Search results for "ab initio"

Theoretical study of stationary structures of acetamidine unimolecular decomposition

1990

Abstract The unimolecular decomposition of acetamidine to ammonia and acetonitrile was examined by ab initio methods. Stationary points, i.e. the reactant, product and transition structures, have been characterized. The process has an asynchronous mechanism, the transition state being described as a four-membered ring. To establish the relevance of different basis sets, calculations with eight standard Gaussian basis sets, STO-3G, 3-21G, 4-21G, 4-31G, 6-31G, 6-311G, 6-31G*, and G-31G**, were carried out.

Q-Chem 2.0: a high-performanceab initio electronic structure program package

2000

ABSTRACT: Q-Chem 2.0 is a new release of an electronic structure programpackage, capable of performing first principles calculations on the ground andexcited states of molecules using both density functional theory and wavefunction-based methods. A review of the technical features contained withinQ-Chem 2.0 is presented. This article contains brief descriptive discussions of thekey physical features of all new algorithms and theoretical models, together withsample calculations that illustrate their performance. c 2000 John Wiley S electronic structure; density functional theory;computer program; computational chemistry Introduction A reader glancing casually at this article mightsuspect on t…

Counter-complementarity control of the weak exchange interaction in a bent {Ni(ii)3 complex with a μ-phenoxide-μ-carboxylate double bridge

2019

We have prepared and structurally characterized a novel {Ni3} bent complex bearing a double μ-phenoxide-μ-carboxylate bridge. Both terminal Ni(ii) sites are symmetry related, offering a simplified exchange interaction scheme. DC magnetic data is consistent with a weak antiferromagnetic interaction between the central and terminal Ni(ii) ions. As expected for a Ni(ii) system, local zero-field splitting is observed, which can be experimentally established. Broken symmetry quantum chemical calculations, as well as ab initio CASSCF-SA-SOC computations that support the magnetic experimental data, were also performed. From the analysis of other reported closely related Ni(ii) systems, a counter-c…

A full conformational space analysis of bilirubin

2009

Ab initio methods were utilized in a gas-phase systematic conformational search of bilirubin conformers. The whole molecule was divided into four fragments. Most stable conformers of them were employed to build 196 conformers of the complete bilirubin molecule. Initial geometries were optimized using HF/3-21G level of theory and the minimum energy conformers were then reoptimized at B3LYP/6-31G(d) level. Ridge-tile conformer was the most stable one, in perfect agreement with X-ray data. We found that while tetrapyrrole backbone shows some flexibility, propionic acid side chains have a greater influence in bilirubin conformation because they can interact through different hydrogen bond patte…

Electronic aspects of the hydride transfer mechanism. Ab initio analytical gradient studies of the cyclopropenyl‐cation/lithium hydride model reactan…

1985

The electronic mechanisms of a model hydride transfer reaction are theoretically studied with ab inito RHF and UHF SCF MO procedures at the 4‐31G basis set level and analytical gradient methods. The model system describes the reduction of cyclopropenyl cation to cyclopropene by the oxidation of lithium hydride to lithium cation. The molecular fragments corresponding to the asymptotic reactive channels characterizing the stepwise mechanisms currently discussed in the literature have been characterized. The binding energy between the fragments is estimated within a simple electrostatic approximate scheme. The results show that a hydride‐ion mechanism is a likely pathway for this particular sy…

Effects of hydrostatic pressure on the thermoelectric properties of the ϵ-polytype of InSe, GaSe, and InGaSe2 semiconductor compounds: anab initiostu…

2017

An ab initio potential energy surface for the C2H2-N2 system

2012

International audience; An ab initio potential energy surface determined at the CCSD(T) level of theory is presented for the van der Waals complex C2H2-N2. Additional calculations performed with the HF- and DFT-SAPT methods compare well with the CCSD(T) results and allow a better understanding of the main features of this interaction potential surface. An expansion of this surface over spherical harmonics has also been performed. The global energy minimum of the complex is obtained for the linear conformation. The T conformations are the least attractive. Such characteristics mainly arise because of the variation, in sign and in absolute value of the electrostatic energy between all these c…

An ab initio study of the tautomeric equilibria of the N-oxides of hydroxypyridines in the vapour phase

1993

Abstract An ab initio self-consistent field molecular orbital study of the N-oxides of hydroxypyridines has been carried out. The optimized structures have been obtained at the 6-31G ∗ level, and the energy values have been computed at the 6-31G ∗ and MP2-6-31G ∗ //6-31G ∗ levels. The tautomerization energies for the three couples of systems in the vapour phase have been evaluated.

A theoretical determination of the dissociation energy of the nitric oxide dimer

1994

Multi-reference CI methods have been applied to determine the dissociation energy and structure of thecis-N2O2 molecule. The convergence of the theoretical result has been checked with respect to a systematic expansion of the one-electron basis set and the multi-reference CI wave function. The best calculated value, 13.8 kJ/mol, is in agreement with the experimental value, 12.2 kJ/mol. It has been obtained with an extended ANO-type basis set [6s5p3d2f], including the effect of the basis set superposition error (BSSE) in the geometry optimization, and additional effects, such as the electron correlation of core electrons and relativistic corrections, using the average coupled pair functional…

High-resolution Fourier transform infrared spectroscopy and analysis of the ν3 fundamental band of P4

1999

Abstract We present the first high-resolution infrared absorption study of the ν 3 fundamental of white phosphorus, P 4 . This spectrum has been analyzed using the STDS (Spherical Top Data System) software. The band center lies at 466.286 cm −1 . With the approximation ( Bζ ) 3 =− B 0 /2, we found that the ground-state bond length is r 0 =219.58 pm. This value is consistent with that of ab initio studies reported previously but significantly different from a value obtained from a Raman study.