are additionally connected through isolated VO4 tetrahedra to form the condensed structure.

Synthesis and characterization of new fluoride-containing manganese vanadates A 2Mn 2V 2O 7F 2 (A=Rb, Cs) and Mn 2VO 4F

DOE PAGES

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.; ...

2016-05-10

In large single crystals of A 2Mn 2V 2O 7F 2 (A=Rb, Cs) and Mn 2VO 4F were grown using a high-temperature (~600 °C) hydrothermal technique. We utilized single crystal X-ray diffraction and powder X-ray diffraction in order to characterize the structures, which both possess MnO 4F 2 building blocks. The A 2Mn 2V 2O 7F 2 series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb 2Mn 2V 2O 7F 2: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs 2Mn 2V 2O 7F 2: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed ofmore » zigzag chains of edge-sharing MnO 4F 2 units running along the a-axis, and interconnected through V 2O 7 pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn 2+ indicated that Cs 2Mn 2V 2O 7F 2 is antiferromagnetic with a Neél temperature, TN=~3 K and a Weiss constant, θ, of -11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs 2Mn 2V 2O 7F 2. Mn 2(VO 4)F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn 2+. Our interpenetrating chains are additionally connected through isolated VO 4 tetrahedra to form the condensed structure.« less

O2 Herzberg State Reaction with N2: A Possible Source of Stratospheric N2O

NASA Technical Reports Server (NTRS)

Slanger, Tom G.; Copeland, Richard A.

1997-01-01

The goal of this one-year investigation was to determine whether N2O is formed in atmospherically significant quantities by the reaction of vibrationally excited levels of the O2((A3 Sigma(sub u)(sup +)) state with nitrogen. O2(A3 Sigma(sub u)(sup +)) is made throughout the upper stratosphere in considerable amounts by solar photoabsorption, and only a very small reactive yield is necessary for this mechanism to be a major N2O source. By long-term 245-252 nm irradiation of O2/N2 mixtures on- and off-resonance with absorption lines in the O2(A3 Sigma(sub u)(sup +) - X3 Sigma(sub g)(sup -)) transition, followed by N2O analysis by frequency-modulated diode laser absorption spectroscopy, we determined an upper limit for the N2O yield of the candidate reaction. This limit, 3 x 10(exp -5), eliminates O2(A3 Sigma(sub u)(sup +)) + N2 as a significant channel for the generation of stratospheric N2O. In further measurements, we established that N2O is stable under our photolysis conditions, showing that the small amounts of ozone generated from the reaction of O2(A) and O2 do not indirectly lead to destruction of N2O.

Conversion of nitrogen oxides in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures subjected to a dc corona discharge

NASA Astrophysics Data System (ADS)

Dors, Mirosław; Mizeraczyk, Jerzy

1996-10-01

This paper concerns the influence of a direct current (dc) corona discharge on production and reduction of NO, NO2 and N2O in N2:O2:CO2 and N2:O2:CO2:NO2 mixtures. The corona discharge was generated in a needle-to-plate reactor. The positively polarized electrode consisted of 7 needles. The grounded electrode was a stainless steel plate. The gas flow rate through the reactor was varied from 28 to 110 cm3/s. The time-averaged discharge current ranged from 0 to 6 mA. It was found that in the N2:O2:CO2 mixture the corona discharge produced NO, NO2 and N2O. In the N2:O2:CO2:NO2 mixture the reduction of NO2 was between 6-56%, depending on the concentration of O2, gas flow rate and corona discharge current. The NO2 reduction was accompanied by production of NO and N2O. The results show that efficient reduction of nitrogen oxides by a corona discharge cannot be expected in the mixtures containing N2 and O2 if reducing additives are not employed.

Activation Strain Analysis of SN2 Reactions at C, N, O, and F Centers.

PubMed

Kubelka, Jan; Bickelhaupt, F Matthias

2017-02-02

Fundamental principles that determine chemical reactivity and reaction mechanisms are the very foundation of chemistry and many related fields of science. Bimolecular nucleophilic substitutions (S N 2) are among the most common and therefore most important reaction types. In this report, we examine the trends in the S N 2 reactions with respect to increasing electronegativity of the reaction center by comparing the well-studied backside S N 2 Cl - + CH 3 Cl with similar Cl - substitutions on the isoelectronic series with the second period elements N, O, and F in place of C. Relativistic (ZORA) DFT calculations are used to construct the gas phase reaction potential energy surfaces (PES), and activation strain analysis, which allows decomposition of the PES into the geometrical strain and interaction energy, is employed to analyze the observed trends. We find that S N 2@N and S N 2@O have similar PES to the prototypical S N 2@C, with the well-defined reaction complex (RC) local minima and a central barrier, but all stationary points are, respectively, increasingly stable in energy. The S N 2@F, by contrast, exhibits only a single-well PES with no barrier. Using the activation strain model, we show that the trends are due to the interaction energy and originate mainly from the decreasing energy of the empty acceptor orbital (σ* A-Cl ) on the reaction center A in the order of C, N, O, and F. The decreasing steric congestion around the central atom is also a likely contributor to this trend. Additional decomposition of the interaction energy using Kohn-Sham molecular orbital (KS-MO) theory provides further support for this explanation, as well as suggesting electrostatic energy as the primary reason for the distinct single-well PES profile for the FCl reaction.

O2-O2 and O2-N2 collision-induced absorption mechanisms unravelled

NASA Astrophysics Data System (ADS)

Karman, Tijs; Koenis, Mark A. J.; Banerjee, Agniva; Parker, David H.; Gordon, Iouli E.; van der Avoird, Ad; van der Zande, Wim J.; Groenenboom, Gerrit C.

2018-05-01

Collision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O2 that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O2-O2 and O2-N2, using analytical models and numerical quantum scattering calculations. We unambiguously identify the underlying absorption mechanism, which is shown to depend explicitly on the collision partner—contrary to textbook knowledge. This explains experimentally observed qualitative differences between O2-O2 and O2-N2 collisions in the overall intensity, line shape and vibrational dependence of the absorption spectrum. It is shown that these results can be used to discriminate between conflicting experimental data and even to identify unphysical results, thus impacting future experimental studies and atmospheric applications.

Selective Encaging of N2O in N2O-N2 Binary Gas Hydrates via Hydrate-Based Gas Separation.

PubMed

Yang, Youjeong; Shin, Donghoon; Choi, Seunghyun; Woo, Yesol; Lee, Jong-Won; Kim, Dongseon; Shin, Hee-Young; Cha, Minjun; Yoon, Ji-Ho

2017-03-21

The crystal structure and guest inclusion behaviors of nitrous oxide-nitrogen (N 2 O-N 2 ) binary gas hydrates formed from N 2 O/N 2 gas mixtures are determined through spectroscopic analysis. Powder X-ray diffraction results indicate that the crystal structure of all the N 2 O-N 2 binary gas hydrates is identified as the structure I (sI) hydrate. Raman spectra for the N 2 O-N 2 binary gas hydrate formed from N 2 O/N 2 (80/20, 60/40, 40/60 mol %) gas mixtures reveal that N 2 O molecules occupy both large and small cages of the sI hydrate. In contrast, there is a single Raman band of N 2 O molecules for the N 2 O-N 2 binary gas hydrate formed from the N 2 O/N 2 (20/80 mol %) gas mixture, indicating that N 2 O molecules are trapped in only large cages of the sI hydrate. From temperature-dependent Raman spectra and the Predictive Soave-Redlich-Kwong (PSRK) model calculation, we confirm the self-preservation of N 2 O-N 2 binary gas hydrates in the temperature range of 210-270 K. Both the experimental measurements and the PSRK model calculations demonstrate the preferential occupation of N 2 O molecules rather than N 2 molecules in the hydrate cages, leading to a possible process for separating N 2 O from gas mixtures via hydrate formation. The phase equilibrium conditions, pseudo-pressure-composition (P-x) diagram, and gas storage capacity of N 2 O-N 2 binary gas hydrates are discussed in detail.

Low-k SiOCH Film Etching Process and Its Diagnostics Employing Ar/C5F10O/N2 Plasma

NASA Astrophysics Data System (ADS)

Nagai, Mikio; Hayashi, Takayuki; Hori, Masaru; Okamoto, Hidekazu

2006-09-01

We proposed an environmental harmonic etching gas of C5F10O (CF3CF2CF2OCFCF2), and demonstrated the etching of low-k SiOCH films employing a dual-frequency capacitively coupled etching system. Dissociative ionization cross sections for the electron impact ionizations of C5F10O and c-C4F8 gases have been measured by quadrupole mass spectroscopy (QMS). The dissociative ionization cross section of CF3+ from C5F10O gas was much higher than those of other ionic species, and 10 times higher than that of CF3+ from C4F8 gas. CF3+ is effective for increasing the etching rate of SiO2. As a result, the etching rate of SiOCH films using Ar/C5F10O/N2 plasma was about 1000 nm/min, which is much higher than that using Ar/C4F8/N2 plasma. The behaviours of fluorocarbon radicals in Ar/C5F10O/N2 plasma, which were measured by infrared diode laser absorption spectroscopy, were similar to those in Ar/C4F8/N2 plasma. The densities of CF and CF3 radicals were markedly decreased with increasing N2 flow rate. Etching rate was controlled by N2 flow rate. A vertical profile of SiOCH with a high etching rate and less microloading was realized using Ar/C5F10O/N2 plasma chemistry.

First-principles calculation on electronic structure and optical property of BaSi{sub 2}O{sub 2}N{sub 2}:Eu{sup 2+} phosphor

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

Tong, Zhi-Fang, E-mail: tongzhifang1998@126.com; Wei, Zhan-Long; Xiao, Cheng

The crystal structure, electronic structure and optical properties of BaSi{sub 2}O{sub 2}N{sub 2}:Eu{sup 2+} with varying Eu doping concentrations are computed by the density functional theory (DFT) and compared with experimental results. The results show that the lattice parameters of primitive cells of Ba{sub 1−x}Si{sub 2}O{sub 2}N{sub 2}:Eu{sub x} become smaller and Eu–N bond length shortens as Eu concentration increases. The band structure of Ba{sub 1−x}Si{sub 2}O{sub 2}N{sub 2}:Eu{sub x} exhibits a direct optical band gap and it's propitious to luminescence. The energy differences from the lowest Eu 5d state to the lowest Eu 4f state decrease with increasing Eumore » concentrations. The analysis of simulative absorption spectra indicates that the electron transition from Eu 4f states to 5d states of both Eu and Ba atoms contributes to the absorption of Ba{sub 1−x}Si{sub 2}O{sub 2}N{sub 2}:Eu{sub x}. Under the coupling effect between Eu and Ba, Ba in BaSi{sub 2}O{sub 2}N{sub 2} exhibits longer wavelength absorption and increases absorption efficiency. The emission wavelength is deduced by measuring energy differences from the lowest Eu 5d state to the lowest Eu 4f state, and the result is in good agreement with experimental value within experimental Eu{sup 2+} doping range. - Graphical abstract: The structure and optical property of BaSi{sub 2}O{sub 2}N{sub 2}:Eu{sup 2+} are computed by DFT and its absorption mechanism is analysed. Results show that absorption peak α is from the host lattice absorption. The absorption peaks β, γ and δ are from Eu 4f to Eu 5d and Ba 6s 5d states. The absorption is attributed to the coupling effect of Eu and Ba atom. - Highlights: • The crystal, electronic structure and optical properties of BaSi{sub 2}O{sub 2}N{sub 2}:Eu{sup 2+} are computed by DFT. • The lattice parameters of primitive cells reduces and Eu–N bond length shortens as Eu{sup 2+} increases. • The energy gap from Eu 5d state to Eu 4f state

Synthesis and characterization of new fluoride-containing manganese vanadates A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F

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

Sanjeewa, Liurukara D.; McGuire, Michael A.; Smith Pellizzeri, Tiffany M.

2016-09-15

Large single crystals of A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}VO{sub 4}F were grown using a high-temperature (~600 °C) hydrothermal technique. Single crystal X-ray diffraction and powder X-ray diffraction were utilized to characterize the structures, which both possess MnO{sub 4}F{sub 2} building blocks. The A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} series crystallizes as a new structure type in space group Pbcn (No. 60), Z=4 (Rb{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.4389(17) Å, b=11.574(3) Å, c=10.914(2) Å; Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}: a=7.5615(15) Å, b=11.745(2) Å, c=11.127(2) Å). The structure is composed of zigzag chains ofmore » edge-sharing MnO{sub 4}F{sub 2} units running along the a-axis, and interconnected through V{sub 2}O{sub 7} pyrovanadate groups. Temperature dependent magnetic susceptibility measurements on this interesting one-dimensional structural feature based on Mn{sup 2+} indicated that Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} is antiferromagnetic with a Neél temperature, T{sub N}=~3 K and a Weiss constant, θ, of −11.7(1) K. Raman and infrared spectra were also analyzed to identify the fundamental V–O vibrational modes in Cs{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2}. Mn{sub 2}(VO{sub 4})F crystalizes in the monoclinic space group of C2/c (no. 15), Z=8 with unit cell parameters of a=13.559(2) Å, b=6.8036(7) Å, c=10.1408(13) Å and β=116.16(3)°. The structure is associated with those of triplite and wagnerite. Dynamic fluorine disorder gives rise to complex alternating chains of five-and six-coordinate Mn{sup 2+}. These interpenetrating chains are additionally connected through isolated VO{sub 4} tetrahedra to form the condensed structure. - Graphical abstract: New vanadate fluorides A{sub 2}Mn{sub 2}V{sub 2}O{sub 7}F{sub 2} (A=Rb, Cs) and Mn{sub 2}(VO{sub 4})F have been synthesized hydrothermally. Upon cooling, the one-dimensional Mn(II) substructure results in

Comparison of Multilayer Dielectric Thin Films for Future Metal-Insulator-Metal Capacitors: Al2O3/HfO2/Al2O3 versus SiO2/HfO2/SiO2

NASA Astrophysics Data System (ADS)

Park, Sang-Uk; Kwon, Hyuk-Min; Han, In-Shik; Jung, Yi-Jung; Kwak, Ho-Young; Choi, Woon-Il; Ha, Man-Lyun; Lee, Ju-Il; Kang, Chang-Yong; Lee, Byoung-Hun; Jammy, Raj; Lee, Hi-Deok

2011-10-01

In this paper, two kinds of multilayered metal-insulator-metal (MIM) capacitors using Al2O3/HfO2/Al2O3 (AHA) and SiO2/HfO2/SiO2 (SHS) were fabricated and characterized for radio frequency (RF) and analog mixed signal (AMS) applications. The experimental results indicate that the AHA MIM capacitor (8.0 fF/µm2) is able to provide a higher capacitance density than the SHS MIM capacitor (5.1 fF/µm2), while maintaining a low leakage current of about 50 nA/cm2 at 1 V. The quadratic voltage coefficient of capacitance, α gradually decreases as a function of stress time under constant voltage stress (CVS). The parameter variation of SHS MIM capacitors is smaller than that of AHA MIM capacitors. The effects of CVS on voltage linearity and time-dependent dielectric breakdown (TDDB) characteristics were also investigated.

The structure, stability, and infrared spectrum of B 2N, B 2N +, B 2N -, BO, B 2O and B 2N 2.

NASA Astrophysics Data System (ADS)

Martin, J. M. L.; François, J. P.; Gijbels, R.

1992-05-01

The structure, infrared spectrum, and heat of formation of B 2N, B 2N -, BO, and B 2O have been studied ab initio. B 2N is very stable; B 2O even more so. B 2N, B 2N -, B 2O, and probably B 2N + have symmetric linear ground-state structures; for B 2O, an asymmetric linear structure lies about 12 kcal/mol above the ground state. B 2N +, B 2N - and B 2O have intense asymmetric stretching frequencies, predicted near 870, 1590 and 1400 cm -1, respectively. Our predicted harmonic frequencies and isotopic shifts for B 2O confirm the recent experimental identification by Andrews and Burkholder. Absorptions at 1889.5 and 1998.5 cm -1 in noble-gas trapped boron nitride vapor belong the BNB and BNBN ( 3Π), respectively; a tentative assignment of 882.5 cm -1 to BNB + is proposed. Total atomization energies Σ De (Σ D0) are computed (accuracy ±2 kcal/mol) as: BO 193.1 (190.4), B 2O 292.5 (288.7), B 2N 225.0 (250.3) kcal/mol. The ionization potential and electron affinity of B 2N are predicted to be 8.62±0.1 and 3.34±0.1 eV. The MP4-level additivity approximations involved in G1 theory results in errors on the order of 1 kcal/mol in the Σ De values.

Structures and Spectroscopic Properties of F-(H2O) n with n = 1-10 Clusters from a Global Search Based On Density Functional Theory.

PubMed

Shi, Ruili; Wang, Pengju; Tang, Lingli; Huang, Xiaoming; Chen, Yonggang; Su, Yan; Zhao, Jijun

2018-04-05

Using a genetic algorithm incorporated in density functional theory, we explore the ground state structures of fluoride anion-water clusters F - (H 2 O) n with n = 1-10. The F - (H 2 O) n clusters prefer structures in which the F - anion remains at the surface of the structure and coordinates with four water molecules, as the F - (H 2 O) n clusters have strong F - -H 2 O interactions as well as strong hydrogen bonds between H 2 O molecules. The strong interaction between the F - anion and adjacent H 2 O molecule leads to a longer O-H distance in the adjacent molecule than in an individual water molecule. The simulated infrared (IR) spectra of the F - (H 2 O) 1-5 clusters obtained via second-order vibrational perturbation theory (VPT2) and including anharmonic effects reproduce the experimental results quite well. The strong interaction between the F - anion and water molecules results in a large redshift (600-2300 cm -1 ) of the adjacent O-H stretching mode. Natural bond orbital (NBO) analysis of the lowest-energy structures of the F - (H 2 O) 1-10 clusters illustrates that charge transfer from the lone pair electron orbital of F - to the antibonding orbital of the adjacent O-H is mainly responsible for the strong interaction between the F - anion and water molecules, which leads to distinctly different geometric and vibrational properties compared with neutral water clusters.

The First Molybdenum(VI) and Tungsten(VI) Oxoazides MO2(N3)2, MO2(N3)2⋅2 CH3CN, (bipy)MO2(N3)2, and [MO2(N3)4](2-) (M=Mo, W).

PubMed

Haiges, Ralf; Skotnitzki, Juri; Fang, Zongtang; Dixon, David A; Christe, Karl O

2015-08-10

Molybdenum(VI) and tungsten(VI) dioxodiazide, MO2(N3)2 (M=Mo, W), were prepared through fluoride-azide exchange reactions between MO2F2 and Me3SiN3 in SO2 solution. In acetonitrile solution, the fluoride-azide exchange resulted in the isolation of the adducts MO2(N3)2⋅2 CH3CN. The subsequent reaction of MO2(N3)2 with 2,2'-bipyridine (bipy) gave the bipyridine adducts (bipy)MO2(N3)2. The hydrolysis of (bipy)MoO2(N3)2 resulted in the formation and isolation of [(bipy)MoO2N3]2O. The tetraazido anions [MO2(N3)4](2-) were obtained by the reaction of MO2(N3)2 with two equivalents of ionic azide. Most molybdenum(VI) and tungsten(VI) dioxoazides were fully characterized by their vibrational spectra, impact, friction, and thermal sensitivity data and, in the case of (bipy)MoO2(N3)2, (bipy)WO2(N3)2, [PPh4]2[MoO2(N3)4], [PPh4]2[WO2(N3)4], and [(bipy)MoO2N3]2O by their X-ray crystal structures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical characterization of Tm(3+) doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2.

PubMed

Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

2016-08-10

In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd-Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm(3+) ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH(-) absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10(-21) cm(2)) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm(3+): (4)F3 → (3)H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation ((3)H6 + (3)H4 → (3)F4 + (3)F4) rate. Our results suggest that the Tm(3+) doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system.

Optical characterization of Tm3+ doped Bi2O3-GeO2-Ga2O3 glasses in absence and presence of BaF2

PubMed Central

Han, Kexuan; Zhang, Peng; Wang, Shunbin; Guo, Yanyan; Zhou, Dechun; Yu, Fengxia

2016-01-01

In this paper, Two new Bi2O3-GeO2-Ga2O3 glasses (one presence of BaF2) doped with 1mol% Tm2O3 were prepared by melt-quenching technique. Differential thermal analysis (DTA), the absorption, Raman, IR spectra and fluorescence spectra were measured. The Judd–Ofelt intensity parameters, emission cross section, absorption cross section, and gain coefficient of Tm3+ ions were comparatively investigated. After the BaF2 introduced, the glass showed a better thermal stability, lower phonon energy and weaker OH− absorption coefficient, meanwhile, a larger ~1.8 μm emission cross section σem (7.56 × 10−21 cm2) and a longer fluorescence lifetime τmea (2.25 ms) corresponding to the Tm3+: 4F3 → 3H6 transition were obtained, which is due to the addition of fluoride in glass could reduce the quenching rate of hydroxyls and raise the cross-relaxation (3H6 + 3H4 → 3F4 + 3F4) rate. Our results suggest that the Tm3+ doped Bi2O3-GeO2-Ga2O3 glass with BaF2 might be potential to the application in efficient ~1.8 μm lasers system. PMID:27506152

Phase transitions in (NH4)2MoO2F4 crystal

NASA Astrophysics Data System (ADS)

Krylov, Alexander; Laptash, Natalia; Vtyurin, Alexander; Krylova, Svetlana

2016-11-01

The mechanisms of temperature and high pressure phase transitions have been studied by Raman spectroscopy. Room temperature (295 K) experiments under high hydrostatic pressure up to 3.6 GPa for (NH4)2 MoO2 F4 have been carried out. Experimental data indicates a phase transition into a new high-pressure phase for (NH4)2 MoO2 F4 at 1.2 GPa. This phase transition is related to the ordering anion octahedron groups [MoO2 F4]2- and is not associated with ammonium group. Raman spectra of small non-oriented crystals ranging from 10 to 350 K have been observed. The experiment shows anion groups [MoO2 F4]2- and ammonium in high temperature phase are disordered. The phase transition at T1 = 269.8 K is of the first-order, close to the tricritical point. The first temperature phase transition is related to the ordering anion octahedron groups [MoO2 F4]2-. Second phase transitions T2 = 180 K are associated with the ordering of ammonium. The data presented within this study demonstrate that 2D correlation analysis combined with traditional Raman spectroscopy are powerful tool to study phase transitions in the crystals.

A2TiF 5· nH 2O ( A=K, Rb, or Cs; n=0 or 1): Synthesis, structure, characterization, and calculations of three new uni-dimensional titanium fluorides

NASA Astrophysics Data System (ADS)

Jo, Vinna; Woo Lee, Dong; Koo, Hyun-Joo; Ok, Kang Min

2011-04-01

Three new uni-dimensional alkali metal titanium fluoride materials, A2TiF 5· nH 2O ( A=K, Rb, or Cs; n=0 or 1) have been synthesized by hydrothermal reactions. The structures of A2TiF 5· nH 2O have been determined by single-crystal X-ray diffraction. The Ti 4+ cations have been reduced to Ti 3+ during the synthesis reactions. All three A2TiF 5· nH 2O materials contain novel 1-D chain structures that are composed of the slightly distorted Ti 3+F 6 corner-sharing octahedra attributable to the Jahn-Teller distortion. The coordination environment of the alkali metal cations plays an important role to determine the degree of turning in the chain structures. Complete structural analyses, Infrared and UV-vis diffuse reflectance spectra, and thermal analyses are presented, as are electronic structure calculations.

