Search results for "ab initio"
showing 10 items of 990 documents
A theoreticalab initiostudy on the H2NO + O3reaction
2003
The deviation of the NH2 pseudo-first-order decay Arrhenius plots of the NH2 + O3 reaction at high ozone pressures measured by experimentalists, has been attributed to the regeneration of NH2 radicals due to the subsequent reactions of the products of this reaction with ozone. Although these products have not yet been characterized experimentally, the radical H2NO has been postulated, because it can regenerate NH2 radicals through the reactions: H2NO + O3 NH2 + O2 and H2NO + O3 HNO + OH + O2. With the purpose of providing a reasonable explanation from a theoretical point of view to the kinetic observed behaviour of the NH2 + O3 system, we have carried ab initio electronic structure calculat…
Ab Initio Study of the Mechanism and Thermochemistry of the Atmospheric Reaction NO + O3 → NO2 + O2
2002
The atmospheric reaction between NO and ozone has been investigated using ab initio methods. The structures of all reactants, products, intermediates, and transition states of reaction 1 have been optimized and characterized at the UMP2(full) level of theory. The 6-31G(d), 6-311G(d), and 6-311G(df) basis sets have also been used to calibrate the effect of the basis set functions on the optimized structures and energies of all stationary points. Finally, we have reoptimized at the UMP4(SDQ, full)/6-31G(d) and 6-311G(d) levels. The energetics of the reaction has been studied more accurately within the G2 and G2(MP2) schemes. Also, QCISD(T)/6-311G(d) single-point calculations have been perform…
First-principles nonequilibrium Green's-function approach to transient photoabsorption: Application to atoms
2015
We put forward a first-principle NonEquilibrium Green's Function (NEGF) approach to calculate the transient photoabsorption spectrum of optically thin samples. The method can deal with pump fields of arbitrary strength, frequency and duration as well as for overlapping and nonoverlapping pump and probe pulses. The electron-electron repulsion is accounted for by the correlation self-energy, and the resulting numerical scheme deals with matrices that scale quadratically with the system size. Two recent experiments, the first on helium and the second on krypton, are addressed. For the first experiment we explain the bending of the Autler-Townes absorption peaks with increasing the pump-probe d…
Ab initio angle- and energy-resolved photoelectron spectroscopy with time-dependent density-functional theory
2012
We present a time-dependent density-functional method able to describe the photoelectron spectrum of atoms and molecules when excited by laser pulses. This computationally feasible scheme is based on a geometrical partitioning that efficiently gives access to photoelectron spectroscopy in time-dependent density-functional calculations. By using a geometrical approach, we provide a simple description of momentum-resolved photoemission including multiphoton effects. The approach is validated by comparison with results in the literature and exact calculations. Furthermore, we present numerical photoelectron angular distributions for randomly oriented nitrogen molecules in a short near-infrared…
Argon broadening of the 13CO R(0) and R(7) transitions in the fundamental band at temperatures between 80 and 297K: comparison between experiment and…
2003
We present measurements of Ar-broadening parameters for the R(0) and R(7) lines in the fundamental band of13CO at eight temperatures from 80 to 297 K. The broadening parameters are determined by simultaneous least-squares fitting of spectra recorded using a frequency stabilized diode laser spectrometer. The comparison of the broadening parameter values for R(7) derived at room temperature and different pressures from different line profiles shows that an empirical line profile, which takes into account narrowing effects (Dicke narrowing and absorber speed dependence) but neglects any correlation between collisions, is able to describe the observed lines with constant values of the narrowing…
Ab initio simulations on Frenkel pairs of radiation defects in corundum
2015
Large scale first principles periodic calculations based on the density functional theory within the localized atomic orbital approach (DFT-LCAO) using the hybrid exchange- correlation potential B3PW have been performed in order to study the structural and electronic properties of radiation-induced Frenkel pairs Oi+VO in corundum crystal. As an initial approach, we have used conventional 2x2x1 supercell for defective α-Al2O3 lattice containing 120 atoms. After relaxation of the ideal supercell structure, the optimized doi-vo distance has been found to be ~4.5 A while the formation energy of Frenkel pair has achieved 11.7 eV. The interstitial Oi atom, both single and a component of Oi+VO pai…
Ab initio study of the C60+Na system
2004
Abstract In this work we present the first CAS-CI calculation of the potential-electronic curves for the lowest states of the C 60 +Na system using a set of local orbitals. These orbitals permit to select a small active space describing the ionic interaction between the C 60 and the Na atom. A binding energy of about 3 eV has been found, a value substantially larger than previous theoretical results.
The characterization of molecular alkaly metal azides
2006
Matrix isolation infrared (IR) studies have been carried out on the vaporisation of the alkali-metal azides MN(3) (M = Na, K, Rb and Cs). The results show that under high vacuum conditions, molecular KN(3), RbN(3) and CsN(3) are present as stable high-temperature vapour species, together with variable amounts of nitrogen gas and the corresponding metal atoms. The characterisation of these molecular azides is supported by ab initio molecular orbital calculations and density functional theory (DFT) calculations, and for CsN(3) in particular, by the detection of the isotopomers CS((14)N(15)N(14)N) and Cs((15)N(14)N(14)N). The IR spectra are assigned to a "side-on" (C(2v)) structure by comparis…
Novel azobenzene precursors for NLO active polyuretanes: Synthesis, quantum chemical and experimental characterization
2009
Abstract For the development of electro optical active polyurethanes six new derivatives of 2-{(2-hydroxyethyl)-[4-(4-nitrophenylazo)phenyl]amino}ethanol and two of 2-{(2-hydroxyethyl)-[4-(5-nitropyridin-2-ylazo)phenyl]amino}ethanol were synthesized by azocoupling reaction. Molecular geometry, hyperpolarizability βFF and ground state dipole moment μg were acquired by RHF ab initio (6–31G∗∗) calculations using HyperChem software package. To characterize NLO performance of synthesized azo compounds second order non linear coefficients d31 and d33 were measured as function of chromophore load in guest–host films (PMMA). Eight synthesized compounds can be grouped in four similar gross formula p…
Systematic trends in (0 0 1) surface ab initio calculations of ABO 3 perovskites
2018
This work was supported by the Latvian Council of Science Grant No. 374/2012 and the Latvian National Research Program IMIS2. Many stimulating discussions with D. Vanderbilt, K.M. Rabe, M. Rohlfing, E. Heifets, J. Maier, G. Borstel and E.A. Kotomin are greatly acknowledged.