Search results for "Ab initio quantum chemistry methods"
showing 10 items of 468 documents
Interplay between local structure, vibrational and electronic properties on CuO under pressure
2020
The electronic and local structural properties of CuO under pressure have been investigated by means of X-ray absorption spectroscopy (XAS) at Cu K edge and ab initio calculations, up to 17 GPa. The crystal structure of CuO consists of Cu motifs within CuO4 square planar units and two elongated apical Cu-O bonds. The CuO4 square planar units are stable in the studied pressure range, with Cu-O distances that are approximately constant up to 5 GPa, and then decrease slightly up to 17 GPa. In contrast, the elongated Cu-O apical distances decrease continuously with pressure in the studied range. An anomalous increase of the mean square relative displacement (EXAFS Debye-Waller, s2) of the elong…
Ab-Initio Calculations of Oxygen Vacancy in Ga2O3 Crystals
2021
The research has been funded by the Science Committee of the Ministry of Education and Science of the Republic of Kazakhstan (Grant No. AP08856540). J. Purans and A.I.Popov acknowledge the ERAF project 1.1.1.1/20/A/057 “Functional Ultrawide Bandgap Gallium Oxide and Zinc Gallate Thin Films and Novel Deposition Technologies”. The Institute of Solid State Physics, University of Latvia (Latvia) as the Centre of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD01-2016-2017-Teaming Phase2 under grant agreement No. 739508, project CAMART2.
A study of the atmospherically important reactions between dimethyl selenide (DMSe) and molecular halogens (X2 = Cl2, Br2, and I2) with ab initio cal…
2012
The atmospherically relevant reactions between dimethyl selenide (DMSe) and the molecular halogens (X(2) = Cl(2), Br(2), and I(2)) have been studied with ab initio calculations at the MP2/aug-cc-pVDZ level of theory. Geometry optimization calculations showed that the reactions proceed from the reagents to the products (CH(3)SeCH(2)X + HX) via three minima, a van der Waals adduct (DMSe:X(2)), a covalently bound intermediate (DMSeX(2)), and a product-like complex (CH(3)SeCH(2)X:HX). The computed potential energy surfaces are used to predict what molecular species are likely to be observed in spectroscopic experiments such as gas-phase photoelectron spectroscopy and infrared matrix isolation s…
Cluster and Periodic Calculations of the Ethene Protonation Reaction Catalyzed by theta-1 Zeolite: Influence of Method, Model Size, and Structural Co…
2001
The protonation of ethene by three different acid sites of theta-1 zeolite was theoretically studied to analyze the extent and relevance of the following aspects of heterogeneous catalysis: the local geometry of the Bronsted acid site in a particular zeolite, the size of the cluster used to model the catalyst, the degree of geometry relaxation around the active site, and the effects related to medium- and long-range interactions between the reaction site and its environment. It has been found that while the reaction energy is very sensitive to the local geometry of the site, the activation energy is mainly affected by the methodology used and by electrostatic effects on account of the carbo…
The bromine nuclear quadrupole moment revisited
2013
For the bromine atom and the hydrogen bromide molecule, we report results for the electric-field gradient at the bromine nucleus based on quantum-chemical calculations. Highly accurate values are obtained by using coupled-cluster methods for the treatment of electron correlation, by minimising remaining basis-set effects through the use of large atomic-orbital sets, and by taking into account relativistic effects. For hydrogen bromide, zero-point vibrational corrections are considered as well. The obtained results for the bromine electric-field gradients are used to derive values for the Br-79 quadrupole moment: 308.1 and 309.3 mb based on data for the bromine atom and hydrogen bromide, res…
Functionalized Tellurium(II) Thiolates: Tellurium Bis(2-hydroxyethanethiolate) Hydrate, the First H2O–TeII Complex
2000
Relationship between Electron Affinity and Half-Wave Reduction Potential: A Theoretical Study on Cyclic Electron-Acceptor Compounds.
2016
A high-level ab initio protocol to compute accurate electron affinities and half-wave reduction potentials is presented and applied for a series of electron-acceptor compounds with potential interest in organic electronics and redox flow batteries. The comprehensive comparison between the theoretical and experimental electron affinities not only proves the reliability of the theoretical G3(MP2) approach employed but also calls into question certain experimental measurements, which need to be revised. By using the thermodynamic cycle for the one-electron attachment reaction A+e- →A- , theoretical estimates for the first half-wave reduction potential have been computed along the series of ele…
Molecular structures and vibrations of m-methylaniline in the S0 and S1 states studied by laser induced fluorescence spectroscopy and ab initio calcu…
2000
Abstract The UV fluorescence excitation and dispersed fluorescence spectra of a jet-cooled m-methylaniline have been obtained for the S1←S0 transition, in which some of the bands have been observed for the first time. The main spectral bands have been assigned by comparison with those of other relevant substituted benzenes. It was found that the spectra exhibit an important feature which is the internal rotation of the methyl group in the electronic ground and excited states. Ab initio calculations at MP2/6-31G* and CIS/6-31G* show that the optimized structure of m-methylaniline in the ground state is not planar with the amino group having sp3 hybridation-like character due to the existence…
Predominance of 2-arylhydrazones of 1,3-diphenylpropane-1,2,3-trione over its proton-transfer products
2001
2-Phenylhydrazones of 1,3-diphenyl-1,2,3-trione are the dominant tautomeric form detected in chloroform solution by 15N NMR chemical shifts. The substituent in the phenylhydrazone moiety does not affect this tautomeric preference. The substituent effect is transmitted effectively only to the hydrazone nitrogen and hydrogen atoms. Ab initio calculations show that the ketohydrazone tautomer is really very much favoured over its proton-transfer products in chloroform solution. The same tautomer was also detected in the crystal state by X-ray crystallography. Copyright © 2001 John Wiley & Sons, Ltd.
Regio- and stereoselective synthesis of constrained enantiomeric β-amino acid derivatives
2008
Abstract Chlorosulfonyl isocyanate addition to (−)- and (+)-apopinene furnished monoterpene-fused β-lactams in highly regio- and stereospecific reactions. β-Lactams 5 and 13 exhibited reactivities similar to those of the cycloalkane-fused analogs and were easily converted to the β-amino acid and its protected derivatives. The base-catalyzed isomerization of the cis -amino ester afforded the corresponding trans -amino acid enantiomers in excellent yields. The complete isomerization is explained by the stability difference, which was estimated by ab initio calculations between the cis- and trans -diastereomers.