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Ab initio and density functional theory calculations of the dipole polarizability and the second dipole hyperpolarizability of benzene
Author(s) -
Soscún Humberto,
Hernández Javier,
Escobar Ramón,
ToroMendoza Carlos,
Alvarado Ysaías,
Hinchliffe Alan
Publication year - 2002
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.931
Subject(s) - hyperpolarizability , polarizability , dipole , basis set , chemistry , density functional theory , ab initio , perturbation theory (quantum mechanics) , electronic correlation , ab initio quantum chemistry methods , computational chemistry , molecular physics , atomic physics , molecule , physics , quantum mechanics , organic chemistry
The linear dipole polarizability α and nonlinear second dipole hyperpolarizability γ of benzene were calculated using the ab initio SCF–MO restricted Hartree–Fock (HF) method. The coupled perturbed HF and time‐dependent HF (TDHF) methods were used for the evaluation of the static and dynamic properties, respectively. The TDHF approach was applied at different optical frequencies, and the second hyperpolarizability γ was evaluated for different optical processes. Electron correlation was taken into account by using the Møller–Plesset perturbation theory (MP2) and the density functional theory B3LYP hybrid approach, with a finite field method, with electric fields of ±0.01, ±0.02, ±0.03, and ±0.04 a.u. used. Benzene was assumed to have a D 6 h geometry, and the standard STO/6‐31+G( d , p ) (A) and optimized STO/6‐31+G( d *, p ) (B) basis sets were employed for the calculations. In the optimized basis set, the d exponent of the C atomic function was varied in order to obtain a maximum static benzene γ at the TDHF level of theory. This optimized basis set was able to gives values for the (hyper)polarizabilities of benzene that agree excellently with experimental results and previous calculations. The calculated properties were analyzed in terms of the Laplacian of the electron density calculated using the atoms in molecules method due to Bader. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002