Ab initio calculations of polarizability and second hyperpolarizability in benzene including electron correlation treated by Møller-Plesset theory

E. Perrin, P. N. Prasad, P. Mougenot, Michel Dupuis

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Abstract

We present an ab initio calculation of polarizability and second hyperpolarizability for the benzene molecule including electron-electron correlation. The finite field method is used. For each selected strength of the applied electric field the energy of the benzene molecule is calculated using the self-consistent field method (SCF) as well as with its Møller-Plesset correction in the second order (MP-2). Then the microscopic optical nonlinear responses are calculated by fitting both the SCF energy and the MP-2 energy to a polynomial in the field strength. We find that electron correlation significantly enhances the second hyperpolarizability. For the polarizability, our computed value shows an excellent agreement with the experimentally measured value. For the second hyperpolarizability, the computed value using MP-2 energy shows a reasonable agreement with that reported by the electrical field induced second harmonic (EFISH) generation but a poor agreement with the result of degenerate four wave mixing (DFWM). Finally, we also compare our ab initio results with those previously reported using semiempirical methods.

Original languageEnglish
Pages (from-to)4728-4732
Number of pages5
JournalJournal of Chemical Physics
Volume91
Issue number8
Publication statusPublished - 1989

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Electron correlations
Benzene
benzene
Molecules
self consistent fields
Four wave mixing
Harmonic generation
energy methods
electrons
Electric fields
Polynomials
four-wave mixing
energy
Electrons
molecules
field strength
harmonic generations
polynomials
electric fields

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Ab initio calculations of polarizability and second hyperpolarizability in benzene including electron correlation treated by Møller-Plesset theory. / Perrin, E.; Prasad, P. N.; Mougenot, P.; Dupuis, Michel.

In: Journal of Chemical Physics, Vol. 91, No. 8, 1989, p. 4728-4732.

Research output: Contribution to journalArticle

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N2 - We present an ab initio calculation of polarizability and second hyperpolarizability for the benzene molecule including electron-electron correlation. The finite field method is used. For each selected strength of the applied electric field the energy of the benzene molecule is calculated using the self-consistent field method (SCF) as well as with its Møller-Plesset correction in the second order (MP-2). Then the microscopic optical nonlinear responses are calculated by fitting both the SCF energy and the MP-2 energy to a polynomial in the field strength. We find that electron correlation significantly enhances the second hyperpolarizability. For the polarizability, our computed value shows an excellent agreement with the experimentally measured value. For the second hyperpolarizability, the computed value using MP-2 energy shows a reasonable agreement with that reported by the electrical field induced second harmonic (EFISH) generation but a poor agreement with the result of degenerate four wave mixing (DFWM). Finally, we also compare our ab initio results with those previously reported using semiempirical methods.

AB - We present an ab initio calculation of polarizability and second hyperpolarizability for the benzene molecule including electron-electron correlation. The finite field method is used. For each selected strength of the applied electric field the energy of the benzene molecule is calculated using the self-consistent field method (SCF) as well as with its Møller-Plesset correction in the second order (MP-2). Then the microscopic optical nonlinear responses are calculated by fitting both the SCF energy and the MP-2 energy to a polynomial in the field strength. We find that electron correlation significantly enhances the second hyperpolarizability. For the polarizability, our computed value shows an excellent agreement with the experimentally measured value. For the second hyperpolarizability, the computed value using MP-2 energy shows a reasonable agreement with that reported by the electrical field induced second harmonic (EFISH) generation but a poor agreement with the result of degenerate four wave mixing (DFWM). Finally, we also compare our ab initio results with those previously reported using semiempirical methods.

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