Medium-size polarized basis sets for high-level-correlated calculations of molecular electric properties

Sadlej, Andrzej J.

doi:10.1007/bf01127101

Cited by 589 publications

(262 citation statements)

References 35 publications

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“…CCSD(T), and the symmetry adapted perturbation method based on monomer orbitals built up with the density functional theory (SAPT(DFT)) [42]. Several atomic basis sets have been tested: the augmented -correlation consistent -polarized triple and quadruple zeta basis sets (augcc-pVXZ with X=T and Q) and the polarization optimized Sadlej basis set [46]. We add to this Sadlej set a polarization orbital "d" for the H atoms taken from the aug-cc-pVTZ basis set to obtain [3s2p1d] contracted Gaussian functions for H atoms and [5s3p2d] for C atoms.…”

Section: Methodsmentioning

confidence: 99%

Linewidths of C2H2 perturbed by H2: experiments and calculations from an ab initio potential

Thibault

Corretja

Viel

et al. 2008

Phys. Chem. Chem. Phys.

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In this work we present a theoretical and experimental study of the acetylene -hydrogen system.A potential surface considering rigid monomers has been obtained by ab initio quantum chemistry methods. This 4-dimensional potential is further employed to compute using the close-clouping approach and the coupled-states approximation pressure broadening coefficients of C 2 H 2 isotropic Raman Q lines over a temperature range of 77 to 2000 K. Experimental data for the acetylene ν 2 Raman lines broadened by molecular hydrogen are obtained using stimulated Raman spectroscopy.The comparison at 143 K of theoretical values with experimental data is promising. Approximations to increase computational efficiency are proposed. *

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Section: Methodsmentioning

confidence: 99%

Linewidths of C2H2 perturbed by H2: experiments and calculations from an ab initio potential

Thibault

Corretja

Viel

et al. 2008

Phys. Chem. Chem. Phys.

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“…We have used the CCSD(T), MP2, PBE, PBE+G06 and PBE0 methods, though the MP2 results are not shown as they are essentially identical to the CCSD(T) values. We have calculated counterpoise-corrected interaction energies using the Boys and Bernardi 32 scheme with a SadlejpVTZ basis 33 augmented with a small set of "bond centered functions" 34 which help to saturate the dispersion energy. 35 Selected calculations with the larger aug-ccpVTZ basis set suggest that the CCSD(T) interaction energies are converged to 5% at the equilibrium geometry and better at larger separations.…”

Section: Beyond the Pbe Functional A Calculations For Molecular mentioning

confidence: 99%

High pressure ionic and molecular crystals of ammonia monohydrate within density functional theory

Griffiths¹,

Misquitta²,

Fortes

et al. 2012

The Journal of Chemical Physics

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The following article has been submitted to The Journal of Chemical Physics. After it is published, it will be found at http://jcp.aip.org/ A combination of first-principles density functional theory calculations and a search over structures predicts the stability of a proton-transfer modification of ammonia monohydrate with space group P 4/nmm. The phase diagram is calculated with the PBE density functional, and the effects of a semi-empirical dispersion correction, zero point motion, and finite temperature are investigated.Comparison with MP2 and coupled cluster calculations shows that the PBE functional over-stabilizes proton transfer phases because too much electronic charge moves with the proton. This over-binding is partially corrected by using the PBE0 hybrid exchange-correlation functional, which increases the enthalpy of P 4/nmm by about 0.6 eV per formula unit relative to phase I of ammonia monohydrate (AMH-I) and shifts the transition to the proton transfer phase from the PBE pressure of 2.8 GPa to about 10 GPa. This is consistent with experiment as proton transfer phases have not been observed at pressures up to ∼9 GPa, while higher pressures have not yet been explored experimentally.

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“…63 As a hybrid functional it averages between the underestimation of the polarizability typical of Hartree-Fock calculations and the opposite behavior of pure density functionals. This was also checked by comparing selected calculations with results from Sadlej's basis sets 64,65 and the PBE1PBE functional. 66 The model chemistries used in our calculations are demonstrated to be accurate also in the evaluation of other quantitites of interest.…”

Section: A Ab Initio Calculationsmentioning

confidence: 99%

On the performance of molecular polarization methods. II. Water and carbon tetrachloride close to a cation

Masia

Probst

Rey

2005

The Journal of Chemical Physics

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Our initial study on the performance of molecular polarization methods close to a positive point charge ͓M. Masia, M. Probst, and R. Rey, J. Chem. Phys. 121, 7362 ͑2004͔͒ is extended to the case in which a molecule interacts with a real cation. Two different methods ͑point dipoles and shell model͒ are applied to both the ion and the molecule. The results are tested against high-level ab initio calculations for a molecule ͑water or carbon tetrachloride͒ close to Li + , Na + , Mg 2+ , and Ca 2+ . The monitored observable is in all cases the dimer electric dipole as a function of the ion-molecule distance for selected molecular orientations. The moderate disagreement previously obtained for point charges at intermediate distances, and attributed to the linearity of current polarization methods ͑as opposed to the nonlinear effects evident in ab initio calculations͒, is confirmed for real cations as well. More importantly, it is found that at short separations the phenomenological polarization methods studied here substantially overestimate the dipole moment induced if the ion is described quantum chemically as well, in contrast to the dipole moment induced by a point-charge ion, for which they show a better degree of accord with ab initio results. Such behavior can be understood in terms of a decrease of atomic polarizabilities due to the repulsion between electronic charge distributions at contact separations. It is shown that a reparametrization of the Thole method for damping of the electric field, used in conjunction with any polarization scheme, allows to satisfactorily reproduce the dimer dipole at short distances. In contrast with the original approach ͑developed for intramolecular interactions͒, the present reparametrization is ion and method dependent, and corresponding parameters are given for each case.

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Medium-size polarized basis sets for high-level-correlated calculations of molecular electric properties

Cited by 589 publications

References 35 publications

Linewidths of C2H2 perturbed by H2: experiments and calculations from an ab initio potential

Linewidths of C2H2 perturbed by H2: experiments and calculations from an ab initio potential

High pressure ionic and molecular crystals of ammonia monohydrate within density functional theory

On the performance of molecular polarization methods. II. Water and carbon tetrachloride close to a cation

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