Reaction of (carbonylimido)sulfur(IV) derivatives with TAS-fluoride, (Me2N)3S+Me3SiF2-.

PubMed

Lork, E; Viets, D; Mews, R; Oberhammer, H

2000-10-16

In the reaction of TAS-fluoride, (Me2N)3S+Me3SiF2-, with carbonyl sulfur difluoride imides RC(O)NSF2 (R = F, CF3), C-N bond, cleavage is observed, and TAS+RC(O)F2- and NSF are the final products. From TASF and RC(O)NS(CF3)F, the salts TAS+RC(O)NS(CF3)F2- (R = F (14), CF3 (15)), with psi-pentacoordinate sulfur centers in the anions, are formed. An X-ray structure investigation of 14 shows that the fluorine atoms occupy axial positions and CF3, NC(O)F, and the sulfur lone pair occupy equatorial positions of the trigonal bipyramid. The -C(O)F group lies in the equatorial plane with the CO bond synperiplanar to the SN bond. According to B3LYP calculations, this structure corresponds to a global minimum and the expected axial orientation of the -C(O)F group represents a transition state. Calculations for the unstable FC(O)NSF3- anion show a different geometry. The -C(O)F group deviates 40 degrees from axial orientation, and the equatorially bonded fluorine is, in contrast to the -CF3 group in 14, syn positioned.

Infrared spectra of seeded hydrogen clusters: (para-H2)N-N2O and (ortho-H2)N-N2O, N = 2-13.

PubMed

Tang, Jian; McKellar, A R W

2005-09-15

High-resolution infrared spectra of clusters containing para-H2 and/or ortho-H2 and a single nitrous oxide molecule are studied in the 2225-cm(-1) region of the upsilon1 fundamental band of N2O. The clusters are formed in pulsed supersonic jet expansions from a cooled nozzle and probed using a tunable infrared diode laser spectrometer. The simple symmetric rotor-type spectra generally show no resolved K structure, with prominent Q-branch features for ortho-H2 but not para-H2 clusters. The observed vibrational shifts and rotational constants are reported. There is no obvious indication of superfluid effects for para-H2 clusters up to N=13. Sharp transitions due to even larger clusters are observed, but no definite assignments are possible. Mixed (para-H2)N-(ortho-H2)M-N2O cluster line positions can be well predicted by linear interpolation between the corresponding transitions of the pure clusters.

Design, synthesis and luminescence properties of Ba2 YB2 O6 Cl- and Ba2 YB2 O6 F-based phosphors.

PubMed

Chen, Wanping; Yang, Xin; Liu, Yan; Dai, Xiaoyan

2015-05-01

Using a high-temperature solid-state reaction, the chlorine in Ba2 YB2 O6 Cl is gradually replaced by F, and a new compound with the nominal chemical formula Ba2 YB2 O6 F and two phosphors doped with Ce(3+) and Eu(3+) , respectively, are obtained. X-Ray diffraction and photoluminescence spectroscopy are used to characterize the as-synthesized samples. The as-synthesized Ba2 YB2 O6 Cl exhibits bright blue emission in the spectral range ~ 330-410 nm with a maximum around 363 nm under X-ray or UV excitation. Ba2 YB2 O6 F:0.01Ce(3+) exhibits blue emission in the range ~ 340-570 nm with a maximum around 383 nm. Ba2 YB2 O6 F:0.01Eu(3+) exhibits a predominantly (5) D0 -(7)  F2 emission (~610 nm) and the relative intensities of the (5) D0 -(7)  F0,1,2 emissions are tunable under different wavelength UV excitation. The luminescence behaviors of the two phosphors are explained simply in terms of the host composition and site occupancy probability of Ce(3+) and Eu(3+) , respectively. The results indicate that these phosphors have potential application as a blue phosphor or as a red phosphor. Copyright © 2014 John Wiley & Sons, Ltd.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy-ethyl)methylamino]ethanolato-2:1κ(4) O (1),N,O (2):O (1)}[μ-2,2'-(methylimino)diethanolato-1:2κ(4) O,N,O':O]dithiocyanato-1κN,2κN-chromium(III)copper(II).

PubMed

Rusanova, Julia A; Semenaka, Valentina V; Dyakonenko, Viktoriya V; Shishkin, Oleg V

2015-09-01

The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal Cu(II)/Cr(III) complex. The mol-ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio-cyanato ligands. The Cu(II) ion adopts a distorted square-pyramidal coordination while the Cr(III) ion has a distorted octa-hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O-H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two -CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1).

SiO2 and CaF2 Behavior During Shielded Metal Arc Welding and Their Effect on Slag Detachability of the CaO-CaF2-SiO2 Type ENiCrFe-7-Covered Electrode

NASA Astrophysics Data System (ADS)

Wang, Huang; Qin, Renyao; He, Guo

2016-09-01

The metallurgical behavior during shielded metal arc welding (SMAW) and the slag detachability of the CaO-CaF2-SiO2 type ENiCrFe-7-covered electrodes was investigated. The results indicated that the slag detachability could be improved as the SiO2 in the flux coatings decreased. When the SiO2 in the flux coating was 10.9 pct, about 28.3 pct CaF2 resulted in the best slag detachability. The CaF2 and SiO2 in the flux coating interacted during SMAW to form gaseous SiF4 to be evacuated. In the reactions, one SiO2 consumed two CaF2, leading to the reduction of the ratio of CaF2/SiO2. After comparing the slag compositions, the best slag detachability was obtained at CaO:CaF2:SiO2 = 1.7:1.8:1, but the worst slag detachability appeared at CaO:CaF2:SiO2 = 1.3:0.9:1. The XRD analysis revealed that the oxides and fluorides in the slags preferred to gather together to form cuspidine and other complex phases. If the CaF2 was dominant in the slags, they intended to form homogenous porous microstructures that were relatively strong and would most likely detach from the weld metal in blocks, exhibiting good slag detachability. If the cuspidine phase was dominant, the slags exhibited a `rock strata'-like microstructure in the intergranular area. Such microstructure was very fragile and could be broken into fine powders that were easily embedded in the weld ripples, leading to slag adhesions. This work provides the researcher with a wealth of information and data, which will also be beneficial to the welding material producers and users.

Fluorine sites in glasses and transparent glass-ceramics of the system Na{sub 2}O/K{sub 2}O/Al{sub 2}O{sub 3}/SiO{sub 2}/BaF{sub 2}

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

Bocker, Christian, E-mail: christian.bocker@uni-jena.d; Munoz, Francisco; Duran, Alicia

2011-02-15

The transparent glass-ceramics obtained in the silicate system Na{sub 2}O/K{sub 2}O/SiO{sub 2}/BaF{sub 2} show homogeneously dispersed BaF{sub 2} nano crystals with a narrow size distribution. The X-ray diffraction and the nuclear magnetic resonance spectroscopy were applied to glasses and the respective glass-ceramics in order to clarify the crystallization mechanism and the role of fluorine during crystallization. With an increasing annealing time, the concentration and also the number of crystals remain approximately constant. With an increasing annealing temperature, the crystalline fraction increases until a saturation limit is reached, while the number of crystals decreases and the size of the crystals increases.more » Fluoride in the glassy network occurs as Al-F-Ba, Al-F-Na and also as Ba-F structures. The latter are transformed into crystalline BaF{sub 2} and fluoride is removed from the Al-F-Ba/Na bonds. However, some fluorine is still present in the glassy phase after the crystallization. -- Graphical abstract: The X-ray diffraction and the nuclear magnetic resonance spectroscopy were applied to glasses in the silicate system Na{sub 2}O/K{sub 2}O/SiO{sub 2}/BaF{sub 2} and the respective glass-ceramics with BaF{sub 2} nano crystals in order to clarify the crystallization mechanism and the role of fluorine during crystallization. Display Omitted Research highlights: {yields} BaF{sub 2} nano crystals are precipitated from a silicate glass system. {yields} Ostwald ripening during the late stage of crystallization does not occur. {yields} Fluorine in the glass is coordinated with Ba as well as Al together with Ba or Na.{yields} In the glass-ceramics, the residual fluorine is coordinated as Al-F-Ba/Na.« less

Vibrational spectroscopy of NO + (H2O)n: Evidence for the intracluster reaction NO + (H2O)n --> H3O + (H2O)n - 2 (HONO) at n => 4

NASA Astrophysics Data System (ADS)

Choi, Jong-Ho; Kuwata, Keith T.; Haas, Bernd-Michael; Cao, Yibin; Johnson, Matthew S.; Okumura, Mitchio

1994-05-01

Infrared spectra of mass-selected clusters NO+(H2O)n for n=1 to 5 were recorded from 2700 to 3800 cm-1 by vibrational predissociation spectroscopy. Vibrational frequencies and intensities were also calculated for n=1 and 2 at the second-order Møller-Plesset (MP2) level, to aid in the interpretation of the spectra, and at the singles and doubles coupled cluster (CCSD) level energies of n=1 isomers were computed at the MP2 geometries. The smaller clusters (n=1 to 3) were complexes of H2O ligands bound to a nitrosonium ion NO+ core. They possessed perturbed H2O stretch bands and dissociated by loss of H2O. The H2O antisymmetric stretch was absent in n=1 and gradually increased in intensity with n. In the n=4 clusters, we found evidence for the beginning of a second solvation shell as well as the onset of an intracluster reaction that formed HONO. These clusters exhibited additional weak, broad bands between 3200 and 3400 cm-1 and two new minor photodissociation channels, loss of HONO and loss of two H2O molecules. The reaction appeared to go to completion within the n=5 clusters. The primary dissociation channel was loss of HONO, and seven vibrational bands were observed. From an analysis of the spectrum, we concluded that the n=5 cluster rearranged to form H3O+(H2O)3(HONO), i.e., an adduct of the reaction products.

The OsO(3)F(+) and mu-F(OsO(3)F)(2)(+) cations: their syntheses and study by Raman and (19)F NMR spectroscopy and electron structure calculations and X-ray crystal structures of [OsO(3)F][PnF(6)] (Pn = As, Sb), [OsO(3)F][HF](2)[AsF(6)], [OsO(3)F][HF][SbF(6)], and [OsO(3)F][Sb(3)F(16)].

PubMed

Gerken, Michael; Dixon, David A; Schrobilgen, Gary J

2002-01-28

The fluoride ion donor properties of OsO(3)F(2) have been investigated. The salts [OsO(3)F][AsF(6)], [OsO(3)F][HF](2)[AsF(6)], mu-F(OsO(3)F)(2)[AsF(6)], [OsO(3)F][HF](2)[SbF(6)], and [OsO(3)F][HF][SbF(6)] have been prepared by reaction of OsO(3)F(2) with AsF(5) and SbF(5) in HF solvent and have been characterized in the solid state by Raman spectroscopy. The single-crystal X-ray diffraction studies of [OsO(3)F][AsF(6)] (P2(1)/n, a = 7.0001(11) A, c = 8.8629(13) A, beta = 92.270(7) degrees, Z = 4, and R(1) = 0.0401 at -126 degrees C), [OsO(3)F][SbF(6)] (P2(1)/c, a = 5.4772(14) A, b = 10.115(3) A, c = 12.234(3) A, beta = 99.321(5) degrees, Z = 4, and R(1) = 0.0325 at -173 degrees C), [OsO(3)F][HF](2)[AsF(6)] (P2(1)/n, a = 5.1491(9) A, b = 8.129(2) A, c = 19.636(7) A, beta = 95.099(7) degrees, Z = 4, and R(1) = 0.0348 at -117 degrees C), and [OsO(3)F][HF][SbF(6)] (Pc, a = 5.244(4) A, b = 9.646(6) A, c = 15.269(10) A, beta = 97.154(13) degrees, Z = 4, and R(1) = 0.0558 at -133 degrees C) have shown that the OsO(3)F(+) cations exhibit strong contacts to the anions and HF solvent molecules giving rise to cyclic, dimeric structures in which the osmium atoms have coordination numbers of 6. The reaction of OsO(3)F(2) with neat SbF(5) yielded [OsO(3)F][Sb(3)F(16)], which has been characterized by (19)F NMR spectroscopy in SbF(5) and SO(2)ClF solvents and by Raman spectroscopy and single-crystal X-ray diffraction in the solid state (P4(1)m, a = 10.076(6) A, c = 7.585(8) A, Z = 2, and R(1) = 0.0858 at -113 degrees C). The weak fluoride ion basicity of the Sb(3)F(16)(-) anion resulted in an OsO(3)F(+) cation (C(3)(v) point symmetry) that is well isolated from the anion and in which the osmium is four-coordinate. The geometrical parameters and vibrational frequencies of OsO(3)F(+), ReO(3)F, mu-F(OsO(3)F)(2)(+), (FO(3)Os--FPnF(5))(2), and (FO(3)Os--(HF)(2)--FPnF(5))(2) (Pn = As, Sb) have been calculated using density functional theory methods.

{μ-2-[(3-Amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1:2κ(5)O(1),O(6):N,N',O(1)}{2-[(3-amino-2,2-dimethyl-prop-yl)imino-meth-yl]-6-meth-oxy-phenolato-1κ(3)N,N',O(1)}-μ-azido-1:2κ(2)N:N-azido-2κN-methanol-2κO-dinickel(II).

PubMed

Ghaemi, Akbar; Rayati, Saeed; Fayyazi, Kazem; Ng, Seik Weng; Tiekink, Edward R T

2012-08-01

Two distinct coordination geometries are found in the binuclear title complex, [Ni(2)(C(13)H(19)N(2)O(2))(2)(N(3))(2)(CH(3)OH)], as one Schiff base ligand is penta-dentate, coordinating via the anti-cipated oxide O, imine N and amine N atoms (as for the second, tridentate, ligand) but the oxide O is bridging and coordination also occurs through the meth-oxy O atom. The Ni(II) atoms are linked by a μ(2)-oxide atom and one end of a μ(2)-azide ligand, forming an Ni(2)ON core. The coordination geometry for the Ni(II) atom coordinated by the tridentate ligand is completed by the meth-oxy O atom derived from the penta-dentate ligand, with the resulting N(3)O(3) donor set defining a fac octa-hedron. The second Ni(II) atom has its cis-octa-hedral N(4)O(2) coordination geometry completed by the imine N and amine N atoms of the penta-dentate Schiff base ligand, a terminally coordinated azide N and a methanol O atom. The arrangement is stabilized by an intra-molecular hydrogen bond between the methanol H and the oxide O atom. Linear supra-molecular chains along the a axis are formed in the crystal packing whereby two amine H atoms from different amine atoms hydrogen bond to the terminal N atom of the monodentate azide ligand.

Activation Strain Analysis of SN2 Reactions at C, N, O, and F Centers

PubMed Central

2017-01-01

Fundamental principles that determine chemical reactivity and reaction mechanisms are the very foundation of chemistry and many related fields of science. Bimolecular nucleophilic substitutions (SN2) are among the most common and therefore most important reaction types. In this report, we examine the trends in the SN2 reactions with respect to increasing electronegativity of the reaction center by comparing the well-studied backside SN2 Cl– + CH3Cl with similar Cl– substitutions on the isoelectronic series with the second period elements N, O, and F in place of C. Relativistic (ZORA) DFT calculations are used to construct the gas phase reaction potential energy surfaces (PES), and activation strain analysis, which allows decomposition of the PES into the geometrical strain and interaction energy, is employed to analyze the observed trends. We find that SN2@N and SN2@O have similar PES to the prototypical SN2@C, with the well-defined reaction complex (RC) local minima and a central barrier, but all stationary points are, respectively, increasingly stable in energy. The SN2@F, by contrast, exhibits only a single-well PES with no barrier. Using the activation strain model, we show that the trends are due to the interaction energy and originate mainly from the decreasing energy of the empty acceptor orbital (σ*A–Cl) on the reaction center A in the order of C, N, O, and F. The decreasing steric congestion around the central atom is also a likely contributor to this trend. Additional decomposition of the interaction energy using Kohn–Sham molecular orbital (KS-MO) theory provides further support for this explanation, as well as suggesting electrostatic energy as the primary reason for the distinct single-well PES profile for the FCl reaction. PMID:28045531

Structures of M2(SO2)6B12F12 (M = Ag or K) and Ag2(H2O)4B12F12: Comparison of the Coordination of SO2 versus H2O and of B12F122- versus Other Weakly Coordinating Anions to Metal Ions in the Solid State.

PubMed

Malischewski, Moritz; Peryshkov, Dmitry V; Bukovsky, Eric V; Seppelt, Konrad; Strauss, Steven H

2016-12-05

The structures of three solvated monovalent cation salts of the superweak anion B 12 F 12 2- (Y 2- ), K 2 (SO 2 ) 6 Y, Ag 2 (SO 2 ) 6 Y, and Ag 2 (H 2 O) 4 Y, are reported and discussed with respect to previously reported structures of Ag + and K + with other weakly coordinating anions. The structures of K 2 (SO 2 ) 6 Y and Ag 2 (SO 2 ) 6 Y are isomorphous and are based on expanded cubic close-packed arrays of Y 2- anions with M(OSO) 6 + complexes centered in the trigonal holes of one expanded close-packed layer of B 12 centroids (⊙). The K + and Ag + ions have virtually identical bicapped trigonal prism MO 6 F 2 coordination spheres, with M-O distances of 2.735(1)-3.032(2) Å for the potassium salt and 2.526(5)-2.790(5) Å for the silver salt. Each M(OSO) 6 + complex is connected to three other cationic complexes through their six μ-SO 2 -κ 1 O,κ 2 O' ligands. The structure of Ag 2 (H 2 O) 4 Y is unique [different from that of K 2 (H 2 O) 4 Y]. Planes of close-packed arrays of anions are offset from neighboring planes along only one of the linear ⊙···⊙···⊙ directions of the close-packed arrays, with [Ag(μ-H 2 O) 2 Ag(μ-H 2 O) 2 )] ∞ infinite chains between the planes of anions. There are two nearly identical AgO 4 F 2 coordination spheres, with Ag-O distances of 2.371(5)-2.524(5) Å and Ag-F distances of 2.734(4)-2.751(4) Å. This is only the second structurally characterized compound with four H 2 O molecules coordinated to a Ag + ion in the solid state. Comparisons with crystalline H 2 O and SO 2 solvates of other Ag + and K + salts of weakly coordinating anions show that (i) N[(SO 2 ) 2 (1,2-C 6 H 4 )] - , BF 4 - , SbF 6 - , and Al(OC(CF 3 ) 3 ) 4 - coordinate much more strongly to Ag + than does Y 2- , (ii) SnF 6 2- coordinates somewhat more strongly to K + than does Y 2- , and (iii) B 12 Cl 12 2- coordinates to K + about the same as, if not slightly weaker than, Y 2- .

Ho3+/Yb3+ co-doped TeO2-BaF2-Y2O3 glasses for ∼1.2 μm laser applications

NASA Astrophysics Data System (ADS)

Wang, Shunbin; Li, Chengzhi; Yao, Chuanfei; Jia, Shijie; Jia, Zhixu; Qin, Guanshi; Qin, Weiping

2017-02-01

Intense ∼1.2 μm fluorescence is observed in Ho3+/Yb3+ co-doped TeO2-BaF2-Y2O3 glasses under 915 nm laser diode excitation. The 1.2 μm emission can be ascribed to the transition 5I6→5I8 of Ho3+. With the introducing of BaF2, the content of OH in the glasses drops markedly, and the 1.2 μm emission intensity increases gradually as increasing the concentration percentage of BaF2. Furthermore, microstructured fibers based on the TeO2-BaF2-Y2O3 glasses are fabricated by using a rod-in-tube method, and a relative positive gain of ∼9.42 dB at 1175.3 nm is obtained in a 5 cm long fiber.

Investigation of N2O Production from 266 and 532 nm Laser Flash Photolysis of O3/N2/O2 Mixtures

NASA Technical Reports Server (NTRS)

Estupinan, E. G.; Nicovich, J. M.; Li, J.; Cunnold, D. M.; Wine, P. H.

2002-01-01

Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and

Spectroscopic properties and energy transfer analysis of Tm3+-doped BaF2-Ga2O3-GeO2-La2O3 glass.

PubMed

Yu, Shenglei; Yang, Zhongmin; Xu, Shanhui

2010-05-01

This paper reports on the spectroscopic properties and energy transfer analysis of Tm(3+)-doped BaF(2)-Ga(2)O(3)-GeO(2)-La(2)O(3) glasses with different Tm(2)O(3) doping concentrations (0.2, 0.5, 2.0, 2.5, 3.0, 3.5, 3.5, 4.0 wt%). Mid-IR fluorescence intensities in the range of 1,300 nm-2,200 nm have been measured when excited under an 808 nm LD for all the samples with the same pump power. Energy level structure and Judd-Ofelt parameters have been calculated based on the absorption spectra of Tm(3+), cross-relaxation rates and multi-phonon relaxation rates have been estimated with different Tm(2)O(3) doping concentrations. The maximum fluorescence intensity at around 1.8 mum has been obtained in Tm(2)O(3)-3 wt% sample and the maximum value of calculated stimulated emission cross-section of Tm(3+) in this sample is about 0.48 x 10(-20) cm(2) at 1,793 nm, and there is not any crystallization peak in the DSC curve of this sample, which indicate the potential utility of Tm(3+)-doped BaF(2)-Ga(2)O(3)-GeO(2)- La(2)O(3) glass for 2.0-microm optical fiber laser.

Quantifying N2O reduction to N2 based on N2O isotopocules - validation with independent methods (helium incubation and 15N gas flux method)

NASA Astrophysics Data System (ADS)

Lewicka-Szczebak, Dominika; Augustin, Jürgen; Giesemann, Anette; Well, Reinhard

2017-02-01

Stable isotopic analyses of soil-emitted N2O (δ15Nbulk, δ18O and δ15Nsp = 15N site preference within the linear N2O molecule) may help to quantify N2O reduction to N2, an important but rarely quantified process in the soil nitrogen cycle. The N2O residual fraction (remaining unreduced N2O, rN2O) can be theoretically calculated from the measured isotopic enrichment of the residual N2O. However, various N2O-producing pathways may also influence the N2O isotopic signatures, and hence complicate the application of this isotopic fractionation approach. Here this approach was tested based on laboratory soil incubations with two different soil types, applying two reference methods for quantification of rN2O: helium incubation with direct measurement of N2 flux and the 15N gas flux method. This allowed a comparison of the measured rN2O values with the ones calculated based on isotopic enrichment of residual N2O. The results indicate that the performance of the N2O isotopic fractionation approach is related to the accompanying N2O and N2 source processes and the most critical is the determination of the initial isotopic signature of N2O before reduction (δ0). We show that δ0 can be well determined experimentally if stable in time and then successfully applied for determination of rN2O based on δ15Nsp values. Much more problematic to deal with are temporal changes of δ0 values leading to failure of the approach based on δ15Nsp values only. For this case, we propose here a dual N2O isotopocule mapping approach, where calculations are based on the relation between δ18O and δ15Nsp values. This allows for the simultaneous estimation of the N2O-producing pathways' contribution and the rN2O value.

