A Higher Level Ab Initio Quantum-Mechanical Study of the Quadrupole Moment Tensor Components of Carbon Dioxide

Rainer Glaser; Zhengyu Wu; Michael A. Lewis

doi:10.1016/S0022-2860(00)00658-X

A Higher Level Ab Initio Quantum-Mechanical Study of the Quadrupole Moment Tensor Components of Carbon Dioxide

Rainer Glaser
, Zhengyu Wu
, Michael A. Lewis

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The quadrupolarity of carbon dioxide has been studied with higher level ab initio methods. Carbon dioxide exhibits {- + -} quadrupolarity in all directions and an explanation is provided of the origin of the sign of the diagonal elements Q ii . The quadrupole moment tensor has been computed using restricted Hartree-Fock theory, second-order Møller-Plesset perturbation theory and quadratic configuration interaction theory. A variety of basis sets have been employed up to basis sets of the type [5s, 4p, 2d, 1f] (23s, 8p, 2d, 1f). The quadrupole moment tensor component Q &spar; of carbon dioxide falls in the range between -18.5 and -20.5 Debye Å. The quadrupole moment tensor components Q &perp; of carbon dioxide are smaller, ranging from -14.5 to -15 Debye Å, and they are less sensitive to the choice of the theoretical model. The correlated methods consistently predict an increase of Q &spar; while they predict a more modest reduction of Q &perp; . It is for the opposing electron correlation effects on Q &spar; and Q &perp; that the average values of the diagonal elements, 〈 Q ii 〉, are essentially independent of the method and exhibit only a small variation depending on the basis set. On the other hand, the anisotropy of the quadrupolarity, the quadrupole moment Θ , is affected most by the opposing electron correlation effects on Q &spar; and Q &perp; . The accurate reproduction of the measured quadrupolarity Θ = -4.3 Debye Å requires a theoretical model that employs both a good method and a good basis set. The results suggest that the use of second-order Møller-Plesset perturbation theory in conjunction with well-polarized triple- ζ basis sets provides a cost-effective and quite accurate method for the estimation of correlation effects on quadrupole moments.

Original language	American English
Journal	Journal of Molecular Structure
Volume	556
DOIs	https://doi.org/10.1016/S0022-2860(00)00658-X
State	Published - Dec 1 2000

Keywords

Ab Initio Calculations
Anisotropy
Atomic Charges
Carbon Dioxide
Catalysis
Deamination
Dehydration
Dipole
Electrostatic Bonding
Hydrogen Bond
Hydrolysis
Molecular Interaction
Nucleotide Metabolism
Quadrupole Moment Tensor Components
Quantum Mechanics
Reaction Analysis

Disciplines

Chemistry

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http://doi.org/10.1016/S0022-2860(00)00658-X

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@article{e88a3ae59049435e873f3ff97f927a19,

title = "A Higher Level Ab Initio Quantum-Mechanical Study of the Quadrupole Moment Tensor Components of Carbon Dioxide",

abstract = " The quadrupolarity of carbon dioxide has been studied with higher level ab initio methods. Carbon dioxide exhibits \{- + -\} quadrupolarity in all directions and an explanation is provided of the origin of the sign of the diagonal elements Q ii . The quadrupole moment tensor has been computed using restricted Hartree-Fock theory, second-order M\øller-Plesset perturbation theory and quadratic configuration interaction theory. A variety of basis sets have been employed up to basis sets of the type [5s, 4p, 2d, 1f] (23s, 8p, 2d, 1f). The quadrupole moment tensor component Q \&spar; of carbon dioxide falls in the range between -18.5 and -20.5 Debye \Å. The quadrupole moment tensor components Q \&perp; of carbon dioxide are smaller, ranging from -14.5 to -15 Debye \Å, and they are less sensitive to the choice of the theoretical model. The correlated methods consistently predict an increase of Q \&spar; while they predict a more modest reduction of Q \&perp; . It is for the opposing electron correlation effects on Q \&spar; and Q \&perp; that the average values of the diagonal elements, 〈 Q ii 〉, are essentially independent of the method and exhibit only a small variation depending on the basis set. On the other hand, the anisotropy of the quadrupolarity, the quadrupole moment \Θ , is affected most by the opposing electron correlation effects on Q \&spar; and Q \&perp; . The accurate reproduction of the measured quadrupolarity \Θ = -4.3 Debye \Å requires a theoretical model that employs both a good method and a good basis set. The results suggest that the use of second-order M\øller-Plesset perturbation theory in conjunction with well-polarized triple- \ζ basis sets provides a cost-effective and quite accurate method for the estimation of correlation effects on quadrupole moments.",

keywords = "Ab Initio Calculations, Anisotropy, Atomic Charges, Carbon Dioxide, Catalysis, Deamination, Dehydration, Dipole, Electrostatic Bonding, Hydrogen Bond, Hydrolysis, Molecular Interaction, Nucleotide Metabolism, Quadrupole Moment Tensor Components, Quantum Mechanics, Reaction Analysis",

author = "Rainer Glaser and Zhengyu Wu and Lewis, \{Michael A.\}",

year = "2000",

month = dec,

day = "1",

doi = "10.1016/S0022-2860(00)00658-X",

language = "American English",

volume = "556",

journal = "Journal of Molecular Structure",

}

TY - JOUR

T1 - A Higher Level Ab Initio Quantum-Mechanical Study of the Quadrupole Moment Tensor Components of Carbon Dioxide

AU - Glaser, Rainer

AU - Wu, Zhengyu

AU - Lewis, Michael A.