Effect of concentration variation on 2.0 µm emission of Ho3+-doped SiO2-Al2O3-Na2CO3-SrF2-CaF2 oxyfluorosilicate glasses

NASA Astrophysics Data System (ADS)

Gelija, Devarajulu; Borelli, Deva Prasad Raju

2018-02-01

The concentration variation of Ho3+ ion-doped SiO2-Al2O3-Na2CO3-SrF2-CaF2 glasses has been prepared by conventional melt quenching method. The thermal stability of 1 mol % of Ho3+-doped oxyfluorosilicate glass has been calculated using the differential thermal analysis (DTA) spectra. The phenomenological Judd-Ofelt intensity parameters Ωλ ( λ = 2, 4 and 6) were calculated for all concentrations of Ho3+ ions. The luminescence spectra in visible region of Ho3+ ion-doped glasses were recorded under the excitation wavelength of 452 nm. The spectra consists of several intense emission bands (5F4, 5S2) → 5I8 (547 nm), 5F3 → 5I8 (647 nm), 5F5 → 5I7 (660 nm) and (5F4, 5S2) → 5I7 (750 nm) in the range 500-780 nm. The fluorescence emission at ˜2.0 µm (5I7 → 5I8) was observed under the excitation of 488 nm Ar-ion laser. The stimulated emission cross section for 5I7 → 5I8 transition (˜2.0 µm) varies from 8.46 to 9.52 × 10-21 cm2, as calculated by the Fuchtbauer-Ladenburg (FL) theory. However, Mc-Cumber theory was used to calculate emission cross section values about 4.24-5.75 × 10-21 cm2 for the 5I7 → 5I8 transition in all concentrations of Ho3+-doped oxyfluorosilicate glasses. Therefore, these results reveal that the 0.5 mol % of Ho3+-doped oxyfluorosilicate glasses, exhibiting higher emission cross section, has potentially been used for laser applications at ˜ 2.0 µm.

A facile method to synthesize nitrogen and fluorine co-doped TiO2 nanoparticles by pyrolysis of (NH4)2TiF6

NASA Astrophysics Data System (ADS)

Chen, Daimei; Jiang, Zhongyi; Geng, Jiaqing; Zhu, Juhong; Yang, Dong

2009-02-01

The nitrogen and fluorine co-doped TiO2 (N-F-TiO2) nanoparticles of anatase crystalline structure were prepared by a facile method of (NH4)2TiF6 pyrolysis, and characterized by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and ultraviolet visible (UV-Vis) spectroscopy etc. With the increase of calcination temperature, (NH4)2TiF6 decomposed into TiOF2 and NH4TiOF3 at first, and then formed anatase-type TiO2 with thin sheet morphology. H3BO3 as oxygen source can promote the formation of anatase TiO2, but decrease the F content in the N-F-TiO2 materials due to the formation of volatile BF3 during the precursor decomposition. The photocatalytic activity of the obtained N-F-TiO2 samples was evaluated by the methylene blue degradation under visible light, and all the samples exhibited much higher photocatalytic activity than P25. Moreover, the merits and disadvantages of this proposed method to prepare doped TiO2 are discussed.

Preparation of MgO-SnO2-TiO2 Materials and Their Corrosion in Na3AlF6-AlF3-K3AlF6 Bath

NASA Astrophysics Data System (ADS)

Xu, Yibiao; Li, Yawei; Sang, Shaobai; Ren, Bo; Qin, Qingwei; Yang, Jianhong

2015-01-01

New types of refractory materials need to be developed for designing the so-called ledge-free sidewalls of the Hall-Héroult cell for aluminum extraction, which are currently constructed using Si3N4 bonded SiC refractories. In the present paper, MgO-based materials as potential candidate sidewalls were prepared using fused magnesia, tin dioxide, and anatase powder as starting materials. The reaction sintering process of the MgO-SnO2-TiO2 materials was investigated by means of X-ray diffraction and scanning electron microscope (SEM). All the specimens were corroded in a Na3AlF6-AlF3-K3AlF6 bath to assess the electrolyte corrosion resistance. The results show that reaction sintering occurs in the MgO-SnO2-TiO2 system in the range of 1373 K to 1873 K (1100 °C to 1600 °C). Firstly, MgO reacts separately with TiO2 and SnO2 to produce the Mg2TiO4 and Mg2SnO4 phases at 1373 K (1100 °C), which in turn react to form the Mg2Ti x Sn1-x O4 composite spinel at temperatures above 1373 K (1100 °C). All the specimens prepared are composed of the composite spinel and periclase phases. Increasing the SnO2 addition from 2 to 10 wt pct enhances densification of the specimens, which is accompanied by the formation of homogeneously distributed composite spinels in the MgO matrix, but the density of the specimen decreases when the amount of SnO2 added is higher than 10 wt pct due to larger volume expansion and agglomeration of the composite spinel. The MgO-SnO2-TiO2 refractories prepared exhibit good corrosion resistance to the electrolyte melts owing to their high density and formation of the composite spinel in the specimens. Their corrosion resistance increases progressively with the increase in the SnO2 addition owing to the formation of more chemically stable composite spinel.

Ae2Sb2X4F2 (Ae = Sr, Ba): new members of the homologous series Ae2M(1+n)X(3+n)F2 designed from rock salt and fluorite 2D building blocks.

PubMed

Kabbour, Houria; Cario, Laurent

2006-03-20

We have designed new compounds within the homologous series Ae2F2M(1+n)X(3+n) (Ae = Sr, Ba; M = main group metal; n = integer) built up from the stacking of 2D building blocks of rock salt and fluorite types. By incrementally increasing the size of the rock salt 2D building blocks, we have obtained two new n = 1 members of this homologous series, namely, Sr2F2Sb2Se4 and Ba2F2Sb2Se4. We then succeeded in synthesizing these compounds using a high-temperature ceramic method. The structure refinements from the powder or single-crystal X-ray diffraction data confirmed presence of the expected alternating stacking of fluorite [Ae2F2] (Ae = Sr, Ba) and rock salt [Sb2Se4] 2D building blocks. However the Ba derivative shows a strong distortion of the [Sb2Se4] block and a concomitant change of the Sb atom coordination likely related to the lone-pair activity.

Manganese Recovery by Silicothermic Reduction of MnO in BaO-MnO-MgO-CaF2 (-SiO2) Slags

NASA Astrophysics Data System (ADS)

Heo, Jung Ho; Park, Joo Hyun

2018-04-01

The effects of reducing agent, CaF2 content, and reaction temperature upon the silicothermic reduction of MnO in the BaO-MnO-MgO-CaF2 (-SiO2) slags were investigated. Mn recovery was proportional to Si activity in the molten alloy. Moreover, 90 pct yield of Mn recovery was obtained under 5 mass pct CaF2 content and 1873 K (1600 °C) reaction temperature. Increasing CaF2 content above 5 pct yielded little or no further increase in Mn recovery, because it was accompanied by increased slag viscosity owing to the precipitation of high melting point compounds such as Ba2SiO4.

Formation of hydroxyapatite onto glasses of the CaO-MgO-SiO2 system with B2O3, Na2O, CaF2 and P2O5 additives.

PubMed

Agathopoulos, S; Tulyaganov, D U; Ventura, J M G; Kannan, S; Karakassides, M A; Ferreira, J M F

2006-03-01

New bioactive glasses with compositions based on the CaO-MgO-SiO(2) system and additives of B(2)O(3), P(2)O(5), Na(2)O, and CaF(2) were prepared. The in vitro mineralization behaviour was tested by immersion of powders or bulk glasses in simulated body fluid (SBF). Monitoring of ionic concentrations in SBF and scanning electron microscopy (SEM) observations at the surface of the glasses were conducted over immersion time. Raman and infrared (IR) spectroscopy shed light on the structural evolution occurring at the surface of the glasses that leads to formation of hydroxyapatite.

Computation provides chemical insight into the diverse hydride NMR chemical shifts of [Ru(NHC)4(L)H]0/+ species (NHC = N-heterocyclic carbene; L = vacant, H2, N2, CO, MeCN, O2, P4, SO2, H-, F- and Cl-) and their [Ru(R2PCH2CH2PR2)2(L)H]+ congeners.

PubMed

Häller, L Jonas L; Mas-Marzá, Elena; Cybulski, Mateusz K; Sanguramath, Rajashekharayya A; Macgregor, Stuart A; Mahon, Mary F; Raynaud, Christophe; Russell, Christopher A; Whittlesey, Michael K

2017-02-28

Relativistic density functional theory calculations, both with and without the effects of spin-orbit coupling, have been employed to model hydride NMR chemical shifts for a series of [Ru(NHC) 4 (L)H] 0/+ species (NHC = N-heterocyclic carbene; L = vacant, H 2 , N 2 , CO, MeCN, O 2 , P 4 , SO 2 , H - , F - and Cl - ), as well as selected phosphine analogues [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 (L)H] + (R = i Pr, Cy; L = vacant, O 2 ). Inclusion of spin-orbit coupling provides good agreement with the experimental data. For the NHC systems large variations in hydride chemical shift are shown to arise from the paramagnetic term, with high net shielding (L = vacant, Cl - , F - ) being reinforced by the contribution from spin-orbit coupling. Natural chemical shift analysis highlights the major orbital contributions to the paramagnetic term and rationalizes trends via changes in the energies of the occupied Ru d π orbitals and the unoccupied σ* Ru-H orbital. In [Ru(NHC) 4 (η 2 -O 2 )H] + a δ-interaction with the O 2 ligand results in a low-lying LUMO of d π character. As a result this orbital can no longer contribute to the paramagnetic shielding, but instead provides additional deshielding via overlap with the remaining (occupied) d π orbital under the L z angular momentum operator. These two effects account for the unusual hydride chemical shift of +4.8 ppm observed experimentally for this species. Calculations reproduce hydride chemical shift data observed for [Ru( i Pr 2 PCH 2 CH 2 P i Pr 2 ) 2 (η 2 -O 2 )H] + (δ = -6.2 ppm) and [Ru(R 2 PCH 2 CH 2 PR 2 ) 2 H] + (ca. -32 ppm, R = i Pr, Cy). For the latter, the presence of a weak agostic interaction trans to the hydride ligand is significant, as in its absence (R = Me) calculations predict a chemical shift of -41 ppm, similar to the [Ru(NHC) 4 H] + analogues. Depending on the strength of the agostic interaction a variation of up to 18 ppm in hydride chemical shift is possible and this factor (that is not necessarily

Combined Embedding of N/F-Doping and CaCO3 Surface Modification in the TiO2 Photoanode for Dye-Sensitized Solar Cells.

PubMed

Park, Su Kyung; Yun, Tae Kwan; Bae, Jae Young

2016-03-01

N/F-doping and CaCO3 surface modification was carried out in TiO2 photoelectrodes for dye-sensitized solar cells (DSSCs). The combined effect of the N/F doped TiO2 and the CaCO3 coating showed a great increase of the short-circuit current (J(sc)), and photoelectric conversion efficiency (η) of the prepared cells; the efficiency (η) was improved from 7.00% of a commercial TiO2 photoelectrode to 7.90% of an uncoated N/F-doped electrode, and to 9.09% of a N/F-doped and CaCO3 surface modified electrode. An enhanced photoresponse in N/F-doped TiO2 nanoparticles generate more photo-excited electrons, as supported by measured UV-Vis diffuse reflectance spectra. A successive CaCO3 surface modification then forms a barrier on the surface of the N/F-doped TiO2 particles; the higher basicity of the CaCO3 modified TiO2 facilitates the dye adsorption, as supported by the direct measurement of the amount of adsorbed dye.

$sup 18$O enrichment process in UO$sub 2$F$sub 2$ utilizing laser light

DOEpatents

DePoorter, G.L.; Rofer-DePoorter, C.K.

1975-12-01

Photochemical reaction induced by laser light is employed to separate oxygen isotopes. A solution containing UO$sub 2$F$sub 2$, HF, H$sub 2$O and a large excess of CH$sub 3$OH is irradiated with laser light of appropriate wavelength to differentially excite the UO$sub 2$$sup 2+$ ions containing $sup 16$O atoms and cause a reaction to proceed in accordance with the reaction 2 UO$sub 2$F$sub 2$ + CH$sub 3$OH + 4 HF $Yields$ 2 UF$sub 4$ down arrow + HCOOH + 3 H$sub 2$O. Irradiation is discontinued when about 10 percent of the UO$sub 2$F$sub 2$ has reacted, the UF$sub 4$ is filtered from the reaction mixture and the residual CH$sub 3$OH and HF plus the product HCOOH and H$sub 2$O are distilled away from the UO$sub 2$F$sub 2$ which is thereby enriched in the $sup 18$O isotope, or the solution containing the UO$sub 2$F$sub 2$ may be photochemically processed again to provide further enrichment in the $sup 18$O isotope.

Synthesis and Physical Properties of the Oxofluoride Cu2(SeO3)F2.

PubMed

Mitoudi-Vagourdi, Eleni; Papawassiliou, Wassilios; Müllner, Silvia; Jaworski, Aleksander; Pell, Andrew J; Lemmens, Peter; Kremer, Reinhard K; Johnsson, Mats

2018-04-16

Single crystals of the new compound Cu 2 (SeO 3 )F 2 were successfully synthesized via a hydrothermal method, and the crystal structure was determined from single-crystal X-ray diffraction data. The compound crystallizes in the orthorhombic space group Pnma with the unit cell parameters a = 7.066(4) Å, b = 9.590(4) Å, and c = 5.563(3) Å. Cu 2 (SeO 3 )F 2 is isostructural with the previously described compounds Co 2 TeO 3 F 2 and CoSeO 3 F 2 . The crystal structure comprises a framework of corner- and edge-sharing distorted [CuO 3 F 3 ] octahedra, within which [SeO 3 ] trigonal pyramids are present in voids and are connected to [CuO 3 F 3 ] octahedra by corner sharing. The presence of a single local environment in both the 19 F and 77 Se solid-state MAS NMR spectra supports the hypothesis that O and F do not mix at the same crystallographic positions. Also the specific phonon modes observed with Raman scattering support the coordination around the cations. At high temperatures the magnetic susceptibility follows the Curie-Weiss law with Curie temperature of Θ = -173(2) K and an effective magnetic moment of μ eff ∼ 2.2 μ B . Antiferromagnetic ordering below ∼44 K is indicated by a peak in the magnetic susceptibility. A second though smaller peak at ∼16 K is tentatively ascribed to a magnetic reorientation transition. Both transitions are also confirmed by heat capacity measurements. Raman scattering experiments propose a structural phase instability in the temperature range 6-50 K based on phonon anomalies. Further changes in the Raman shift of modes at ∼46 K and ∼16 K arise from transitions of the magnetic lattice in accordance with the susceptibility and heat capacity measurements.

The denitrification paradox: The role of O2 in sediment N2O production

NASA Astrophysics Data System (ADS)

Barnes, Jonathan; Upstill-Goddard, Robert C.

2018-01-01

We designed a novel laboratory sediment flux chamber in which we maintained the headspace O2 partial pressure at preselected values, allowing us to experimentally regulate "in-situ" O2 to evaluate its role in net N2O production by an intertidal estuarine sediment (Tyne, UK). In short-term (30 h) incubations with 10 L of overlying estuarine water (∼3 cm depth) and headspace O2 regulation (headspace: sediment/water ratio ∼9:1), net N2O production was highest at 1.2% O2 (sub-oxic; 32.3 nmol N2O m-2 d-1), an order of magnitude higher than at either 0.0% (anoxic; 2.5 N2O nmol m-2 d-1) or 20.85% (ambient; 2.3 nmol N2O m-2 d-1) O2. In a longer-term sealed incubation (∼490 h) without O2 control, time-dependent behaviour of N2O in the tank headspace was highly non-linear with time, showing distinct phases: (i) an initial period of no or little change in O2 or N2O up to ∼ 100 h; (ii) a quasi-linear, inverse correlation between O2 and N2O to ∼360 h, in which O2 declined to ∼2.1% and N2O rose to ∼7800 natm; (iii) over the following 50 h a slower O2 decline, to ∼1.1%, and a more rapid N2O increase, to ∼12000 natm; (iv) over the next 24 h a slowed O2 decline towards undetectable levels and a sharp fall in N2O to ∼4600 natm; (iv) a continued N2O decrease at zero O2, to ∼3000 natm by ∼ 490 h. These results show clearly that rapid N2O consumption (∼115 nmol m-2 d-1), presumably via heterotrophic denitrification (HD), occurs under fully anoxic conditions and therefore that N2O production, which was optimal for sub-oxic O2, results from other nitrogen transformation processes. In experiments in which we amended sediment overlying water to either 1 mM NH4+ or 1 mM NO3-, N2O production rates were 2-134 nmol N2O m-2 d-1 (NH4+ addition) and 0.4-2.2 nmol N2O m-2 d-1 (NO3- addition). We conclude that processes involving NH4+ oxidation (nitrifier nitrification; nitrifier denitrification; nitrification-coupled denitrification) are principally responsible for N2O

Anionic ordering and thermal properties of FeF3·3H2O.

PubMed

Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; Wattiaux, Alain; Demourgues, Alain; Salanne, Mathieu; Groult, Henri; Dambournet, Damien

2015-10-05

Iron fluoride trihydrate can be used to prepare iron hydroxyfluoride with the hexagonal-tungsten-bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF3·3H2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF6]n and [FeF2(H2O)4]n. The decomposition of FeF3·3H2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF3-x(OH)x with the HTB structure. The release of H2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF3·3H2O. An average distribution of FeF4(OH)2 distorted octahedra in HTB-FeF3-x(OH)x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F(-) and H2O. This study provides a clear understanding of the structure and thermal properties of FeF3·3H2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.

Crystal structure of aqua-1κO-{μ-2-[(2-hydroxy­ethyl)methylamino]ethanolato-2:1κ4 O 1,N,O 2:O 1}[μ-2,2′-(methylimino)diethanolato-1:2κ4 O,N,O′:O]dithiocyanato-1κN,2κN-chromium(III)copper(II)

PubMed Central

Rusanova, Julia A.; Semenaka, Valentina V.; Dyakonenko, Viktoriya V.; Shishkin, Oleg V.

2015-01-01

The title compound, [CrCu(C5H11NO2)(C5H12NO2)(NCS)2(H2O)] or [Cr(μ-mdea)Cu(μ-Hmdea)(NCS)2H2O], (where mdeaH2 is N-methylethanolamine, C5H13NO2) is formed as a neutral heterometal CuII/CrIII complex. The mol­ecular structure of the complex is based on a binuclear {CuCr(μ-O)2} core. The coordination environment of each metal atom involves the N,O,O atoms of the tridentate ligand, one bridging O atom of the ligand and the N atom of the thio­cyanato ligands. The CuII ion adopts a distorted square-pyramidal coordination while the CrIII ion has a distorted octa­hedral coordination geometry completed by the aqua ligand. In the crystal, the binuclear complexes are linked via two pairs of O—H⋯O hydrogen bonds to form inversion dimers, which are arranged in columns parallel to the a axis. In the μ-mdea ligand two –CH2 groups and the methyl group were refined as disordered over two sets of sites with equal occupancies. The structure was refined as a two-component twin with a twin scale factor of 0.242 (1). PMID:26396853

Expansion of antimonato polyoxovanadates with transition metal complexes: (Co(N3C5H15)2)2[{Co(N3C5H15)2}V15Sb6O42(H2O)]·5H2O and (Ni(N3C5H15)2)2[{Ni(N3C5H15)2}V15Sb6O42(H2O)]·8H2O.

PubMed

Antonova, Elena; Näther, Christian; Kögerler, Paul; Bensch, Wolfgang

2012-02-20

Two new polyoxovanadates (Co(N(3)C(5)H(15))(2))(2)[{Co(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·5H(2)O (1) and (Ni(N(3)C(5)H(15))(2))(2)[{Ni(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)]·8H(2)O (2) (N(3)C(5)H(15) = N-(2-aminoethyl)-1,3-propanediamine) were synthesized under solvothermal conditions and structurally characterized. In both structures the [V(15)Sb(6)O(42)(H(2)O)](6-) shell displays the main structural motif, which is strongly related to the {V(18)O(42)} archetype cluster. Both compounds crystallize in the triclinic space group P1 with a = 14.3438(4), b = 16.6471(6), c = 18.9186(6) Å, α = 87.291(3)°, β = 83.340(3)°, γ = 78.890(3)°, and V = 4401.4(2) Å(3) (1) and a = 14.5697(13), b = 15.8523(16), c = 20.2411(18) Å, α = 86.702(11)°, β = 84.957(11)°, γ = 76.941(11)°, and V = 4533.0(7) Å(3) (2). In the structure of 1 the [V(15)Sb(6)O(42)(H(2)O)](6-) cluster anion is bound to a [Co(N(3)C(5)H(15))(2)](2+) complex via a terminal oxygen atom. In the Co(2+)-centered complex, one of the amine ligands coordinates in tridentate mode and the second one in bidentate mode to form a strongly distorted CoN(5)O octahedron. Similarly, in compound 2 an analogous NiN(5)O complex is joined to the [V(15)Sb(6)O(42)(H(2)O)](6-) anion via the same attachment mode. A remarkable difference between the two compounds is the orientation of the noncoordinated propylamine group leading to intermolecular Sb···O contacts in 1 and to Sb···N interactions in 2. In the solid-state lattices of 1 and 2, two additional [M(N(3)C(5)H(15))(2)](2+) complexes act as countercations and are located between the [{M(N(3)C(5)H(15))(2)}V(15)Sb(6)O(42)(H(2)O)](4-) anions. Between the anions and cations strong N-H···O hydrogen bonds are observed. In both compounds the clusters are stacked along the b axis in an ABAB fashion with cations and water molecules occupying the space between the clusters. Magnetic characterization demonstrates that the Ni(2+) and Co(2+) cations do not

Theoretical characterization of stable eta1-N2O-, eta2-N2O-, eta1-N2-, and eta2-N2-bound species: intermediates in the addition reactions of nitrogen hydrides with the pentacyanonitrosylferrate(II) ion.

PubMed

Olabe, José A; Estiú, Guillermina L

2003-08-11

The addition of nitrogen hydrides (hydrazine, hydroxylamine, ammonia, azide) to the pentacyanonitrosylferrate(II) ion has been analyzed by means of density functional calculations, focusing on the identification of stable intermediates along the reaction paths. Initial reversible adduct formation and further decomposition lead to the eta(1)- and eta(2)-linkage isomers of N(2)O and N(2), depending on the nucleophile. The intermediates (adducts and gas-releasing precursors) have been characterized at the B3LYP/6-31G level of theory through the calculation of their structural and spectroscopic properties, modeling the solvent by means of a continuous approach. The eta(2)-N(2)O isomer is formed at an initial stage of adduct decompositions with the hydrazine and azide adducts. Further conversion to the eta(1)-N(2)O isomer is followed by Fe-N(2)O dissociation. Only the eta(1)-N(2)O isomer is predicted for the reaction with hydroxylamine, revealing a kinetically controlled N(2)O formation. eta(1)-N(2) and eta(2)-N(2) isomers are also predicted as stable species.

A study of low threshold and high gain Nd3+ ions doped SiO2-B2O3-Na2CO3-NaF-CaF2 glasses for NIR laser applications

NASA Astrophysics Data System (ADS)

Megala, Rajesh; Gowthami, T.; John Sushma, N.; Kamala, S.; Deva Prasad Raju, B.

2018-05-01

Fluoroborosilicate glasses of composition 35SiO2-25B2O3-10Na2CO3-15NaF-15CaF2-xNd2O3 (where x = 0.1, 0.5. 1.0, 2.0 mol%) were prepared by melt quenching technique and various physical properties have been calculated. From the absorption spectra J-O Intensity parameters Ωλ (λ = 2, 4, 6) and radiative properties are evaluated by using J-O theory. The high values of Ω2 = 4.213 × 10-20 cm2, Ω4 = 5.345 × 10-20 cm2, Ω6 = 5.526 × 10-20 cm2 suggest that among the prepared glasses 0.5 mol% Nd glass is more asymmetric, more covalent and rigid in nature. The emission spectra were recorded with 808 nm laser as excitation source. The strong NIR emissions were observed at 876 nm, 1056 nm, 1328 nm corresponding to the transitions 4F3/2 → 4I9/2, 4F3/2 → 4I11/2, 4F3/2 → 4I13/2 respectively. Stimulated emission cross -section (σemi) and Gain bandwidth (σemi × Δλeff) were calculated. For 0.5 mol% Nd these values are found to be 3.30 × 10-20 cm2, 11 × 10-26 cm2. From the decay curve analysis the lifetime values for 4F3/2 level have been determined and these values are decreased with increase in Nd3+ ions concentration. These results may suggest that the prepared SBNCNd05 (Nd = 0.5 mol%) glass could be useful for 1056 nm laser applications.

(Carbonato-κ(2)O,O')bis-(5,5'-dimethyl-2,2'-bipyridyl-κ(2)N,N')cobalt(III) bromide trihydrate.

PubMed

Arun Kumar, Kannan; Meera, Parthsarathi; Amutha Selvi, Madhavan; Dayalan, Arunachalam

2012-04-01

In the title complex, [Co(CO(3))(C(12)H(12)N(2))(2)]Br·3H(2)O, the Co(III) cation has a distorted octa-hedral coordination environment. It is chelated by four N atoms of two different 5,5'-dimethyl-2,2'-bipyridyl (dmbpy) ligands in axial and equatorial positions, and by two O atoms of a carbonate anion completing the equatorial positions. Although the water mol-ecules are disordered and their H atoms were not located, there are typical O⋯O distances between 2.8 and 3.0 Å, indicating O-H⋯O hydrogen bonding. The crystal packing is consolidated by C-H⋯O and C-H⋯Br hydrogen bonds, as well as π-π stacking inter-actions between adjacent pyridine rings of the dmbpy ligands, with centroid-centroid distances of 3.694 (3) and 3.7053 (3) Å.

Characterization of Water Coordination to Ferrous Nitrosyl Complexes with fac-N2O, cis-N2O2, and N2O3 Donor Ligands.

PubMed

McCracken, John; Cappillino, Patrick J; McNally, Joshua S; Krzyaniak, Matthew D; Howart, Michael; Tarves, Paul C; Caradonna, John P

2015-07-06

Electron paramagnetic resonance (EPR) experiments were done on a series of S = (3)/2 ferrous nitrosyl model complexes prepared with chelating ligands that mimic the 2-His-1-carboxylate facial triad iron binding motif of the mononuclear nonheme iron oxidases. These complexes formed a comparative family, {FeNO}(7)(N2Ox)(H2O)3-x with x = 1-3, where the labile coordination sites for the binding of NO and solvent water were fac for x = 1 and cis for x = 2. The continuous-wave EPR spectra of these three complexes were typical of high-spin S = (3)/2 transition-metal ions with resonances near g = 4 and 2. Orientation-selective hyperfine sublevel correlation (HYSCORE) spectra revealed cross peaks arising from the protons of coordinated water in a clean spectral window from g = 3.0 to 2.3. These cross peaks were absent for the {FeNO}(7)(N2O3) complex. HYSCORE spectra were analyzed using a straightforward model for defining the spin Hamiltonian parameters of bound water and showed that, for the {FeNO}(7)(N2O2)(H2O) complex, a single water conformer with an isotropic hyperfine coupling, Aiso = 0.0 ± 0.3 MHz, and a dipolar coupling of T = 4.8 ± 0.2 MHz could account for the data. For the {FeNO}(7)(N2O)(H2O)2 complex, the HYSCORE cross peaks assigned to coordinated water showed more frequency dispersion and were analyzed with discrete orientations and hyperfine couplings for the two water molecules that accounted for the observed orientation-selective contour shapes. The use of three-pulse electron spin echo envelope modulation (ESEEM) data to quantify the number of water ligands coordinated to the {FeNO}(7) centers was explored. For this aspect of the study, HYSCORE spectra were important for defining a spectral window where empirical integration of ESEEM spectra would be the most accurate.

The Seasonal and Interannual Variability of the Budgets of N2O and CCl3F

NASA Technical Reports Server (NTRS)

Wong, Sun; Prather, Michael J.; Rind, David H.

1999-01-01

The 6-year wind archives from the Goddard Institute for Space Studies/Global Climate-Middle Atmosphere Model (GISS/GCMAM) were in- put to the GISS/Harvard/Irvine Chemical Transport Model (G/H/I CTM) to study the seasonal and interannual variability of the budgets and distributions of nitrous oxide (N2O) and trichlorofluoromethane (CCl3F), with the corresponding chemical loss frequencies recycled and boundary conditions kept unchanged from year to year. The effects of ozone feedback and quasi-biennial oscillation (QBO) were not included. However, the role of circulation variation in driving the lifetime variability is investigated. It was found that the global loss rates of these tracers are related to the extratropical planetary wave activity, which drives the tropical upward mass flux. For N2O, a semiannual signal in the loss rate variation is associated with the interhemispheric asymmetry in the upper stratospheric wave activity. For CCl3F, the semiannual signal is weaker, associated with the comparatively uniform wave episodes in the lower stratosphere. The loss rates lag behind the wave activity by about 1-2 months. The interannual variation of the GCM generated winds drives the interannual variation of the annually averaged lifetime. The year-to-year variations of the annually averaged lifetimes can be about 3% for N2O and 4% for CCl3F.

Collisional Removal of OH (X (sup 2)Pi, nu=7) by O2, N2, CO2, and N2O

NASA Technical Reports Server (NTRS)

Knutsen, Karen; Dyer, Mark J.; Copeland, Richard A.

1996-01-01

Collisional removal rate constants for the OH (X 2PI, nu = 7) radical are measured for the colliders O2, CO2, and N2O, and an upper limit is established for N2. OH(nu = 4) molecules, generated in a microwave discharge flow cell by the reaction of hydrogen atoms with ozone, are excited to v = 7 by the output of a pulsed infrared laser via direct vibrational overtone excitation. The temporal evolution of the P = 7 population is probed as a function of the collider gas partial pressure by a time-delayed pulsed ultraviolet laser. Fluorescence from the B 21 + state is detected in the visible spectral region.

Anionic ordering and thermal properties of FeF 3·3H 2O

DOE PAGES

Burbano, Mario; Duttine, Mathieu; Borkiewicz, Olaf; ...

2015-09-17

In this study, iron fluoride tri-hydrate can be used to prepare iron hydroxyfluoride with the Hexagonal-Tungsten-Bronze (HTB) type structure, a potential cathode material for batteries. To understand this phase transformation, a structural description of β-FeF 3·3H 2O is first performed by means of DFT calculations and Mössbauer spectroscopy. The structure of this compound consists of infinite chains of [FeF 6]n and [FeF 2(H2O) 4] n. The decomposition of FeF 3·3H 2O induces a collapse and condensation of these chains, which lead to the stabilization, under specific conditions, of a hydroxyfluoride network FeF 3-x(OH) x with the HTB structure. The releasemore » of H 2O and HF was monitored by thermal analysis and physical characterizations during the decomposition of FeF 3·3H 2O. An average distribution of FeF 4(OH) 2 distorted octahedra in HTB-FeF 3-x(OH) x was obtained subsequent to the thermal hydrolysis/olation of equatorial anionic positions involving F- and H 2O. This study provides a clear understanding of the structure and thermal properties of FeF 3·3H 2O, a material that can potentially bridge the recycling of pickling sludge from the steel industry by preparing battery electrodes.« less

Microcosm N2O emissions wth calibration

EPA Pesticide Factsheets

The dataset consists of measurements of soil nitrous oxide emissions from soils under three different amendments: glucose, cellulose, and manure. Data includes the four isotopomers of nitrous oxide (14N15N16O, 15N14N16O, 14N14N18O, 14N14N16O), and the site preference.This dataset is associated with the following publication:Chen , H., D. Williams , P. Deshmukh , F. Birgand, B. Maxwell, and J. Walker. Probing the Biological Sources of Soil N2O Emissions by Quantum Cascade Laser-Based 15N Isotopocule Analysis. SOIL SCIENCE SOCIETY OF AMERICA JOURNAL. Soil Science Society of America, Madison, WI, USA, 100(0): 175-181, (2016).

Properties and Crystallization Phenomena in Li2Si2O5-Ca5(PO4)3F and Li2Si2O5-Sr5(PO4)3F Glass-Ceramics Via Twofold Internal Crystallization.

PubMed

Rampf, Markus; Dittmer, Marc; Ritzberger, Christian; Schweiger, Marcel; Höland, Wolfram

2015-01-01

The combination of specific mechanical, esthetic, and chemical properties is decisive for the application of materials in prosthodontics. Controlled twofold crystallization provides a powerful tool to produce special property combinations for glass-ceramic materials. The present study outlines the potential of precipitating Ca5(PO4)3F as well as Sr5(PO4)3F as minor crystal phases in Li2Si2O5 glass-ceramics. Base glasses with different contents of CaO/SrO, P2O5, and F(-) were prepared within the glasses of the SiO2-Li2O-K2O-CaO/SrO-Al2O3-P2O5-F system. Preliminary studies of nucleation by means of XRD and scanning electron microscopy (SEM) of the nucleated base glasses revealed X-ray amorphous phase separation phenomena. Qualitative and quantitative crystal phase analyses after crystallization were conducted using XRD in combination with Rietveld refinement. As a main result, a direct proportional relationship between the content of apatite-forming components in the base glasses and the content of apatite in the glass-ceramics was established. The microstructures of the glass-ceramics were investigated using SEM. Microstructural and mechanical properties were found to be dominated by Li2Si2O5 crystals and quite independent of the content of the apatite present in the glass-ceramics. Biaxial strengths of up to 540 MPa were detected. Ca5(PO4)3F and Sr5(PO4)3F influence the translucency of the glass-ceramics and, hence, help to precisely tailor the properties of Li2Si2O5 glass-ceramics. The authors conclude that the twofold crystallization of Li2Si2O5-Ca5(PO4)3F or Li2Si2O5-Sr5(PO4)3F glass-ceramics involves independent solid-state reactions, which can be controlled via the chemical composition of the base glasses. The influence of the minor apatite phase on the optical properties helps to achieve new combinations of features of the glass-ceramics and, hence, displays new potential for dental applications.

KCd2[N(CN)2]5(H2O)4: an enmeshed honeycomb grid.

PubMed

Schlueter, John A; Geiser, Urs; Funk, Kylee A

2008-02-01

The title compound, poly[potassium [diaquapenta-micro(2)-dicyanamido-dicadmium(II)] dihydrate], {K[Cd(2)(C(2)N(3))(5)(H(2)O)(2)].2H(2)O}(n), contains two-dimensional anionic sheets of {[Cd(2){N(CN)(2)}(H(2)O)(2)](-)}(n) with a modified (6,3)-net (layer group cm2m, No. 35). Two sets of equivalent sheets interpenetrate orthogonally to form a tetragonal enmeshed grid.

Effect of ZrO(2) additions on the crystallization, mechanical and biological properties of MgO-CaO-SiO(2)-P(2)O(5)-CaF(2) bioactive glass-ceramics.

PubMed

Li, H C; Wang, D G; Meng, X G; Chen, C Z

2014-06-01

A series of ZrO(2) doped MgO-CaO-SiO(2)-P(2)O(5)-CaF(2) bioactive glass-ceramics were obtained by sintering method. The crystallization behavior, phase composition, morphology and structure of glass-ceramics were characterized. The bending strength, elastic modulus, fracture toughness, micro-hardness and thermal expansion coefficient (TEC) of glass-ceramics were investigated. The in vitro bioactivity and cytotoxicity tests were used to evaluate the bioactivity and biocompatibility of glass-ceramics. The sedimentation mechanism and growth process of apatites on sample surface were discussed. The results showed that the mainly crystalline phases of glass-ceramics were Ca(5)(PO4)3F (fluorapatite) and β-CaSiO(3). (β-wollastonite). m-ZrO(2) (monoclinic zirconia) declined the crystallization temperatures of glasses. t-ZrO(2) (tetragonal zirconia) increased the crystallization temperature of Ca(5)(PO4)(3)F and declined the crystallization temperature of β-CaSiO(3). t-ZrO(2) greatly increased the fracture toughness, bending strength and micro-hardness of glass-ceramics. The nanometer apatites were induced on the surface of glass-ceramic after soaking 28 days in SBF (simulated body fluid), indicating the glass-ceramic has good bioactivity. The in vitro cytotoxicity test demonstrated the glass-ceramic has no toxicity to cell. Copyright © 2014 Elsevier B.V. All rights reserved.

On the production of N2O from the reaction of O/1D/with N2.

NASA Technical Reports Server (NTRS)

Simonaitis, R.; Lissi, E.; Heicklen, J.

1972-01-01

Ozone was photolyzed at 2537 A and at 25 C in the presence of 42-115 torr of O2 and about 880 torr of N2 to test the relative importance of the two reactions O(1D) + N2 + M leading to N2O + M and O(1D) + N2 leading to O(3P) + N2. In this study N2O was not found as a product. Thus from our detectability limit for N2O an upper limit to the efficiency of the first reaction relative to the second of 2.5 times 10 to the -6 power at 1000-torr total pressure was computed.

On the production of N2O from the reaction of O(1 D) with N2

NASA Technical Reports Server (NTRS)

Simonaitis, R.; Lissi, E.; Heicklen, J.

1972-01-01

Ozone was photolyzed at 2537 A and 25 C in the presence of 42-115 torr of O2 and about 880 torr of N2 to test the relative importance of the two reactions: (1) O(1D) + N2 + M yields N2O + M, and (2) O(1D) + N2 yields O(3P) + N2. N2O was not found as a product. Thus from our detectability limit for N2O (0.3 micron), an upper limit to the efficiency of the first reaction relative to the second of 0.0000025 at 1000 torr total pressure was computed. This corresponds to k1/k2 smaller than 0.8 x 10 to the minus 25 power cu cm/particle.

Photocatalytic degradation of pentachlorophenol in aqueous solution by visible light sensitive N-F-codoped TiO{sub 2} photocatalyst

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

Govindan, Kadarkarai, E-mail: govindanmu@gmail.com; Water Chemistry Lab, Water Institute, Karunya University, Coimbatore 641 114; Murugesan, Sepperumal

Graphical abstract: Schematic representation for the visible light photocatalytic process of N and F codoped TiO{sub 2}. Highlights: ► Visible light sensitive N-F-codoped TiO{sub 2}. ► Photocatalytic degradation of pentachlorophenol. ► Effect of oxidants on photocatalytic degradation of pentachlorophenol. ► PMS is a more efficient oxidant for the photodegradation of PCP. - Abstract: In this present study, N-F-codoped titanium dioxide nanocatalyst (NFTO) has been synthesized by simple sol–gel assisted solvothermal method for the effective utilization of visible light in photocatalytic reactions. Structural characterization of the photocatalyst is analyzed by XRD, UV–vis diffuse reflectance spectra (DRS), SEM and TEM. Moreover themore » chemical statuses of NFTO are gathered by X-ray photoelectron spectroscopy (XPS). The results show that a high surface area with photoactive anatase phase crystalline is obtained. In addition, nitrogen and fluorine atoms are doped into TiO{sub 2} crystal lattice to extend the visible light absorption and higher photocatalytic activity. The photocatalytic degradation of pentachlorophenol in aqueous solution is examined under visible light irradiation, the addition of oxidants such as PMS, PDS and H{sub 2}O{sub 2} is analyzed in detail. The rate of photocatalytic degradation of pentachlorophenol is obtained in the following order: PMS > PDS > H{sub 2}O{sub 2}.« less

N2/O2/H2 Dual-Pump Cars: Validation Experiments

NASA Technical Reports Server (NTRS)

OByrne, S.; Danehy, P. M.; Cutler, A. D.

2003-01-01

The dual-pump coherent anti-Stokes Raman spectroscopy (CARS) method is used to measure temperature and the relative species densities of N2, O2 and H2 in two experiments. Average values and root-mean-square (RMS) deviations are determined. Mean temperature measurements in a furnace containing air between 300 and 1800 K agreed with thermocouple measurements within 26 K on average, while mean mole fractions agree to within 1.6 % of the expected value. The temperature measurement standard deviation averaged 64 K while the standard deviation of the species mole fractions averaged 7.8% for O2 and 3.8% for N2, based on 200 single-shot measurements. Preliminary measurements have also been performed in a flat-flame burner for fuel-lean and fuel-rich flames. Temperature standard deviations of 77 K were measured, and the ratios of H2 to N2 and O2 to N2 respectively had standard deviations from the mean value of 12.3% and 10% of the measured ratio.

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

Potassium (2,2'-bipyridine-κN,N')bis-(carbonato-κO,O')cobaltate(III) dihydrate.

PubMed

Wang, Jian-Fei; Lin, Jian-Li

2010-09-30

In the title compound, K[Co(CO(3))(2)(C(10)H(8)N(2))]·2H(2)O, the Co(III) atom is coordinated by two bipyridine N atoms and four O atoms from two bidentate chelating carbonate anions, and thus adopts a distorted octa-hedral N(2)O(4) environment. The [Co(bipy)(CO(3))(2)](-) (bipy is 2,2'-bipyridine) -units are stacked along [100] via π-π stacking inter-actions, with inter-planar distances between the bipyridine rings of 3.36 (4) and 3.44 (6) Å, forming chains. Classical O-H⋯O hydrogen-bonding inter-actions link the chains, forming channels along (100) in which the K(+) ions reside and leading to a three-dimensional supra-molecular architecture.

Uptake properties of Ni2+ by nCaO.Al2O3.2SiO2 (n=1-4) prepared from solid-state reaction of kaolinite and calcite.

PubMed

Jha, Vinay Kumar; Kameshima, Yoshikazu; Nakajima, Akira; Okada, Kiyoshi; MacKenzie, Kenneth J D

2005-08-31

A series of nCaO.Al2O3.2SiO2 samples (n=1-4) were prepared by solid-state reaction of mechanochemically treated mixtures of kaolinite and calcite fired at 600-1000 degrees C for 24 h. All the samples were X-ray amorphous after firing at 600-800 degrees C but had crystallized by 900 degrees C. The main crystalline phases were anorthite (n=1), gehlenite (n=2 and 3) and larnite (n=4). The uptake of Ni2+ by nCaO.Al2O3.2SiO2 samples fired at 800 and 900 degrees C was investigated at room temperature using solutions with initial Ni2+ concentrations of 0.1-50 mmol/l. Amorphous samples (fired at 800 degrees C) showed a higher Ni2+ uptake capacity than crystalline samples (fired at 900 degrees C). Ni2+ uptake was found to increase with increasing of CaO content. Amorphous 4CaO.Al2O3.2SiO2 showed the highest Ni2+ uptake capacity (about 9 mmol/g). The Ni2+ uptake abilities of the present samples are higher than those of other materials reported in the literature. Since the sorbed Ni2+/released Ca2+ ratios of these samples are close to unity, ion replacement of Ni2+ for Ca2+ is thought to be the principal mechanism of Ni2+ uptake by the present samples.

O2(b1Σg+) Quenching by O2, CO2, H2O, and N2 at Temperatures of 300-800 K.

PubMed

Zagidullin, M V; Khvatov, N A; Medvedkov, I A; Tolstov, G I; Mebel, A M; Heaven, M C; Azyazov, V N

2017-10-05

Rate constants for the removal of O 2 (b 1 Σ g + ) by collisions with O 2 , N 2 , CO 2 , and H 2 O have been determined over the temperature range from 297 to 800 K. O 2 (b 1 Σ g + ) was excited by pulses from a tunable dye laser, and the deactivation kinetics were followed by observing the temporal behavior of the b 1 Σ g + -X 3 Σ g - fluorescence. The removal rate constants for CO 2 , N 2 , and H 2 O were not strongly dependent on temperature and could be represented by the expressions k CO2 = (1.18 ± 0.05) × 10 -17 × T 1.5 × exp[Formula: see text], k N2 = (8 ± 0.3) × 10 -20 × T 1.5 × exp[Formula: see text], and k H2O = (1.27 ± 0.08) × 10 -16 × T 1.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . Rate constants for O 2 (b 1 Σ g + ) removal by O 2 (X), being orders of magnitude lower, demonstrated a sharp increase with temperature, represented by the fitted expression k O2 = (7.4 ± 0.8) × 10 -17 × T 0.5 × exp[Formula: see text] cm 3 molecule -1 s -1 . All of the rate constants measured at room temperature were found to be in good agreement with previously reported values.

Partial nitrogen loss in SrTaO2N and LaTiO2N oxynitride perovskites

NASA Astrophysics Data System (ADS)

Chen, Daixi; Habu, Daiki; Masubuchi, Yuji; Torii, Shuki; Kamiyama, Takashi; Kikkawa, Shinichi

2016-04-01

SrTaO2N heated in a helium atmosphere began to release nitrogen of approximately 30 at% at 950 °C while maintaining the perovskite structure and its color changed from orange to dark green. Then it decomposed above 1200 °C to a black mixture of Sr1.4Ta0.6O2.73, Ta2N, and Sr5Ta4O15. The second decomposition was not clearly observed when SrTaO2N was heated in a nitrogen atmosphere below 1550 °C. After heating at 1500 °C for 3 h under a 0.2 MPa nitrogen atmosphere, the perovskite product became dark green and conductive. Structure refinement results suggested that the product was a mixture of tetragonal and cubic perovskites with a decreased ordering of N3-/O2-. The sintered body was changed to an n-type semiconductor after a partial loss of nitrogen to be reduced from the originally insulating SrTaO2N perovskite lattice. LaTiO2N was confirmed to have a similar cis-configuration of the TiO4N2 octahedron as that of TaO4N2 in SrTaO2N. It also released some of its nitrogen at 800 °C changing its color from brown to black and then decomposed to a mixture of LaTiO3, La2O3, and TiN at 1100 °C. These temperatures are lower than those in SrTaO2N.