PY - 2000/12/1

Y1 - 2000/12/1

N2 - The quadrupolarity of carbon dioxide has been studied with higher level ab initio methods. Carbon dioxide exhibits {- + -} quadrupolarity in all directions and an explanation is provided of the origin of the sign of the diagonal elements Q ii . The quadrupole moment tensor has been computed using restricted Hartree-Fock theory, second-order Møller-Plesset perturbation theory and quadratic configuration interaction theory. A variety of basis sets have been employed up to basis sets of the type [5s, 4p, 2d, 1f] (23s, 8p, 2d, 1f). The quadrupole moment tensor component Q &spar; of carbon dioxide falls in the range between -18.5 and -20.5 Debye Å. The quadrupole moment tensor components Q &perp; of carbon dioxide are smaller, ranging from -14.5 to -15 Debye Å, and they are less sensitive to the choice of the theoretical model. The correlated methods consistently predict an increase of Q &spar; while they predict a more modest reduction of Q &perp; . It is for the opposing electron correlation effects on Q &spar; and Q &perp; that the average values of the diagonal elements, 〈 Q ii 〉, are essentially independent of the method and exhibit only a small variation depending on the basis set. On the other hand, the anisotropy of the quadrupolarity, the quadrupole moment Θ , is affected most by the opposing electron correlation effects on Q &spar; and Q &perp; . The accurate reproduction of the measured quadrupolarity Θ = -4.3 Debye Å requires a theoretical model that employs both a good method and a good basis set. The results suggest that the use of second-order Møller-Plesset perturbation theory in conjunction with well-polarized triple- ζ basis sets provides a cost-effective and quite accurate method for the estimation of correlation effects on quadrupole moments.

AB - The quadrupolarity of carbon dioxide has been studied with higher level ab initio methods. Carbon dioxide exhibits {- + -} quadrupolarity in all directions and an explanation is provided of the origin of the sign of the diagonal elements Q ii . The quadrupole moment tensor has been computed using restricted Hartree-Fock theory, second-order Møller-Plesset perturbation theory and quadratic configuration interaction theory. A variety of basis sets have been employed up to basis sets of the type [5s, 4p, 2d, 1f] (23s, 8p, 2d, 1f). The quadrupole moment tensor component Q &spar; of carbon dioxide falls in the range between -18.5 and -20.5 Debye Å. The quadrupole moment tensor components Q &perp; of carbon dioxide are smaller, ranging from -14.5 to -15 Debye Å, and they are less sensitive to the choice of the theoretical model. The correlated methods consistently predict an increase of Q &spar; while they predict a more modest reduction of Q &perp; . It is for the opposing electron correlation effects on Q &spar; and Q &perp; that the average values of the diagonal elements, 〈 Q ii 〉, are essentially independent of the method and exhibit only a small variation depending on the basis set. On the other hand, the anisotropy of the quadrupolarity, the quadrupole moment Θ , is affected most by the opposing electron correlation effects on Q &spar; and Q &perp; . The accurate reproduction of the measured quadrupolarity Θ = -4.3 Debye Å requires a theoretical model that employs both a good method and a good basis set. The results suggest that the use of second-order Møller-Plesset perturbation theory in conjunction with well-polarized triple- ζ basis sets provides a cost-effective and quite accurate method for the estimation of correlation effects on quadrupole moments.

KW - Ab Initio Calculations

KW - Anisotropy

KW - Atomic Charges

KW - Carbon Dioxide

KW - Catalysis

KW - Deamination

KW - Dehydration

KW - Dipole

KW - Electrostatic Bonding

KW - Hydrogen Bond

KW - Hydrolysis

KW - Molecular Interaction

KW - Nucleotide Metabolism

KW - Quadrupole Moment Tensor Components

KW - Quantum Mechanics

KW - Reaction Analysis

UR - https://scholarsmine.mst.edu/chem_facwork/2726

UR - http://doi.org/10.1016/S0022-2860(00)00658-X

U2 - 10.1016/S0022-2860(00)00658-X

DO - 10.1016/S0022-2860(00)00658-X

M3 - Article

VL - 556

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

ER -

A Higher Level Ab Initio Quantum-Mechanical Study of the Quadrupole Moment Tensor Components of Carbon Dioxide

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