Centrosymmetric [N(CH3)4]2TiF6 vs. noncentrosymmetric polar [C(NH2)3]2TiF6: A hydrogen-bonding effect on the out-of-center distortion of TiF6 octahedra

NASA Astrophysics Data System (ADS)

Kim, Eun-ah; Lee, Dong Woo; Ok, Kang Min

2012-11-01

The syntheses, structures, and characterization of organically templated zero-dimensional titanium fluoride materials, A2TiF6 (A[N(CH3)4] or [C(NH2)3]), are reported. Phase pure samples of A2TiF6 were synthesized by either solvothermal reaction method or a simple mixing method. While [N(CH3)4]2TiF6 crystallizes in a centrosymmetric space group, R-3, [C(NH2)3]2TiF6 crystallizes in a noncentrosymmetric polar space group, Cm. The asymmetric out-of-center distortion of TiF6 octahedra in polar [C(NH2)3]2TiF6 are attributable to the hydrogen-bonding interactions between the fluorine atoms in TiF6 octahedra and the nitrogen atoms in the [C(NH2)3]+ cation. Powder second-harmonic generation (SHG) measurements on the [C(NH2)3]2TiF6, using 1064 nm radiation, indicate the material has SHG efficiency of 25× that of α-SiO2, which indicates an average nonlinear optical susceptibility, exp of 2.8 pm/V. Additional SHG measurements reveal that the material is not phase-matchable (Type 1). The magnitudes of out-of-center distortions and dipole moment calculations for TiF6 octahedra will be also reported.

A facile photoassisted route to synthesis N, F-codoped oxygen-deficient TiO2 with enhanced photocatalytic performance under visible light irradiation

NASA Astrophysics Data System (ADS)

Kang, Xiaolan; Han, Ying; Song, Xuezhi; Tan, Zhenquan

2018-03-01

Herein, we report a facile and economical photoassisted strategy for synthesizing the highly active N, F-codoped oxygen-deficient TiO2 with coexposed {001} and {101} facets. NH4TiOF3 mesocrystals were used to act as the resource of dopants and the intermediate to fabricate TiO2 with highly active {001} facets. Comprehensive analysis based on X-ray photoelectron spectroscopy, transmission electron microscopy and electron spin resonances manifested that F, N and oxygen vacancies were simultaneously introduced to TiO2 through the photoassisted process. The test of phenol and Rhodamine B (RhB) degradation under visible light demonstrates that the as-prepared N, F codoped oxygen-deficient TiO2 exhibits higher photocatalytic activity than its references. The increased photocatalytic performances results from the synergetic effect of the induced Vo's and N, F codoping in TiO2 with co-exposed {001} and {101} facets, favoring the visible light utilization as well as the separation of photogenerated carriers. This strategy is expected to provide a new insight into the design of high performance photocatalysts.

Triaqua-1κO,2κ2 O-bis­(2,2′-bipyridine)-1κ2 N,N′;2κ2 N,N′-chlorido-1κCl-μ-terephthalato-1:2κ2 O 1:O 4-dicopper(II) nitrate monohydrate

PubMed Central

Liu, Yang; Feng, Yong-Lan; Kuang, Dai-Zhi

2012-01-01

In the binuclear title compound, [Cu2(C8H4O4)Cl(C10H8N2)2(H2O)3]NO3·H2O, the two crystallographically independent CuII ions have similar coordination environments. One of the CuII ions has a square-pyramidal arrangement, which is defined by a water mol­ecule occupying the apical position, with the equatorial ligators consisting of two N atoms from a 2,2′-bipyridine mol­ecule, one carboxyl­ate O atom from a terephthalate ligand and one O atom from a water mol­ecule. The other CuII ion has a similar coordination environment, except that the apical position is occupied by a chloride ligand instead of a water mol­ecule. An O—H⋯O and O—H⋯Cl hydrogen-bonded three-dimensional network is formed between the components. PMID:22719307

Optimization of preparation of NDV F Gene encapsulated in N-2-HACC-CMC nanoparticles

NASA Astrophysics Data System (ADS)

Li, S. S.; Zhang, Y.; Zhao, K.; Wang, X. H.

2018-01-01

In this study, the biodegradable materials N-2-hydroxypropyl trimethyl ammonium chloride chitosan (N-2-HACC) and N, O-carboxymethyl chitosan (CMC) are used as delivery carrier for the pVAX I -F(o)-C3d6. The optimal preparation condition is as follows: concentration of N-2-HACC is 1.0 mg/ml, concentration of CMC is 0.85 mg/ml, concentration of pVAX I -F(o)-C3d6 is 100 μg ml. The results show that the prepared N-2-HACC-CMC/pFDNA NPs have regular round shape, smooth surface and good dispersion, the particle size is 310 nm, Zeta potential is 50 mV, the entrapment efficiency is 92 %, the loading capacity is 51 % (n=3).

A density functional study of silicon fullerene endohedral X@Si20F20 and exohedral X-Si20F20 (X=O2-, S2-, Se2-) complexes

NASA Astrophysics Data System (ADS)

Behzadi, Hadi; Esrafili, Mehdi D.; Manzetti, Sergio; Roonasi, Payman

2014-02-01

This study reports the structure and electronic properties of three stable endohedral X@Si20F20 and exohedral X-Si20F20 (X=O2-, S2-, Se2-) complexes. The study revealed that the endohedral complexes with S2- and Se2- result as energy minimum structures, with the guest anion located in the cage center. In the case of endohedral O2--complexes, the pattern is quite different whereas the O2- complexes dramatically deviated from the architecture of S2- and Se2-, by having O2- located toward one of silicon atoms in the cage. With respect to the exohedral form, the energy minimized structure is obtained by positioning the anion between two silicon atoms and forming two Si-X bonds. For both cases, the strength of the interactions is calculated to increase accordingly to the pattern: Se2-@Si20F20 (Se2--Si20F20)2-@Si20F20 (S2--Si20F20)<O2-@Si20F20 (O2--Si20F20). Additionally, the calculated HOMO-LUMO energy gaps of the exohedral complexes show lower values than endohedral forms, indicating higher chemical reactivity. This study reports relevant details for the synthesis and structuring of silica based endohedral complexes and serves for the further developments of silica-based particles for energy and microengineering purposes.

Infrared spectra and tunneling dynamics of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O.

PubMed

Zhu, Yu; Zheng, Rui; Li, Song; Yang, Yu; Duan, Chuanxi

2013-12-07

The rovibrational spectra of the N2-D2O and OC-D2O complexes in the v2 bend region of D2O have been measured in a supersonic slit jet expansion using a rapid-scan tunable diode laser spectrometer. Both a-type and b-type transitions were observed for these two complexes. All transitions are doubled, due to the heavy water tunneling within the complexes. Assuming the tunneling splittings are the same in K(a) = 0 and K(a) = 1, the band origins, all three rotational and several distortion constants of each tunneling state were determined for N2-D2O in the ground and excited vibrational states, and for OC-D2O in the excited vibrational state, respectively. The averaged band origin of OC-D2O is blueshifted by 2.241 cm(-1) from that of the v2 band of the D2O monomer, compared with 1.247 cm(-1) for N2-D2O. The tunneling splitting of N2-D2O in the ground state is 0.16359(28) cm(-1), which is about five times that of OC-D2O. The tunneling splittings decrease by about 26% for N2-D2O and 23% for OC-D2O, respectively, upon excitation of the D2O bending vibration, indicating an increase of the tunneling barrier in the excited vibrational state. The tunneling splittings are found to have a strong dependence on intramolecular vibrational excitation as well as a weak dependence on quantum number K(a).

The relation between residual stress, interfacial structure and the joint property in the SiO2f/SiO2-Nb joints.

PubMed

Ma, Qiang; Li, Zhuo Ran; Yang, Lai Shan; Lin, Jing Huang; Ba, Jin; Wang, Ze Yu; Qi, Jun Lei; Feng, Ji Cai

2017-06-23

In order to achieve a high-quality joint between SiO 2f /SiO 2 and metals, it is necessary to address the poor wettability of SiO 2f /SiO 2 and the high residual stress in SiO 2f /SiO 2 -Nb joint. Here, we simultaneously realize good wettability and low residual stress in SiO 2f /SiO 2 -Nb joint by combined method of HF etching treatment and Finite Element Analysis (FEA). After etching treatment, the wettability of E-SiO 2f /SiO 2 was improved, and the residual stress in the joint was decreased. In order to better control the quality of joints, efforts were made to understand the relationship between surface structure of E-SiO 2f /SiO 2 and residual stress in joint using FEA. Based on the direction of FEA results, a relationship between residual stress, surface structure and joint property in the brazed joints were investigated by experiments. As well the FEA and the brazing test results both realized the high-quality joint of E-SiO 2f /SiO 2 -Nb and the shear strength of the joint reached 61.9 MPa.

Emission analysis of RE3+ (RE = Sm, Dy):B2O3-TeO2-Li2O-AlF3 glasses.

PubMed

Raju, C Nageswara; Sailaja, S; Kumari, S Pavan; Dhoble, S J; Kumar, V Ramesh; Ramanaiah, M V; Reddy, B Sudhakar

2013-01-01

This article reports on the optical properties of 0.5% mol of Sm(3+), Dy(3+) ion-doped B2O3-TeO2-Li2O-AlF3 (LiAlFBT) glasses. The glass samples were characterized by optical absorption and emission spectra. Judd-Ofelt theory was applied to analyze the optical absorption spectra and calculate the intensity parameters and radiative properties of the emission transitions. The emission spectra of Sm(3+) and Dy(3+):LiAlFBT glasses showed a bright reddish-orange emission at 598 nm ((4)G5/2 → (6)H7/2) and an intense yellow emission at 574 nm ((4)F9/2 → (6)H13/2), respectively. Full width at half maximum (FWHM), stimulated emission cross section, gain bandwidth and optical gain values were also calculated to extend the applications of the Sm(3+) and Dy(3+):LiAlFBT glasses. Copyright © 2012 John Wiley & Sons, Ltd.

Development of AlN and TiB2 Composites with Nb2O5, Y2O3 and ZrO2 as Sintering Aids

PubMed Central

González, José C.; Rodríguez, Miguel Á.; Figueroa, Ignacio A.; Villafuerte-Castrejón, María-Elena; Díaz, Gerardo C.

2017-01-01

The synthesis of AlN and TiB2 by spark plasma sintering (SPS) and the effect of Nb2O5, Y2O3 and ZrO2 additions on the mechanical properties and densification of the produced composites is reported and discussed. After the SPS process, dense AlN and TiB2 composites with Nb2O5, Y2O3 and ZrO2 were successfully prepared. X-ray diffraction analysis showed that in the AlN composites, the addition of Nb2O5 gives rise to Nb4N3 during sintering. The compound Y3Al5O12 (YAG) was observed as precipitate in the sample with Y2O3. X-ray diffraction analysis of the TiB2 composites showed TiB2 as a single phase in these materials. The maximum Vickers and toughness values were 14.19 ± 1.43 GPa and 27.52 ± 1.75 GPa for the AlN and TiB2 composites, respectively. PMID:28772681

Crystal structure and optical property of complex perovskite oxynitrides ALi0.2Nb0.8O2.8N0.2, ANa0.2Nb0.8O2.8N0.2, and AMg0.2Nb0.8O2.6N0.4 (A = Sr, Ba)

NASA Astrophysics Data System (ADS)

Moon, Keon Ho; Avdeev, Maxim; Kim, Young-Il

2017-10-01

Oxynitride type complex perovskites AM0.2Nb0.8O3-xNx (A = Sr, Ba; M = Li, Na, Mg) were newly synthesized by the solid state diffusion of Li+, Na+, or Mg2+ into the layered oxide, A5Nb4O15, with concurrent O/N substitution. Neutron and synchrotron X-ray Rietveld refinement showed that SrLi0.2Nb0.8O2.8N0.2, SrNa0.2Nb0.8O2.8N0.2, and SrMg0.2Nb0.8O2.6N0.4 had body-centered tetragonal symmetry (I4/mcm), while those with A = Ba had simple cubic symmetry (Pm 3 ̅ m). In the tetragonal Sr-compounds, the nitrogen atoms were localized on the c-axial 4a site. However, the octahedral cations, M/Nb (M = Li, Na, Mg) were distributed randomly in all six compounds. The lattice volume of AM0.2Nb0.8O3-xNx was dependent on various factors including the type of A and the electronegativity of M. Compared to the simple perovskites, ANbO2N (A = Sr, Ba), AM0.2Nb0.8O3-xNx had wider band gaps (1.76-2.15 eV for A = Sr and 1.65-2.10 eV for A = Ba), but significantly lower sub-gap absorption.

Infrared absorption spectra of N(CxF2x+1)3, x = 2-5 perfluoroamines

NASA Astrophysics Data System (ADS)

Bernard, François; Papanastasiou, Dimitrios K.; Papadimitriou, Vassileios C.; Burkholder, James B.

2018-05-01

Infrared absorption spectra of the perfluoroamines (N(C2F5)3, N(C3F7)3, N(C4F9)3, and N(C5F11)3) were measured over the 500-4000 cm-1 spectral region at 294 K using Fourier transform infrared (FTIR) spectroscopy at 1 cm-1 resolution. Spectral measurements were performed using static measurements of dilute perfluoroamines mixtures and by infusion of the pure compound into a calibrated gas flow. The perfluoroamines absorb strongly in the "atmospheric window" with integrated band strengths (10-17 cm2 molecule-1 cm-1) between 570 and 1500 cm-1 of 59.9, 74.9, 88.9, and 98.7 for N(C2F5)3, N(C3F7)3, N(C4F9)3, and N(C5F11)3, respectively. Radiative efficiencies (RE) for the perfluoroamines were estimated to be 0.61, 0.75, 0.87, and 0.95 W m-2 ppb-1 for atmospherically well-mixed conditions and including a +10% stratospheric temperature correction for N(C2F5)3, N(C3F7)3, N(C4F9)3, and N(C5F11)3, respectively. Theoretical calculations of the perfluoroamines were performed at the B97-1/6-311++G(2df,2p) level of theory and optimized perfluoroamine geometries, vibrational band positions, and band strengths are reported. The theoretically calculated infrared spectra are in good agreement with the experimental spectra, while comparison of individual bands was not attempted due to the significant overlap of vibrational bands in the experimental spectra.

Raman spectroscopy, thermal and optical properties of TeO2-ZnO-Nb2O5-Nd2O3 glasses

NASA Astrophysics Data System (ADS)

Kamalaker, V.; Upender, G.; Ramesh, Ch.; Chandra Mouli, V.

2012-04-01

The glasses with composition 75TeO2-10ZnO-(15-x)Nb2O5-xNd2O3 (0 ≤ x ≤ 9 mol%) were prepared using melt quenching method and their physical properties such as density (ρ), molar volume (VM), average crosslink density (n¯), oxygen packing density (OPD) and number of bonds per unit volume (nb) were determined. Raman spectroscopic studies showed that the glass network consists of TeO4, TeO3+1, TeO3 and NbO6 units as basic structural units. The glass transition temperature (Tg), crystallization onset (To) and thermal stability (ΔT) were determined from DSC thermograms. The Raman and DSC results were found to be correlated with the physical properties. In the optical absorption spectra six absorption bands were observed with different relative intensities at around 464, 522, 576, 742, 801 and 871 nm which are assigned to the transition of electrons from (ground state) 4I9/2 → G11/2; 4I9/2 → 2K3/2, 2G7/2; 4I9/2 → 4G5/2, 4G7/2; 4I9/2 → 4S3/2; 4F7/2 → 2H9/2, 4F5/2 and 4I9/2 → 2F3/2 respectively. From optical absorption data the energy band gap (Eopt) and Urbach energy (ΔE) were calculated.

Bis(2,2'-bipyridyl-κN,N')(carbonato-κO,O')cobalt(III) bromide trihydrate.

PubMed

Ma, Peng-Tao; Wang, Yu-Xia; Zhang, Guo-Qian; Li, Ming-Xue

2007-12-06

The title complex, [Co(CO(3))(C(10)H(8)N(2))(2)]Br·3H(2)O, is isostructural with the chloride analogue. The six-coordinated octahedral [Co(2,2'-bipy)(2)CO(3)](+) cation (2,2'-bipy is 2,2'-bipyrid-yl), bromide ion and water mol-ecules are linked together via O-H⋯Br and O-H⋯O hydrogen bonds, generating a one-dimensional chain.

Theoretical study of the interaction of N/sub 2/ with water molecules. (H/sub 2/O)/sub n/:N/sub 2/, n = 1--8

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

Curtiss, L.A.; Eisgruber, C.L.

1984-03-01

Ab initio molecular orbital calculations including correlation energy have been carried out on the interaction of a single H/sub 2/O molecule with N/sub 2/. The potential energy surface for H/sub 2/O:N/sub 2/ is found to have a minimum corresponding to a HOH xxx N/sub 2/ structure with a weak (<2 kcal mol/sup -1/) hydrogen bond. A second, less stable, configuration corresponding to a H/sub 2/O xxx N/sub 2/ structure with N/sub 2/ bonded side on to the oxygen of H/sub 2/O was found to be either a minimum or a saddle point in the potential energy surface depending on themore » level of calculation. The minimal STO-3G basis set was used to investigate the interaction of up to eight H/sub 2/O molecules with N/sub 2/. Two types of clusters, one containing only HOH xxx N/sub 2/ interactions and the other containing both HOH xxxN/sub 2/ and H/sub 2/O xxx N/sub 2/ interactions, were investigated for (N/sub 2/:(H/sub 2/O)/sub n/, n = 2--8).« less

Magnetoelectric effect in antiferromagnetic multiferroic Pb (F e1 /2N b1 /2)O3 and its solid solutions with PbTi O3

NASA Astrophysics Data System (ADS)

Laguta, V. V.; Stephanovich, V. A.; Raevski, I. P.; Raevskaya, S. I.; Titov, V. V.; Smotrakov, V. G.; Eremkin, V. V.

2017-01-01

Antiferromagnets (AFMs) are presently considered as promising materials for applications in spintronics and random access memories due to the robustness of information stored in the AFM state against perturbing magnetic fields. In this respect, AFM multiferroics may be attractive alternatives for conventional AFMs as the coupling of magnetism with ferroelectricity (magnetoelectric effect) offers an elegant possibility of electric-field control and switching of AFM domains. Here we report the results of comprehensive experimental and theoretical investigations of the quadratic magnetoelectric (ME) effect in single crystals and highly resistive ceramics of Pb (F e1 /2N b1 /2)O3 (PFN) and (1 -x ) Pb (F e1 /2N b1 /2) O3-x PbTi O3(PFN -x PT ) . We are interested primarily in the temperature range of the multiferroic phase, T <150 K , where the ME coupling coefficient is extremely large (as compared to the well-known multiferroic BiFe O3 ) and shows sign reversal at the paramagnetic-to-antiferromagnetic phase transition. Moreover, we observe strong ME response nonlinearity in the AFM phase in the magnetic fields of only a few kOe. To describe the temperature and magnetic field dependencies of the above unusual features of the ME effect in PFN and PFN-x PT , we use a simple phenomenological Landau approach which explains experimental data surprisingly well. Our ME measurements demonstrate that the electric field of only 20-25 kV/cm is able to switch the AFM domains and align them with ferroelectric ones even in PFN ceramic samples.

Emission analysis of Tb3+ -and Sm3+ -ion-doped (Li2 O/Na2 O/K2 O) and (Li2 O + Na2 O/Li2 O + K2 O/K2 O + Na2 O)-modified borosilicate glasses.

PubMed

Naveen Kumar Reddy, B; Sailaja, S; Thyagarajan, K; Jho, Young Dahl; Sudhakar Reddy, B

2018-05-01

Four series of borosilicate glasses modified by alkali oxides and doped with Tb 3+ and Sm 3+ ions were prepared using the conventional melt quenching technique, with the chemical composition 74.5B 2 O 3 + 10SiO 2 + 5MgO + R + 0.5(Tb 2 O 3 /Sm 2 O 3 ) [where R = 10(Li 2 O /Na 2 O/K 2 O) for series A and C, and R = 5(Li 2 O + Na 2 O/Li 2 O + K 2 O/K 2 O + Na 2 O) for series B and D]. The X-ray diffraction (XRD) patterns of all the prepared glasses indicate their amorphous nature. The spectroscopic properties of the prepared glasses were studied by optical absorption analysis, photoluminescence excitation (PLE) and photoluminescence (PL) analysis. A green emission corresponding to the 5 D 4 → 7 F 5 (543 nm) transition of the Tb 3+ ions was registered under excitation at 379 nm for series A and B glasses. The emission spectra of the Sm 3+ ions with the series C and D glasses showed strong reddish-orange emission at 600 nm ( 4 G 5/2 → 6 H 7/2 ) with an excitation wavelength λ exci = 404 nm ( 6 H 5/2 → 4 F 7/2 ). Furthermore, the change in the luminescence intensity with the addition of an alkali oxide and combinations of these alkali oxides to borosilicate glasses doped with Tb 3+ and Sm 3+ ions was studied to optimize the potential alkali-oxide-modified borosilicate glass. Copyright © 2017 John Wiley & Sons, Ltd.

A novel amido-pyrophosphate Mn(II) chelate complex with the synthetic ligand O{P(O)[NHC(CH3)3]2}2 (L): [Mn(L)2{OC(H)N(CH3)2}2]Cl2·2H2O.

PubMed

Tarahhomi, Atekeh; Pourayoubi, Mehrdad; Fejfarová, Karla; Dušek, Michal

2013-03-01

The title complex, trans-bis(dimethylformamide-κO)bis{N,N'-N'',N'''-tetra-tert-butyl[oxybis(phosphonic diamide-κO)]}manganese(II) dichloride dihydrate, [Mn(C16H40N4O3P2)2(C3H7NO)2]Cl2·2H2O, is the first example of a bis-chelate amido-pyrophosphate (pyrophosphoramide) complex containing an O[P(O)(NH)2]2 fragment. Its asymmetric unit contains half of the complex dication, one chloride anion and one water molecule. The Mn(II) atom, located on an inversion centre, is octahedrally coordinated, with a slight elongation towards the monodentate dimethylformamide ligand. Structural features of the title complex, such as the P=O bond lengths and the planarity of the chelate ring, are compared with those of previously reported complexes with six-membered chelates involving the fragments C(O)NHP(O), (X)NP(O) [X = C(O), C(S), S(O)2 and P(O)] and O[P(O)(N)2]2. This analysis shows that the six-membered chelate rings are less puckered in pyrophosphoramide complexes containing a P(O)OP(O) skeleton, such as the title compound. The extended structure of the title complex involves a linear aggregate mediated by N-H...O and N-H...Cl hydrogen bonds, in which the chloride anion is an acceptor in two additional O-H...Cl hydrogen bonds.

Enhanced phosphorescence in N contained Ba 2SiO 4:Eu 2+ for X-ray and cathode ray tubes

NASA Astrophysics Data System (ADS)

Wang, Meiyuan; Zhang, Xia; Hao, Zhendong; Ren, Xinguang; Luo, Yongshi; Wang, Xiaojun; Zhang, Jiahua

2010-07-01

A bluish-green color long-lasting phosphorescent phosphor of N contained Ba 2SiO 4:Eu 2+ for X-ray and cathode ray tubes are prepared with the chemical component formula Ba 2SiO 4:0.01Eu 2+ - xSi 3N 4 - 2BaCO 3 ( x = 0.1 to 1.0) by the conventional high-temperature solid-state method. The phosphorescence and fluorescence properties as a function of Si 3N 4 content and temperature are investigated. The emission spectra show a single broad band peaking at 505 nm, which are ascribed to the 4f 65d 1 → 4f 7 transition of Eu 2+. Thermoluminescence (TL) glow-curves show that Ba 2SiO 4:0.01Eu 2+ without N holds a high-temperature peak at 417 K. With increasing the content of Si 3N 4, the phosphorescence grows super-linearly and some new TL peaks appear at low temperatures of about 400, 355, 365, and 335 K. These peaks are ascribed to the formation of new traps related to N substitution for O.

Photocatalytic decomposition of N2O over TiO2/g-C3N4 photocatalysts heterojunction

NASA Astrophysics Data System (ADS)

Kočí, K.; Reli, M.; Troppová, I.; Šihor, M.; Kupková, J.; Kustrowski, P.; Praus, P.

2017-02-01

TiO2/g-C3N4 photocatalysts with the various TiO2/g-C3N4 weight ratios from 1:2 to 1:6 were fabricated by mechanical mixing in water suspension followed by calcination. Pure TiO2 was prepared by thermal hydrolysis and pure g-C3N4 was prepared from commercial melamine by thermal annealing at 620 °C. All the nanocomposites were characterized by X-ray powder diffraction, UV-vis diffuse reflectance spectroscopy, Raman spectroscopy, infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, photoelectrochemical measurements and nitrogen physisorption. The prepared mixtures along with pure TiO2 and g-C3N4 were tested for the photocatalytic decomposition of nitrous oxide under UVC (λ = 254 nm), UVA (λ = 365 nm) and Vis (λ > 400 nm) irradiation. The TiO2/g-C3N4 nanocomposites showed moderate improvement compared to pure g-C3N4 but pure TiO2 proved to be a better photocatalyst under UVC irradiation. However, under UVA irradiation conditions, the photocatalytic activity of TiO2/g-C3N4 (1:2) nanocomposite exhibited an increase compared to pure TiO2. Nevertheless, further increase of g-C3N4 amount leads/led to a decrease in reactivity. These results are suggesting the nanocomposite with the optimal weight ratio of TiO2 and g-C3N4 have shifted absorption edge energy towards longer wavelengths and decreased the recombination rate of charge carriers compared to pure g-C3N4. This is probably due to the generation of heterojunction on the TiO2/g-C3N4 interface.

Effects of N2-O2 and CO2-O2 tensions on growth of fungi isolated from damaged flue-cured tobacco.

PubMed

Yang, H; Lucas, G B

1970-02-01

Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N(2)-O(2) or CO(2)-O(2). A 1 to 5% concentration of O(2) in an N(2) atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O(2) for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O(2). High O(2) concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O(2) in the N(2) atmosphere, furrows formed in mycelial mats between 5 and 40% O(2) in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O(2) decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO(2)-O(2) mixtures radial growth of all species increased with each quantitative decrease of CO(2). All species except A. niger grew faster in air than in 10% CO(2). In contrast to N(2)-O(2) mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O(2) concentrations.

Enhanced photoluminescence and phosphorescence properties of green phosphor Zn2GeO4:Mn(2+)via composition modification with GeO2 and MgF2.

PubMed

Pan, Yuexiao; Li, Li; Lu, Jing; Pang, Ran; Wan, Li; Huang, Shaoming

2016-06-21

A green long-lasting phosphorescence (LLP) phosphor Zn2GeO4:Mn(2+) (ZGOM) has been synthesized by a solid-state method at 1100 °C in air. The luminescence intensity has been improved up to 9 and 6 times through mixing GeO2 and MgF2 into the composition, respectively. The phosphorescence duration of the sample has been prolonged to 5 h. The phosphor, composed of a mixture of Zn2GeO4 (ZGO), GeO2, and MgGeO3 phases, emits enhanced green luminescence with a broad excitation band between 250 nm to 400 nm. Under identical measurement conditions, the optimized phosphor ZGOM has a higher emission intensity and shows longer wavelength emission than those of the commercial green LLP phosphor SrAl2O4:Eu,Dy (SAOED) under an excitation at 336 nm. The quantum yield of the sample modified by GeO2 and MgF2 is as high as 95.0%. Understanding of the formation mechanism for enhancement of emission intensity and prolonging of phosphorescence duration of ZGOM is fundamentally important, which might be extended to other identified solid-state inorganic phosphor materials for advanced properties.

Estimating N2O processes during grassland renewal and grassland conversion to maize cropping using N2O isotopocules

NASA Astrophysics Data System (ADS)

Buchen, Caroline; Well, Reinhard; Flessa, Heinz; Fuß, Roland; Helfrich, Mirjam; Lewicka-Szczebak, Dominika

2017-04-01

Grassland break-up due to grassland renewal and grassland conversion to cropland can lead to a flush of mineral nitrogen from decomposition of the old grass sward and the decomposition of soil organic matter. Moreover, increased carbon and nitrogen mineralisation can result in enhanced nitrous oxide (N2O) emissions. As N2O is known to be an important greenhouse gas and a major precursor for ozone depletion, its emissions need to be mitigated by adjusting agricultural management practices. Therefore, it is necessary to understand the N2O processes involved, as well as the contribution of N2O reduction to N2. Apart from the widely used 15N gas flux method, natural abundance isotopic analysis of the four most abundant isotopocules of N2O species is a promising alternative to assess N2O production pathways. We used stable isotope analyses of soil-emitted N2O (δ18ON2O, δ15NN2Obulk and δ15NN2OSP= intramolecular distribution of 15N within the linear N2O molecule) with an isotopocule mapping approach to simultaneously estimate the magnitude of N2O reduction to N2 and the fraction of N2O originating from the bacterial denitrification pathway or fungal denitrification and/or nitrification. This approach is based on endmember areas of isotopic values for the N2O produced from different sources reported in the literature. For this purpose, we calculated two main scenarios with different assumptions for N2O produced: N2O is reduced to N2 before residual N2O is mixed with N2O of various sources (Scenario a) and vice versa (Scenario b). Based on this, we applied seven different scenario variations, where we evaluated the range of possible values for the potential N2O production pathways (heterotrophic bacterial denitrification and/or nitrifier denitrification and fungal denitrification and/or nitrification). This was done by using a range of isotopic endmember values and assuming different fractionation factors of N2O reduction in order to find the most reliable scenario

Spatial variability in groundwater N2 and N2O in the San Joaquin River

NASA Astrophysics Data System (ADS)

Hinshaw, S.; Dahlgren, R. A.

2010-12-01

The San Joaquin River is surrounded by nearly 2 million acres of irrigated agricultural land. Groundwater inputs from agricultural areas can have severe negative effects on water quality with high nitrate concentrations being a major concern. Riparian zones are important ecological habitats that mitigate nitrogen loading from groundwater discharging into rivers primarily by denitrification. Denitrification is a permanent removal of nitrate by anaerobic microbial communities via the reduction to NO, N2O and N2. However, previous studies have shown that these areas can be source of N2O emissions. Although removal of nitrate through denitrification is advantageous from a water quality perspective, N2O is a harmful greenhouse gas. This study aimed to investigate nitrogen dynamics and dissolved N gases in surface and groundwater of the riparian zones of the San Joaquin River. Excess N2 and N2O concentrations were measured in surface and groundwater at 4 locations along a 33 km reach of the river. Samples were collected within bank sediments and 5 transect points across the river at depth intervals between 2-3 cm and 150 cm. Dissolved N2 and Ar were measured by membrane inlet mass spectrometry and used to estimate excess dissolved N2 concentrations. Dissolved N2O concentrations were measured using the headspace equilibrium technique and analyzed with a gas chromatograph. Both N2 uptake and excess N2 were present, ranging from -3.40 to 8.65 N2 mg/L with a median concentration of 1.20 N2 mg/L. Significantly lower concentrations of N2O were present ranging from 0.0 to 0.12 N2O mg/L. Deeper groundwater sites had significantly higher N2 and N2O concentrations coinciding with decreased O2. The presence of excess N2 and low N2O concentrations documents the importance of denitrification in removing nitrate from groundwater. Further investigation will examine N2O emissions from riparian soils and benthic sediments using static chambers and focus on nitrogen pathways that

Biomedical bandpass filter for fluorescence microscopy imaging based on TiO2/SiO2 and TiO2/MgF2 dielectric multilayers

NASA Astrophysics Data System (ADS)

Butt, M. A.; Fomchenkov, S. A.; Ullah, A.; Verma, P.; Khonina, S. N.

2016-08-01

We report a design for creating a multilayer dielectric optical filters based on TiO2 and SiO2/MgF2 alternating layers. We have selected Titanium dioxide (TiO2) for high refractive index (2.5), Silicon dioxide (SiO2) and Magnesium fluoride (MgF2) as a low refractive index layer (1.45 & 1.37) respectively. Miniaturized visible spectrometers are useful for quick and mobile characterization of biological samples. Such devices can be fabricated by using Fabry-Perot (FP) filters consisting of two highly reflecting mirrors with a central cavity in between. Distributed Bragg Reflectors (DBRs) consisting of alternating high and low refractive index material pairs are the most commonly used mirrors in FP filters, due to their high reflectivity. However, DBRs have high reflectivity for a selected range of wavelengths known as the stopband of the DBR. This range is usually much smaller than the sensitivity range of the spectrometer range. Therefore a bandpass filters are required to restrict wavelength outside the stopband of the FP DBRs. The proposed filter shows a high quality with average transmission of 97.4% within the passbands and the transmission outside the passband is around 4%. Special attention has been given to keep the thickness of the filters within the economic limits. It can be suggested that these filters are exceptional choice for florescence imaging and Endoscope narrow band imaging.

Properties and Crystallization Phenomena in Li2Si2O5–Ca5(PO4)3F and Li2Si2O5–Sr5(PO4)3F Glass–Ceramics Via Twofold Internal Crystallization

PubMed Central

Rampf, Markus; Dittmer, Marc; Ritzberger, Christian; Schweiger, Marcel; Höland, Wolfram

2015-01-01

The combination of specific mechanical, esthetic, and chemical properties is decisive for the application of materials in prosthodontics. Controlled twofold crystallization provides a powerful tool to produce special property combinations for glass–ceramic materials. The present study outlines the potential of precipitating Ca5(PO4)3F as well as Sr5(PO4)3F as minor crystal phases in Li2Si2O5 glass–ceramics. Base glasses with different contents of CaO/SrO, P2O5, and F− were prepared within the glasses of the SiO2–Li2O–K2O–CaO/SrO–Al2O3–P2O5–F system. Preliminary studies of nucleation by means of XRD and scanning electron microscopy (SEM) of the nucleated base glasses revealed X-ray amorphous phase separation phenomena. Qualitative and quantitative crystal phase analyses after crystallization were conducted using XRD in combination with Rietveld refinement. As a main result, a direct proportional relationship between the content of apatite-forming components in the base glasses and the content of apatite in the glass–ceramics was established. The microstructures of the glass–ceramics were investigated using SEM. Microstructural and mechanical properties were found to be dominated by Li2Si2O5 crystals and quite independent of the content of the apatite present in the glass–ceramics. Biaxial strengths of up to 540 MPa were detected. Ca5(PO4)3F and Sr5(PO4)3F influence the translucency of the glass–ceramics and, hence, help to precisely tailor the properties of Li2Si2O5 glass–ceramics. The authors conclude that the twofold crystallization of Li2Si2O5–Ca5(PO4)3F or Li2Si2O5–Sr5(PO4)3F glass–ceramics involves independent solid-state reactions, which can be controlled via the chemical composition of the base glasses. The influence of the minor apatite phase on the optical properties helps to achieve new combinations of features of the glass–ceramics and, hence, displays new potential for dental applications. PMID:26389112

Life on N2O: deciphering the ecophysiology of N2O respiring bacterial communities in a continuous culture.

PubMed

Conthe, Monica; Wittorf, Lea; Kuenen, J Gijs; Kleerebezem, Robbert; van Loosdrecht, Mark C M; Hallin, Sara

2018-04-01

Reduction of the greenhouse gas N 2 O to N 2 is a trait among denitrifying and non-denitrifying microorganisms having an N 2 O reductase, encoded by nosZ. The nosZ phylogeny has two major clades, I and II, and physiological differences among organisms within the clades may affect N 2 O emissions from ecosystems. To increase our understanding of the ecophysiology of N 2 O reducers, we determined the thermodynamic growth efficiency of N 2 O reduction and the selection of N 2 O reducers under N 2 O- or acetate-limiting conditions in a continuous culture enriched from a natural community with N 2 O as electron acceptor and acetate as electron donor. The biomass yields were higher during N 2 O limitation, irrespective of dilution rate and community composition. The former was corroborated in a continuous culture of Pseudomonas stutzeri and was potentially due to cytotoxic effects of surplus N 2 O. Denitrifiers were favored over non-denitrifying N 2 O reducers under all conditions and Proteobacteria harboring clade I nosZ dominated. The abundance of nosZ clade II increased when allowing for lower growth rates, but bacteria with nosZ clade I had a higher affinity for N 2 O, as defined by μ max /K s . Thus, the specific growth rate is likely a key factor determining the composition of communities living on N 2 O respiration under growth-limited conditions.

Surface passivation of n-type doped black silicon by atomic-layer-deposited SiO2/Al2O3 stacks

NASA Astrophysics Data System (ADS)

van de Loo, B. W. H.; Ingenito, A.; Verheijen, M. A.; Isabella, O.; Zeman, M.; Kessels, W. M. M.

2017-06-01

Black silicon (b-Si) nanotextures can significantly enhance the light absorption of crystalline silicon solar cells. Nevertheless, for a successful application of b-Si textures in industrially relevant solar cell architectures, it is imperative that charge-carrier recombination at particularly highly n-type doped black Si surfaces is further suppressed. In this work, this issue is addressed through systematically studying lowly and highly doped b-Si surfaces, which are passivated by atomic-layer-deposited Al2O3 films or SiO2/Al2O3 stacks. In lowly doped b-Si textures, a very low surface recombination prefactor of 16 fA/cm2 was found after surface passivation by Al2O3. The excellent passivation was achieved after a dedicated wet-chemical treatment prior to surface passivation, which removed structural defects which resided below the b-Si surface. On highly n-type doped b-Si, the SiO2/Al2O3 stacks result in a considerable improvement in surface passivation compared to the Al2O3 single layers. The atomic-layer-deposited SiO2/Al2O3 stacks therefore provide a low-temperature, industrially viable passivation method, enabling the application of highly n- type doped b-Si nanotextures in industrial silicon solar cells.

Hydrothermal synthesis, structural elucidation, spectroscopic studies, thermal behavior and luminescence properties of a new 3-d compound: FeAlF2(C10H8N2)(HPO4)2(H2O)

NASA Astrophysics Data System (ADS)

Bouzidia, Nabaa; Salah, Najet; Hamdi, Besma; Ben Salah, Abdelhamid

2017-04-01

The study of metal phosphate has been a proactive field of research thanks to its applied and scientific importance, especially in terms of the development of optical devices such as solid state lasers as well as optical fibers. The present paper seeks to investigate the synthesis, crystal structure, elemental analysis and properties of FeAlF2(C10H8N2)(HPO4)2(H2O) compound investigated by spectroscopic studies (FT-IR and FT-Raman), thermal behavior and luminescence. The Hirshfeld surface analysis and 2-D fingerprint plot have been performed to explore the behavior of these weak interactions and crystal cohesion. This investigation shows that the molecules are connected by hydrogen bonds of the type Osbnd H⋯O and Osbnd H⋯F. In addition, the 2,2'‒bipyridine ligand plays a significant role in the construction of 3-D supramolecular framework via π‒π stacking. FT‒IR and FT‒Raman spectra were used so as to ease the responsibilities of the vibration modes of the title compound. The thermal analysis (TGA) study shows a mass loss evolution as a temperature function. Finally, the optical properties were evaluated by photoluminescence spectroscopy.

Structure Characterization and Catalytic Properties of Cr2O3 Doped with MgO Supported on MgF2

NASA Astrophysics Data System (ADS)

Goslar, J.; Wojciechowska, M.; Zieliński, M.; Tomska-Foralewska, I.; Przystajko, W.

2006-08-01

A characterization of double oxide systems containing Cr2O3 doped with MgO and supported on MgF2 was carried out. The catalysts were prepared by impregnation and co-impregnation methods and characterized by the Brunauer-Emmett-Teller method, EPR, and temperature programmed reduction. The results proved the interactions between supported oxides and the presence of spinel-like phase after treatment at 400 ºC. Magnesium oxide clearly influences the catalytic activity as well as selectivity of chromium catalysts supported on MgF2. The MgO-Cr2O3/MgF2 systems were active and selective in the reaction of CO oxidation at the room temperature and in the dehydrogenation of cyclohexene.

[Pb2F2](SeO4): a heavier analogue of grandreefite, the first layered fluoride selenate

NASA Astrophysics Data System (ADS)

Charkin, Dmitri O.; Plokhikh, Igor V.; Zadoya, Anastasiya I.; Kazakov, Sergey M.; Zaloga, Alexander N.; Kozin, Michael S.; Depmeier, Wulf; Siidra, Oleg I.

2018-01-01

Co-precipitation of PbF2 and PbSeO4 in weakly acidic media results in the formation of [Pb2F2](SeO4), the selenate analogue of the naturally occurring mineral grandreefite, [Pb2F2](SO4). The new compound is monoclinic, C2/ c, a = 14.0784(2) Å, b = 4.6267(1) Å, c = 8.8628(1) Å, β = 108.98(1)°, V = 545.93(1) Å3. Its structure has been refined from powder data to R B = 1.55%. From thermal studies, it is established that the compound is stable in air up to about 300 °C, after which it gradually converts into a single phase with composition [Pb2O](SeO4), space group C2/ m, and lattice parameters a = 14.0332(1) Å, b = 5.7532(1) Å, c = 7.2113(1) Å, β = 115.07(1)°, V = 527.37(1) Å3. It is the selenate analogue of lanarkite, [Pb2O](SO4), and phoenicochroite, [Pb2O](CrO4), and its crystal structure was refined to R B = 1.21%. The formation of a single decomposition product upon heating in air suggests that this happens by a thermal hydrolysis mechanism, i.e., Pb2F2SeO4 + H2O (vapor) → Pb2OSeO4 + 2HF↑. This relatively low-temperature process involves complete rearrangement of the crystal structure—from a 2D architecture featuring slabs [Pb2F2]2+ formed by fluorine-centered tetrahedra into a structure characterized by 1D motifs based on [OPb2]2+ chains of oxocentered tetrahedra. The comparative crystal chemistry of the obtained anion-centered structural architectures is discussed.

Fundamental Insulation Characteristics of Air, N2, CO2, N2/O2 and SF6/N2 Mixed Gases

NASA Astrophysics Data System (ADS)

Rokunohe, Toshiaki; Yagihashi, Yoshitaka; Endo, Fumihiro; Oomori, Takashi

SF6 gas has excellent dielectric strength and interruption performance. For these reasons, it has been widely used for gas insulated switchgear (GIS). However, use of SF6 gas has become regulated under agreements set at the 1997 COP3. Presently, development of a gas circuit breaker (GCB) using CO2 gas and development of a high voltage vacuum circuit breaker (VCB) are being pursued. GIS consists of disconnectors (DS), earthing switches (ES) and buses in addition to GCB. Since the interruption performance is not an important requirement for DS, ES and BUS, use of a gas with high dielectric strength is better than use of a gas with good interruption performance. Air and N2 are not greenhouse gases, and their dielectric strengths are higher than those of other SF6 alternative gases, but only about one-third of the dielectric strength of SF6 gas. This paper deals with a suitable insulation gas which has no greenhouse effect as an SF6 alternative gas. The N2/O2 mixed gas was investigated by changing the ratio of O2. Moreover, the effect of an insulation coating was investigated and compared with the dielectric strength of SF6/N2 mixed gas. The dielectric strength of air under the coating condition was equal to that of 10%SF6/N2 mixed gas.

Structure of (Ga2O3)2(ZnO)13 and a unified description of the homologous series (Ga2O3)2(ZnO)(2n + 1).

PubMed

Michiue, Yuichi; Kimizuka, Noboru; Kanke, Yasushi; Mori, Takao

2012-06-01

The structure of (Ga(2)O(3))(2)(ZnO)(13) has been determined by a single-crystal X-ray diffraction technique. In the monoclinic structure of the space group C2/m with cell parameters a = 19.66 (4), b = 3.2487 (5), c = 27.31 (2) Å, and β = 105.9 (1)°, a unit cell is constructed by combining the halves of the unit cell of Ga(2)O(3)(ZnO)(6) and Ga(2)O(3)(ZnO)(7) in the homologous series Ga(2)O(3)(ZnO)(m). The homologous series (Ga(2)O(3))(2)(ZnO)(2n + 1) is derived and a unified description for structures in the series is presented using the (3+1)-dimensional superspace formalism. The phases are treated as compositely modulated structures consisting of two subsystems. One is constructed by metal ions and another is by O ions. In the (3 + 1)-dimensional model, displacive modulations of ions are described by the asymmetric zigzag function with large amplitudes, which was replaced by a combination of the sawtooth function in refinements. Similarities and differences between the two homologous series (Ga(2)O(3))(2)(ZnO)(2n + 1) and Ga(2)O(3)(ZnO)(m) are clarified in (3 + 1)-dimensional superspace. The validity of the (3 + 1)-dimensional model is confirmed by the refinements of (Ga(2)O(3))(2)(ZnO)(13), while a few complex phenomena in the real structure are taken into account by modifying the model.

C=C bond cleavage on neutral VO3(V2O5)n clusters.

PubMed

Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

2009-01-28

The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

Structural and spectral analyses of N,N'-(2,2'-dithiodi-o-phenylene)bis-(furan-2-carboxamide)

NASA Astrophysics Data System (ADS)

Yıldırım, Sema Öztürk; Büyükmumcu, Zeki; Pekdur, Özlem Savaş; Butcher, Ray J.; Doǧan, Şengül Dilem

2018-02-01

In this study we report structure determination of N,N'-(2,2'-dithiodi-o-phenylene)bis-(furan-2-carboxamide). 2,2'-Dithiobis(benzamide) derivatives have been reported to possess important biological properties such as antibacterial, antifungal activities and inhibition of blood platelet aggregation and redeterrmined at 100(2)K from the data published by Raftery, Lallbeeharry, Bhowon, Laulloo & Joulea [Acta Cryst. 2009, E65, o16]. 2,2'-Dithiobis(N-butyl-benzamide) has been reported to be useful as an antiseptic for cosmetics. The structural properties of the compound have been characterized by using 1H NMR and the structure were determined by single-crystal X-ray diffraction. Molecular structure crystallizes in triclinic form, space group with a = 9.6396(7) Å, b = 9.9115(7) Å, c = 12.0026(8) Å, α = 109.743(6)°, β = 103.653(6)°, γ = 104.633(6)° and V = 977.15(13) Å3. In the solid state of the molecular structure N-H…S, N-H…O and C-H…O, type interactions provide for stabilization. The geometries of the title compound have been optimized using density functional theory (DFT) method. The calculated values were found to be in agreement with the experimental data.

Removal of NO in NO/N2, NO/N2/O2, NO/CH4/N2, and NO/CH4/O2/N2 systems by flowing microwave discharges.

PubMed

Hueso, José L; Gonzalez-Elipe, Agustín R; Cotrino, José; Caballero, Alfonso

2007-02-15

In this paper, continuing previous work, we report on experiments carried out to investigate the removal of NO from simulated flue gas in nonthermal plasmas. The plasma-induced decomposition of small concentrations of NO in N2 used as the carrier gas and O2 and CH4 as minority components has been studied in a surface wave discharge induced with a surfatron launcher. The reaction products and efficiency have been monitored by mass spectrometry as a function of the composition of the mixture. NO is effectively decomposed into N2 and O2 even in the presence of O2, provided always that enough CH4 is also present in the mixture. Other majority products of the plasma reactions under these conditions are NH3, CO, and H2. In the absence of O2, decomposition of NO also occurs, although in that case HCN accompanies the other reaction products as a majority component. The plasma for the different reaction mixtures has been characterized by optical emission spectroscopy. Intermediate excited species of NO*, C*, CN*, NH*, and CH* have been monitored depending on the gas mixture. The type of species detected and their evolution with the gas composition are in agreement with the reaction products detected in each case. The observations by mass spectrometry and optical emission spectroscopy are in agreement with the kinetic reaction models available in literature for simple plasma reactions in simple reaction mixtures.

Volatile organic compounds emission control in industrial pollution source using plasma technology coupled with F-TiO2/γ-Al2O3.

PubMed

Zhu, Tao; Chen, Rui; Xia, Ni; Li, Xiaoyang; He, Xianxian; Zhao, Wenjuan; Carr, Tim

2015-01-01

Volatile organic compounds' (VOCs) effluents, which come from many industries, are triggering serious environmental problems. As an emerging technology, non-thermal plasma (NTP) technology is a potential technology for VOCs emission control. NTP coupled with F-TiO2/γ-Al2O3 is used for toluene removal from a gaseous influent at normal temperature and atmospheric pressure. NTP is generated by dielectric barrier discharge, and F-TiO2/γ-Al2O3 can be prepared by sol-gel method in the laboratory. In the experiment, the different packed materials were packed into the plasma reactor, including γ-Al2O3, TiO2/γ-Al2O3 and F-TiO2/γ-Al2O3. Through a series of characterization methods such as X-ray diffraction, scanning electronic microscopy and Brunner-Emmet-Teller measurements, the results show that the particle size distribution of F-TiO2 is relatively smaller than that of TiO2, and the pore distribution of F-TiO2 is more uniformly distributed than that of TiO2. The relationships among toluene removal efficiency, reactor input energy density, and the equivalent capacitances of air gap and dielectric barrier layer were investigated. The results show that the synergistic technology NTP with F-TiO2/γ-Al2O3 resulted in greater enhancement of toluene removal efficiency and energy efficiency. Especially, when packing with F-TiO2/γ-Al2O3 in NTP reactor, toluene removal efficiency reaches 99% and higher. Based on the data analysis of Fourier Transform Infrared Spectroscopy, the experimental results showed that NTP reactor packed with F-TiO2/γ-Al2O3 resulted in a better inhibition for by-products formation effectively in the gas exhaust.

Overlap corrections for emissivity calculations of H2O-CO2-CO-N2 mixtures

NASA Astrophysics Data System (ADS)

Alberti, Michael; Weber, Roman; Mancini, Marco

2018-01-01

Calculations of total gas emissivities of gas mixtures containing several radiatively active species require corrections for band overlapping. In this paper, we generate such overlap correction charts for H2O-CO2-N2, H2O-CO-N2, and CO2-CO-N2 mixtures. These charts are applicable in the 0.1-40 bar total pressure range and in the 500 K-2500 K temperature range. For H2O-CO2-N2 mixtures, differences between our charts and Hottel's graphs as well as models of Leckner and Modak are highlighted and analyzed.

CsFe3(SeO3)2F6 with S = 5/2 Cube Tile Lattice.

PubMed

Lu, Hongcheng; Kageyama, Hiroshi

2018-05-21

A layered iron selenite fluoride CsFe 3 (SeO 3 ) 2 F 6 1 was hydrothermally synthesized. Single-crystal X-ray diffraction studies show that 1 has a trigonal ( P3̅ m1) lattice, where [Fe 3 (SeO 3 ) 2 F 6 ] - blocks of three iron sublayers are separated by Cs cations. Within the block, only Fe(2)F 6 and Fe(1)O 3 F 3 octahedra are magnetically connected via superexchange Fe(1) -F -Fe(2) pathways, giving an S = 5/2 cube tile (dice) lattice. At low magnetic field, 1 exhibits an antiferromagnetic transition at ∼130 K, where ferrimagnetic cube tile layers are arranged in a staggered manner. At low temperatures, we observed a field-induced transition to a ferrimagnetic state with a one-third magnetization plateau.

Reaction of N2O5 with H2O on carbonaceous surfaces

NASA Technical Reports Server (NTRS)

Brouwer, L.; Rossi, M. J.; Golden, D. M.

1986-01-01

The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

Statistical modeling of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2.

PubMed

Ushakov, Vladimir G; Troe, Jürgen; Johnson, Ryan S; Guo, Hua; Ard, Shaun G; Melko, Joshua J; Shuman, Nicholas S; Viggiano, Albert A

2015-08-14

The rates of the reactions Fe(+) + N2O → FeO(+) + N2 and FeO(+) + CO → Fe(+) + CO2 are modeled by statistical rate theory accounting for energy- and angular momentum-specific rate constants for formation of the primary and secondary cationic adducts and their backward and forward reactions. The reactions are both suggested to proceed on sextet and quartet potential energy surfaces with efficient, but probably not complete, equilibration by spin-inversion of the populations of the sextet and quartet adducts. The influence of spin-inversion on the overall reaction rate is investigated. The differences of the two reaction rates mostly are due to different numbers of entrance states (atom + linear rotor or linear rotor + linear rotor, respectively). The reaction Fe(+) + N2O was studied either with (6)Fe(+) or with (4)Fe(+) reactants. Differences in the rate constants of (6)Fe(+) and (4)Fe(+) reacting with N2O are attributed to different contributions from electronically excited potential energy surfaces, such as they originate from the open-electronic shell reactants.

Hardness properties and microscopic investigation of crack- crystal interaction in SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F glass ceramic system.

PubMed

Roy, Shibayan; Basu, Bikramjit

2010-01-01

In view of the potential engineering applications requiring machinability and wear resistance, the present work focuses to evaluate hardness property and to understand the damage behavior of some selected glass-ceramics having different crystal morphologies with SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F composition, using static micro-indentation tests as well as dynamic scratch tests, respectively. Vickers hardness of up to 5.5 GPa has been measured in glass-ceramics containing plate like mica crystals. Scratch tests at a high load of 50 Nin artificial saliva were carried out in order to simulate the crack-microstructure interaction during real-time abrasion wear and machining operation. The experimental observations indicate that the novel "spherulitic-dendritic shaped "crystals, similar to the plate like crystals, have the potential to hinder the scratching induced crack propagation. In particular, such potential of the 'spherulitic-dendritic' crystals become more effective due to the larger interfacial area with the glass matrix as well as the dendritic structure of each mica plate, which helps in crack deflection and crack blunting, to a larger extent.While modest damage tolerant behavior is observed in case of 'spherulitic-dendritic' crystal containing material, severe brittle fracture of plate like crystals were noted, when both were scratched at 50 N load.

Octa-akis(4-amino-pyridine)-1κN,2κN-aqua-2κO-μ-carbonato-1:2κO,O':O''-dinickel(II) dichloride penta-hydrate.

PubMed

Fun, Hoong-Kun; Sinthiya, A; Jebas, Samuel Robinson; Ravindran Durai Nayagam, B; Alfred Cecil Raj, S

2008-10-18

In the title compound, [Ni(2)(CO(3))(C(5)H(6)N(2))(8)(H(2)O)]Cl(2)·5H(2)O, one of the the Ni(II) ions is six-coordinated in a distorted octa-hedral geometry, with the equatorial plane defined by four pyridine N atoms from four amino-pyridine ligands, the axial positions being occupied by one water O and a carbonate O atom. The other Ni(II) ion is also six-coordinated, by four other pyridine N atoms from four other amino-pyridine ligands and two carbonate O atoms to complete a distorted octa-hedral geometry. In the crystal structure, mol-ecules are linked into an infinite three-dimensional network by O-H⋯O, N-H⋯Cl, N-H⋯O, O-H⋯N, C-H⋯O, C-H⋯N and C/N-H⋯π inter-actions involving the pyridine rings.

Decreased N2O reduction by low soil pH causes high N2O emissions in a riparian ecosystem.

PubMed

Van den Heuvel, R N; Bakker, S E; Jetten, M S M; Hefting, M M

2011-05-01

Quantification of harmful nitrous oxide (N(2)O) emissions from soils is essential for mitigation measures. An important N(2)O producing and reducing process in soils is denitrification, which shows deceased rates at low pH. No clear relationship between N(2)O emissions and soil pH has yet been established because also the relative contribution of N(2)O as the denitrification end product decreases with pH. Our aim was to show the net effect of soil pH on N(2)O production and emission. Therefore, experiments were designed to investigate the effects of pH on NO(3)(-) reduction, N(2)O production and reduction and N(2) production in incubations with pH values set between 4 and 7. Furthermore, field measurements of soil pH and N(2)O emissions were carried out. In incubations, NO(3)(-) reduction and N(2) production rates increased with pH and net N(2)O production rate was highest at pH 5. N(2)O reduction to N(2) was halted until NO(3)(-) was depleted at low pH values, resulting in a built up of N(2)O. As a consequence, N(2)O:N(2) production ratio decreased exponentially with pH. N(2)O reduction appeared therefore more important than N(2)O production in explaining net N(2)O production rates. In the field, a negative exponential relationship for soil pH against N(2)O emissions was observed. Soil pH could therefore be used as a predictive tool for average N(2)O emissions in the studied ecosystem. The occurrence of low pH spots may explain N(2)O emission hotspot occurrence. Future studies should focus on the mechanism behind small scale soil pH variability and the effect of manipulating the pH of soils. © 2011 Blackwell Publishing Ltd.

Effects of N2-O2 and CO2-O2 Tensions on Growth of Fungi Isolated from Damaged Flue-Cured Tobacco 1

PubMed Central

Yang, H.; Lucas, G. B.

1970-01-01

Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N2-O2 or CO2-O2. A 1 to 5% concentration of O2 in an N2 atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O2 for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O2. High O2 concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O2 in the N2 atmosphere, furrows formed in mycelial mats between 5 and 40% O2 in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O2 decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO2-O2 mixtures radial growth of all species increased with each quantitative decrease of CO2. All species except A. niger grew faster in air than in 10% CO2. In contrast to N2-O2 mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O2 concentrations. PMID:5461786

Anharmonic Vibrational Spectroscopy of the F-(H20)n, complexes, n=1,2

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Xantheas, Sotiris; Gerber, R. Benny; Kwak, Dochan (Technical Monitor)

2003-01-01

We report anharmonic vibrational spectra (fundamentals, first overtones) for the F-(H(sub 2)O) and F-(H(sub 2)O)2 clusters computed at the MP2 and CCSD(T) levels of theory with basis sets of triple zeta quality. Anharmonic corrections were estimated via the correlation-corrected vibrational self-consistent field (CC-VSCF) method. The CC-VSCF anharmonic spectra obtained on the potential energy surfaces evaluated at the CCSD(T) level of theory are the first ones reported at a correlated level beyond MP2. We have found that the average basis set effect (TZP vs. aug-cc-pVTZ) is on the order of 30-40 cm(exp -1), whereas the effects of different levels of electron correlation [MP2 vs. CCSD(T)] are smaller, 20-30 cm(exp -1). However, the basis set effect is much larger in the case of the H-bonded O-H stretch of the F-(H(sub 2)O) cluster amounting to 100 cm(exp -1) for the fundamentals and 200 cm (exp -1) for the first overtones. Our calculations are in agreement with the limited available set of experimental data for the F-(H(sub 2)O) and F-(H(sub 2)O)2 systems and provide additional information that can guide further experimental studies.

Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

PubMed

Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

2016-02-01

This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

Equation of state for Eu-doped SrSi2O2N2

NASA Astrophysics Data System (ADS)

Ermakova, Olga; Paszkowicz, Wojciech; Kaminska, Agata; Barzowska, Justyna; Szczodrowski, Karol; Grinberg, Marek; Minikayev, Roman; Nowakowska, Małgorzata; Carlson, Stefan; Li, Guogang; Liu, Ru-Shi; Suchocki, Andrzej

2014-07-01

α-SrSi2O2N2 is one of the recently studied oxonitridosilicates applicable in optoelectronics, in particular in white LEDs. Its elastic properties remain unknown. A survey of literature shows that, up to now, nine oxonitridosilicate materials have been identified. For most of these compounds, doped with rare earths and manganese, a luminescence has been reported at a wavelength characteristic for the given material; all together cover a broad spectral range. The present study focuses on the elastic properties of one of these oxonitridosilicates, the Eu-doped triclinic α-SrSi2O2N2. High-pressure powder diffraction experiments are used in order to experimentally determine, for the first time, the equation of state of this compound. The in situ experiment was performed for pressures ranging up to 9.65 GPa, for Eu-doped α-SrSi2O2N2 sample mounted in a diamond anvil cell ascertaining the hydrostatic compression conditions. The obtained experimental variation of volume of the triclinic unit cell of α-SrSi2O2N2:Eu with rising pressure served for determination of the Birch-Murnaghan equation of state. The determined above quoted bulk modulus is 103(5) GPa, its first derivative is 4.5(1.1). The above quoted bulk modulus value is found to be comparable to that of earlier reported oxynitrides of different composition.

Ignition and Combustion of Pulverized Coal and Biomass under Different Oxy-fuel O2/N2 and O2/CO2 Environments

NASA Astrophysics Data System (ADS)

Khatami Firoozabadi, Seyed Reza

This work studied the ignition and combustion of burning pulverized coals and biomasses particles under either conventional combustion in air or oxy-fuel combustion conditions. Oxy-fuel combustion is a 'clean-coal' process that takes place in O2/CO2 environments, which are achieved by removing nitrogen from the intake gases and recirculating large amounts of flue gases to the boiler. Removal of nitrogen from the combustion gases generates a high CO2-content, sequestration-ready gas at the boiler effluent. Flue gas recirculation moderates the high temperatures caused by the elevated oxygen partial pressure in the boiler. In this study, combustion of the fuels took place in a laboratory laminar-flow drop-tube furnace (DTF), electrically-heated to 1400 K, in environments containing various mole fractions of oxygen in either nitrogen or carbon-dioxide background gases. The experiments were conducted at two different gas conditions inside the furnace: (a) quiescent gas condition (i.e., no flow or inactive flow) and, (b) an active gas flow condition in both the injector and furnace. Eight coals from different ranks (anthracite, semi-snthracite, three bituminous, subbituminous and two lignites) and four biomasses from different sources were utilized in this work to study the ignition and combustion characteristics of solid fuels in O2/N2 or O2/CO2 environments. The main objective is to study the effect of replacing background N2 with CO2, increasing O2 mole fraction and fuel type and rank on a number of qualitative and quantitative parameters such as ignition/combustion mode, ignition temperature, ignition delay time, combustion temperatures, burnout times and envelope flame soot volume fractions. Regarding ignition, in the quiescent gas condition, bituminous and sub-bituminous coal particles experienced homogeneous ignition in both O2/N 2 and O2/CO2 atmospheres, while in the active gas flow condition, heterogeneous ignition was evident in O2/CO 2. Anthracite, semi

trans-Bis(azido-kappaN)bis(pyridine-2-carboxamide-kappa2N1,O2)nickel(II).

PubMed

Daković, Marijana; Popović, Zora

2007-11-01

In the title compound, [Ni(N(3))(2)(C(6)H(6)N(2)O)(2)], the Ni(II) atom lies on an inversion centre. The distorted octahedral nickel(II) coordination environment contains two planar trans-related N,O-chelating picolinamide ligands in one plane and two monodentate azide ligands perpendicular to this plane. Molecules are linked into a three-dimensional framework by N-H...N hydrogen bonds.

48 CFR 47.305-2 - Solicitations f.o.b. origin and f.o.b. destination-lowest overall cost.

Code of Federal Regulations, 2010 CFR

2010-10-01

... 48 Federal Acquisition Regulations System 1 2010-10-01 2010-10-01 false Solicitations f.o.b. origin and f.o.b. destination-lowest overall cost. 47.305-2 Section 47.305-2 Federal Acquisition... Contracts 47.305-2 Solicitations f.o.b. origin and f.o.b. destination—lowest overall cost. (a) Solicitations...

Characterization of the N2O isotopic composition (15N, 18O and N2O isotopomers) emitted from incubated Amazon forest soils. Implications for the global N2O isotope budget

NASA Astrophysics Data System (ADS)

Pérez, T.; García, D.; Trumbore, S.; Tyler, S.; de Camargo, P.; Moreira, M.; Piccolo, M.; Park, S.; Boering, K.; Cerri, C.

2003-04-01

Tropical rain forest soils are the largest natural source of N2O to the atmosphere. Uncertainty in the signature of this source limits the utility of isotopes in constraining the global N2O budget. Differentiating the relative contribution of nitrification and denitrification to the emitted N2O using stable isotopes has been difficult due to the lack of enrichment factors values for each process measured in situ. We have devised a method for measuring enrichment factors using soil incubation experiments. We selected three Amazon rain forest soils: (1) Clay and (2) Sandy from Santarem, Pará State, and (3) Sandy from Nova Vida Farm, Rondonia State, Brazil. The enrichment factor values for nitrification and denitrification are: -97.8±4.2 and -9.9±3.8 per mil for clay Santarem soil, -86.8±4.3 and -45.2±4.5 per mil for sandy Santarem soil and-112.6±3.8 and -10.4±3.5 per mil for Nova Vida Farm soils, respectively. Our results show that enrichment factors for both processes differ with soil texture and location. The enrichment factors for nitrification are significantly smaller than the range reported in the literature (-66 to -42 per mil). Also, the enrichment factors for the Santarem soils (clay and sandy) differ significantly implying that soil texture (which will affect the soil air filled pore space at a given water content) is influencing the bacteria isotopic discrimination. However, the enrichment factors for the Santarem clay sand Nova Vida sandy soils do not differ by much. This suggests that the enrichment factors not only can be affected by texture but also by the microbial fauna present in these soils. We also determined the measurement of the N2O positional dependence. N2O is a linear molecule with two nitrogen atoms. The 15N isotope can be located in either the central nitrogen (alpha position) or in the terminal nitrogen (beta position). The isotopomer site preference (15N alpha - 15N beta) can be used to differentiate processes of production and

Excessive use of nitrogen in Chinese agriculture results in high N2O/(N2O+N2) product ratio of denitrification, primarily due to acidification of the soils

PubMed Central

Qu, Zhi; Wang, Jingguo; Almøy, Trygve; Bakken, Lars R

2014-01-01

China is the world's largest producer and consumer of fertilizer N, and decades of overuse has caused nitrate leaching and possibly soil acidification. We hypothesized that this would enhance the soils' propensity to emit N2O from denitrification by reducing the expression of the enzyme N2O reductase. We investigated this by standardized oxic/anoxic incubations of soils from five long-term fertilization experiments in different regions of China. After adjusting the nitrate concentration to 2 mM, we measured oxic respiration (R), potential denitrification (D), substrate-induced denitrification, and the denitrification product stoichiometry (NO, N2O, N2). Soils with a history of high fertilizer N levels had high N2O/(N2O+N2) ratios, but only in those field experiments where soil pH had been lowered by N fertilization. By comparing all soils, we found a strong negative correlation between pH and the N2O/(N2O+N2) product ratio (r2 = 0.759, P < 0.001). In contrast, the potential denitrification (D) was found to be a linear function of oxic respiration (R), and the ratio D/R was largely unaffected by soil pH. The immediate effect of liming acidified soils was lowered N2O/(N2O+N2) ratios. The results provide evidence that soil pH has a marginal direct effect on potential denitrification, but that it is the master variable controlling the percentage of denitrified N emitted as N2O. It has been known for long that low pH may result in high N2O/(N2O+N2) product ratios of denitrification, but our documentation of a pervasive pH-control of this ratio across soil types and management practices is new. The results are in good agreement with new understanding of how pH may interfere with the expression of N2O reductase. We argue that the management of soil pH should be high on the agenda for mitigating N2O emissions in the future, particularly for countries where ongoing intensification of plant production is likely to acidify the soils. PMID:24249526

Crystal structure of tri-aqua-(1,10-phen-anthroline-κ(2) N,N')(2,4,5-tri-fluoro-3-meth-oxy-benzoato-κO (1))cobalt(II) 2,4,5-tri-fluoro-3-meth-oxy-benzoate.

PubMed

Sun, Junshan

2014-11-01

The title salt, [Co(C8H4F3O3)(C12H8N2)(H2O)3](C8H4F3O3), was obtained under solvothermal conditions by the reaction of 2,4,5-tri-fluoro-3-meth-oxy-benzoic acid with CoCl2 in the presence of 1,10-phenanthroline (phen). The Co(II) ion is octa-hedrally coordinated by two N atoms [Co-N = 2.165 (2) and 2.129 (2) Å] from the phen ligand, by one carboxyl-ate O atom [Co-O = 2.107 (1) Å] and by three O atoms from water mol-ecules [Co-O = 2.093 (1), 2.102 (1) and 2.114 (1) Å]. The equatorial positions of the slightly distorted octa-hedron are occupied by the N atoms, the carboxyl-ate O and one water O atom. An intra- and inter-molecular O-H⋯O hydrogen-bonding network between the water-containing complex cation and the organic anion leads to the formation of ribbons parallel to [010].

Theoretical characterization of the F(2)O(3) molecule by coupled-cluster methods.

PubMed

Huang, Ming-Ju; Watts, John D

2010-09-23

Coupled-cluster calculations with extended basis sets that include noniterative connected triple excitations (CCSD(T)) have been used to study the FOOOF isomer of F(2)O(3). Second-order Moller-Plessett perturbation theory (MP2) and density-functional theory (B3LYP functional) calculations have also been performed for comparison. Two local minima of similar energy, namely, conformers of C(2) and C(s) symmetry have been located. Structures, harmonic vibrational frequencies, and standard enthalpies and free energies of formation have been calculated. The calculated bond lengths of F(2)O(3) are more characteristic of those in F(2)O and a "normal" peroxide than the unusual bond lengths in F(2)O(2). Both conformers have equal F-O and O-O bond lengths, contrary to a recent suggestion of an unsymmetrical structure. The harmonic vibrational frequencies can aid possible identification of gaseous F(2)O(3). The calculated Δ(f)H° and Δ(f)G° are 110 and 173 kJ mol(-1), respectively. These values are based on extrapolation of CCSD(T) results with augmented triple- and quadruple-ζ basis sets and are expected to be within chemical accuracy (i.e., 1 kcal mol(-1) or 4 kJ mol(-1)). F(2)O(3) is calculated to be stable to decomposition to either FO + FOO or F(2) + O(3), but unstable to decomposition to its elements, to F(2)O(2) + (1)/(2)O(2), and to F(2)O + O(2).

BPS states in N = 2 supersymmetric G2 and F4 models

NASA Astrophysics Data System (ADS)

Ahl Laamara, R.; Mellal, O.; Saidi, E. H.

2017-07-01

In BPS quiver theory of N = 2 supersymmetric pure gauge models with gauge invariance G, primitive BPS quivers Q0G are of two types: Q0ADE and Q0BCFG. In this study, we first show that Q0ADE have outer-automorphism symmetries inherited from the outer-automorphisms of the Dynkin diagrams of ADE Lie algebras. Then, we extend the usual folding operation of Dynkin diagrams ADE → BCFG to obtain the two following things: (i) relate Q0BCFG quivers and their mutations to the Q0ADE ones and their mutations; and (ii) link the BPS chambers of the N = 2ADE theories with the corresponding BCFG ones. As an illustration of this construction, we derive the BPS and anti-BPS states of the strong chambers QstgG2 and QstgF4 of the 4d N = 2 pure G2 and F4 gauge models.

Silver(I) complexes of the weakly coordinating solvents SO(2) and CH(2)Cl(2): crystal structures, bonding, and energetics of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)].

PubMed

Decken, Andreas; Knapp, Carsten; Nikiforov, Grigori B; Passmore, Jack; Rautiainen, J Mikko; Wang, Xinping; Zeng, Xiaoqing

2009-06-22

Pushing the limits of coordination chemistry: The most weakly coordinated silver complexes of the very weakly coordinating solvents dichloromethane and liquid sulfur dioxide were prepared. Special techniques at low temperatures and the use of weakly coordinating anions allowed structural characterization of [Ag(OSO)][Al{OC(CF(3))(3)}(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(Cl(2)CH(2))(2)][SbF(6)] (see figure). An investigation of the bonding shows that these complexes are mainly stabilized by electrostatic monopole-dipole interactions.The synthetically useful solvent-free silver(I) salt Ag[Al(pftb)(4)] (pftb=--OC(CF(3))(3)) was prepared by metathesis reaction of Li[Al(pftb)(4)] with Ag[SbF(6)] in liquid SO(2). The solvated complexes [Ag(OSO)][Al(pftb)(4)], [Ag(OSO)(2/2)][SbF(6)], and [Ag(CH(2)Cl(2))(2)][SbF(6)] were prepared and isolated by special techniques at low temperatures and structurally characterized by single-crystal X-ray diffraction. The SO(2) complexes provide the first examples of coordination of the very weak Lewis base SO(2) to silver(I). The SO(2) molecule in [Ag(OSO)][Al(pftb)(4)] is eta(1)-O coordinated to Ag(+), while the SO(2) ligands in [Ag(OSO)(2/2)][SbF(6)] bridge two Ag(+) ions in an eta(2)-O,O' (trans,trans) manner. [Ag(CH(2)Cl(2))(2)][SbF(6)] contains [Ag(CH(2)Cl(2))(2)](+) ions linked through [SbF(6)](-) ions to give a polymeric structure. The solid-state silver(I) ion affinities (SIA) of SO(2) and CH(2)Cl(2), based on bond lengths and corresponding valence units in the corresponding complexes and tensimetric titrations of Ag[Al(pftb)(4)] and Ag[SbF(6)] with SO(2) vapor, show that SO(2) is a weaker ligand to Ag(+) than the commonly used weakly coordinating solvent CH(2)Cl(2) and indicated that binding strength of SO(2) to silver(I) in the silver(I) salts increases with increasing size of the corresponding counteranion ([Al(pftb)(4)](-)>[SbF(6)](-)). The experimental findings are in good agreement with theoretical gas-phase ligand

Ab initio studies on Al(+)(H(2)O)(n), HAlOH(+)(H(2)O)(n-1), and the size-dependent H(2) elimination reaction.

PubMed

Siu, Chi-Kit; Liu, Zhi-Feng; Tse, John S

2002-09-11

We report computational studies on Al(+)(H(2)O)(n), and HAlOH(+)(H(2)O)(n-1), n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H(2) elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of Al(+)(H(2)O)(n), into HAlOH(+)(H(2)O)(n-1) is discovered for n > or = 8. This is because of the presence of a fairly stable six-water-ring structure in Al(+)(H(2)O)(n) with 12 members, including the Al(+). This structure promotes acidic dissociation and, for n > or = 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31G* and 6-31G** basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G** level, with zero-point energy corrections. Second, the experimentally observed size-dependent H(2) elimination reaction is related to the conformation of HAlOH(+)(H(2)O)(n-1), instead of Al(+)(H(2)O)(n). As n increases from 6 to 14, the structure of the HAlOH(+)(H(2)O)(n-1) cluster changes into a caged structure, with the Al-H bond buried inside, and protons produced in acidic dissociation could then travel through the H(2)O network to the vicinity of the Al-H bond and react with the hydride H to produce H(2). The structural transformation is completed at n = 13, coincident approximately with the onset of the H(2) elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H(2) elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and 4.5 eV (100 kcal/mol) at n = 8. The existence of transition structures for the H(2) elimination has also been verified by ab initio calculations

Superconducting Sr 2- xAxCuO 2F 2+ δ( A=Ca, Ba): Synthetic Pathways and Associated Structural Rearrangements

NASA Astrophysics Data System (ADS)

Francesconi, M. G.; Slater, P. R.; Hodges, J. P.; Greaves, C.; Edwards, P. P.; Al-Mamouri, M.; Slaski, M.

1998-01-01

The low-temperature fluorination of a range of insulating alkaline earth cuprates Sr2-xAxCuO3(A=Ca (0≤x≤2);A=Ba (0≤x≤0.6)) can result in superconducting oxide fluorides Sr2-xAxCuO2F2+δ. In contrast, conventional high-temperature solid-state reactions produce thermodynamically more stable mixtures of oxides and fluorides. Various soft-chemistry fluorination pathways (utilizing F2gas, NH4F,MF2[M=Cu, Zn, Ni, Ag]) are compared with respect to their efficacy and mechanisms. Attention is also focused on the structural features of the mixed-oxide precursor and the final-oxide fluorides to highlight the remarkable structural rearrangements that occur during the low-temperature fluorination. The effects of fluorination of other Sr-Cu-O systems are used to identify the structural requirements of the precursor oxide in order to achieve such transformations.

Synthesis, bioactivity and preliminary biocompatibility studies of glasses in the system CaO-MgO-SiO2-Na2O-P2O5-CaF2.

PubMed

Tulyaganov, D U; Agathopoulos, S; Valerio, P; Balamurugan, A; Saranti, A; Karakassides, M A; Ferreira, J M F

2011-02-01

New compositions of bioactive glasses are proposed in the CaO-MgO-SiO(2)-Na(2)O-P(2)O(5)-CaF(2) system. Mineralization tests with immersion of the investigated glasses in simulated body fluid (SBF) at 37°C showed that the glasses favour the surface formation of hydroxyapatite (HA) from the early stages of the experiments. In the case of daily renewable SBF, monetite (CaHPO(4)) formation competed with the formation of HA. The influence of structural features of the glasses on their mineralization (bioactivity) performance is discussed. Preliminary in vitro experiments with osteoblasts' cell-cultures showed that the glasses are biocompatible and there is no evidence of toxicity. Sintering and devitrification studies of glass powder compacts were also performed. Glass-ceramics with attractive properties were obtained after heat treatment of the glasses at relatively low temperatures (up to 850°C).

Crafting biochars to reduce N2O and CO2 emissions while also improving soil quality

NASA Astrophysics Data System (ADS)

Novak, Jeff; Ippolito, Jim; Spokas, Kurt; Sigua, Gilbert; Kammann, Claudia; Wrage-Monnig, Nicole; Borchard, Nils; Schirrmann, Michael; Estavillo, Jose Maria; Fuertes-Mendizabal, Teresa; Menendez, Sergio; Cayuela, Maria Luz

2017-04-01

Biochar used as an amendment has been linked to nitrous oxide (N2O) emission reductions, a decrease in nitrogen (N) leaching, and soil quality improvements (e.g., soil carbon sequestration, pH, etc.). While numerous articles will support these three facts, conversely, there are reports of no to marginal influences. One reason for the mixed biochar performance could be related to applying biochar with incorrect chemical and physical characteristics. As a means to increase biochar efficiency, we introduced the concept of crafting biochars with properties attuned to specific soil deficiencies. Implementing this concept requires a literature review to identify salient biochar characteristics that reduces N2O emissions, impacts N availability, while also improving soil quality. Thus, scientists from the USDA-ARS and through a coalition of European scientists under the FACCE-JPI umbrella have conceived the DesignChar4food (d4f) project. In this project, scientists are working collaboratively to further this concept to match the appropriate biochar for selective soil quality improvement, retain N for crops, and promote greenhouse gas reductions. This presentation will highlight results from the d4f team compromising a meta-analysis of articles on biochar:N2O dynamics, N availability, and how designer biochars can target specific soil quality improvements.

In vitro evaluation of bioactivity of SiO2-CaO-P2O5-Na2O-CaF2-ZnO glass-ceramics

NASA Astrophysics Data System (ADS)

Riaz, Madeeha; Zia, Rehana; Saleemi, Farhat; Bashir, Farooq; Hossain, Tousif; Kayani, Zohra

2014-09-01

Zinc is an essential trace element that stimulates bone formation but it is also known as an inhibitor of apatite crystal growth. In this work addition of ZnO to SiO2-CaO-P2O5-Na2O-CaF2 glass-ceramic system was made by conventional melt-quenching technique. DSC curves showed that the addition of ZnO moved the endothermic and exothermic peaks to lower temperatures. X-ray diffraction analysis did not reveal any additional phase caused by ZnO addition and showed the presence of wollastonite and hydroxyapatite crystalline phases only in all the glass-ceramic samples. As bio-implant apatite forming ability is an essential condition, the surface reactivity of the prepared glass-ceramic specimens was studied in vitro in Kokubo's simulated body fluid (SBF) [1] with ion concentration nearly equal to human blood plasma for 30 days at 37 °C under static condition. Atomic absorption spectroscopy (AAS) was used to study the changes in element concentrations in soaking solutions and XRD, FT-IR and SEM were used to elucidate surface properties of prepared glass-ceramics, which confirmed the formation of HCAp on the surface of all glass-ceramics. It was found that the addition of ZnO had a positive effect on bioactivity of glass-ceramics and made it a potential candidate for restoration of damaged bones.

Reactions of hydrated electrons (H2O)n- with carbon dioxide and molecular oxygen: hydration of the CO2- and O2- ions.

PubMed

Balaj, O Petru; Siu, Chi-Kit; Balteanu, Iulia; Beyer, Martin K; Bondybey, Vladimir E

2004-10-04

The gas-phase reactions of hydrated electrons with carbon dioxide and molecular oxygen were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Both CO2 and O2 react efficiently with (H2O)n- because they possess low-lying empty pi* orbitals. The molecular CO2- and O2- anions are concurrently solvated and stabilized by the water ligands to form CO2(-)(H2O)n and O2(-)(H2O)n. Core exchange reactions are also observed, in which CO2(-)(H2O)n is transformed into O2(-)(H2O)n upon collision with O2. This is in agreement with the prediction based on density functional theory calculations that O2(-)(H2O)n clusters are thermodynamically favored with respect to CO2(-)(H2O)n. Electron detachment from the product species is only observed for CO2(-)(H2O)2, in agreement with the calculated electron affinities and solvation energies.

A theoretical study of the molecular structures and vibrational spectra of the N 2O⋯(HF) 2

NASA Astrophysics Data System (ADS)

de Lima, Nathália B.; Ramos, Mozart N.

2012-01-01

Theoretical calculations using both the MP2 and B3LYP levels of calculation with a 6-311++G(3df,3pd) basis set have been performed to determine stable structures and molecular properties for the H-bonded complexes involving nitrous oxide (N 2O) and two HF molecules. Five complex have been characterized as minima since no imaginary frequency was found. Three complex are predicted to be relatively more stable with binding energies varying from 14 kJ mol -1 to 23 kJ mol -1 after BSSE and ZPE corrections. Our calculations have revealed that the second complexation with HF preferably occurs with the first complexed HF molecule, i.e., forming the X⋯H sbnd F⋯H sbnd F skeleton with X = O or N instead the F sbnd H⋯N sbnd N sbnd O⋯H sbnd F one. As expected, the H sbnd F chemical bonds are increased after complexation due to intermolecular charge transfer from "n" isolated pair of the X atom (X = N, O or F) to the σ ∗ anti-bonding orbital of HF. For the strongly bounded complex, the doubly complexed HF molecule acts as a bridge between the two end molecules while transferring electrons from N 2O to HF. Both possess the same amount of residual charge but with opposite signs. The H sbnd F stretching frequency of the monoprotic acid is shifted downward after complexation whereas its IR intensity is much enhanced. This increase has been adequately interpreted in terms of equilibrium hydrogen charge and charge-flux associated to the H sbnd F stretching using the CCFOM model for infrared intensities. This procedure has also allowed to analyze the new vibrational modes arising upon H-bond formation, especially those associated with the out-of-plane and in-plane HF bending modes, which are pure rotations in the HF isolated molecule.

Nanostructured bilayer anodic TiO2/Al2O3 metal-insulator-metal capacitor.

PubMed

Karthik, R; Kannadassan, D; Baghini, Maryam Shojaei; Mallick, P S

2013-10-01

This paper presents the fabrication of high performance bilayer TiO2/Al2O3 Metal-Insulator-Metal capacitor using anodization technique. A high capacitance density of 7 fF/microm2, low quadratic voltage coefficient of capacitance of 150 ppm/V2 and a low leakage current density of 9.1 nA/cm2 at 3 V are achieved which are suitable for Analog and Mixed signal applications. The influence of anodization voltage on structural and electrical properties of dielectric stack is studied in detail. At higher anodization voltages, we have observed the transformation of amorphous to crystalline state of TiO2/Al2O3 and improvement of electrical properties.

CW EC-QCL-based sensor for simultaneous detection of H 2O, HDO, N 2O and CH 4 using multi-pass absorption spectroscopy

DOE PAGES

Yu, Yajun; Sanchez, Nancy P.; Griffin, Robert J.; ...

2016-05-03

A sensor system based on a continuous wave, external-cavity quantum-cascade laser (CW EC-QCL) was demonstrated for simultaneous detection of atmospheric H 2O, HDO, N 2O and CH 4 using a compact, dense pattern multi-pass gas cell with an effective path-length of 57.6 m. The EC-QCL with a mode-hop-free spectral range of 1225-1285 cm -1 operating at similar to 7.8 mu m was scanned covering four neighboring absorption lines, for H 2O at 1281.161 cm -1, HDO at 1281.455 cm -1, N 2O at 1281.53 cm -1 and CH 4 at 1281.61 cm -1. A first-harmonic-normalized wavelength modulation spectroscopy with second-harmonicmore » detection (WMS-2f/1f) strategy was employed for data processing. An Allan-Werle deviation analysis indicated that minimum detection limits of 1.77 ppmv for H 2O, 3.92 ppbv for HDO, 1.43 ppbv for N 2O, and 2.2 ppbv for CH 4 were achieved with integration times of 50-s, 50-s, 100-s and 129-s, respectively. In conclusion, experimental measurements of ambient air are also reported.« less

The diversity of the N2O reducers matters for the N2O:N2 denitrification end-product ratio across an annual and a perennial cropping system.

PubMed

Domeignoz-Horta, Luiz A; Spor, Aymé; Bru, David; Breuil, Marie-Christine; Bizouard, Florian; Léonard, Joël; Philippot, Laurent

2015-01-01

Agriculture is the main source of terrestrial emissions of N2O, a potent greenhouse gas and the main cause of ozone layer depletion. The reduction of N2O into N2 by microorganisms carrying the nitrous oxide reductase gene (nosZ) is the only biological process known to eliminate this greenhouse gas. Recent studies showed that a previously unknown clade of N2O-reducers was related to the capacity of the soil to act as an N2O sink, opening the way for new strategies to mitigate emissions. Here, we investigated whether the agricultural practices could differently influence the two N2O reducer clades with consequences for denitrification end-products. The abundance of N2O-reducers and producers was quantified by real-time PCR, and the diversity of both nosZ clades was determined by 454 pyrosequencing. Potential N2O production and potential denitrification activity were used to calculate the denitrification gaseous end-product ratio. Overall, the results showed limited differences between management practices but there were significant differences between cropping systems in both the abundance and structure of the nosZII community, as well as in the [rN2O/r(N2O+N2)] ratio. More limited differences were observed in the nosZI community, suggesting that the newly identified nosZII clade is more sensitive than nosZI to environmental changes. Potential denitrification activity and potential N2O production were explained mainly by the soil properties while the diversity of the nosZII clade on its own explained 26% of the denitrification end-product ratio, which highlights the importance of understanding the ecology of this newly identified clade of N2O reducers for mitigation strategies.

2'-O-[2-[2-(N,N-Dimethylamino)ethoxy]ethyl] Modified Antisense Oligonucleotides: Symbiosis of Charge Interaction Factors and Stereoelectronic Effects

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

Prhavc, M.; Prakash, T.P.; Minasov, G.

Oligonucleotides with a novel, 2'-O-[2-[2-(N,N-dimethylamino)ethoxy]ethyl] (2'-O-DMAEOE) modification have been synthesized. This modification, a cationic analogue of the 2'-O-(2-methoxyethyl) (2'-O-MOE) modification, exhibits high binding affinity to target RNA (but not to DNA) and exceptional resistance to nuclease degradation. Analysis of the crystal structure of a self-complementary oligonucleotide containing a single 2'-O-DMAEOE modification explains the importance of charge factors and gauche effects on the observed antisense properties. 2'-O-DMAEOE modified oligonucleotides are ideal candidates for antisense drugs.

Estimated critical conditions for UO{sub 2}F{sub 2}--H{sub 2}O systems in fully water-reflected spherical geometry

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

Jordan, W.C.; Turner, J.C.

1992-12-01

The purpose of this report is to document reference calculations performed using the SCALE-4.0 code system to determine the critical parameters of UO{sub 2}F{sub 2}-H{sub 2}O spheres. The calculations are an extension of those documented in ORNL/CSD/TM-284. Specifically, the data for low-enriched UO{sub 2}F{sub 2}-H{sub 2}O spheres have been extended to highly enriched uranium. These calculations, together with those reported in ORNL/CSD/TM-284, provide a consistent set of critical parameters (k{sub {infinity}}, volume, mass, mass of water) for UO{sub 2}F{sub 2} and water over the full range of enrichment and moderation ratio.

Polymorph (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho-Lu, Y) and REF{sub 3} nanocrystals: Hydrothermal synthesis, characterization and luminescence

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

Jia, Li-Ping; Zhang, Qiang; Yan, Bing, E-mail: byan@tongji.edu.cn

Graphical abstract: A hydrothermal system is developed to prepare one new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O and known rare earth fluorides involving REF{sub 3} nanocrystals under mild condition. Highlights: ► A new polymorph of (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}RE{sub 3}F{sub 10}·xH{sub 2}O has been synthesized. ► The RE{sup 3+} radius decides the shape evolution and phase control for REF{sub 3} NCs. ► The RE{sup 3+} radius has influence on the microstructure and morphology of REF{sub 3} NCs. -- Abstract: In this paper, a solvents-thermal system is developed to prepare one new polymorph of (C{sub 2}N{submore » 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O and rare earth fluorides REF{sub 3} nanocrystals under mild condition. It is found that the ionic radius of RE{sup 3+} is the key factor responsible for the shape evolution and phase control for rare earth fluorides nanocrystals at selected temperatures, which has an influence on the microstructure and morphology of the products to some extent. With the increase of the atomic number, the shape of fluoride changes from hexagonal REF{sub 3} phase (RE = La, Sm) to orthorhombic REF{sub 3} phase (RE = Eu-Dy), and finally to diamond structure (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}Ho{sub 3}F{sub 10}·xH{sub 2}O (RE = Ho, Er, Tm, Yb, Lu, Y). In addition, the characteristic energy level transition {sup 5}D{sub 0}–{sup 7}F{sub 1} of Eu{sup 3+} splits into 585 and 591 nm emission peaks, and the dominant peak is the orange emission at 591 nm.« less

Isotopic Monitoring of N2O Emissions from Wastewater Treatment: Evidence for N2O Production Associated with Anammox Metabolism?

NASA Astrophysics Data System (ADS)

Harris, E. J.; Wunderlin, P.; Joss, A.; Emmenegger, L.; Kipf, M.; Wolf, B.; Mohn, J.

2015-12-01

Microbial production is the major source of N2O, the strongest greenhouse gas produced within the nitrogen cycle, and the most important stratospheric ozone destructant released in the 21st century. Wastewater treatment is an important and growing source of N2O, with best estimates predicting N2O emissions from this sector will have increased by >25% by 2020. Novel treatment employing partial nitritation-anammox, rather than traditional nitrification-denitrification, has the potential to achieve a neutral carbon footprint due to increased biogas production - if N2O production accounts for <0.5-1% of total nitrogen turnover. As a further motivation for this research, microbial pathways identified from wastewater treatment can be applied to our understanding of N cycling in the natural environment. This study presents the first online isotopic measurements of offgas N2O from a partial-nitritation anammox reactor 1. The measured N2O isotopic composition - in particular the N2O isotopic site preference (SP = δ15Nα - δ15Nβ) - was used to understand N2O production pathways in the reactor. When N2O emissions peaked due to high dissolved oxygen concentrations, low SP showed that N2O was produced primarily via nitrifier denitrification by ammonia oxidizing bacteria (AOBs). N2O production by AOBs via NH2OH oxidation, in contrast, did not appear to be important under any conditions. Over the majority of the one-month measurement period, the measured SP was much higher than expected following our current understanding of N2O production pathways 2. SP reached 41‰ during normal operating conditions and achieved a maximum of 45‰ when nitrite was added under anoxic conditions. These results could be explained by unexpectedly strong heterotrophic N2O reduction despite low dissolved organic matter concentrations, or by an incomplete understanding of isotopic fractionation during N2O production from NH2OH oxidation by AOBs - however the explanation most consistent with all