SCF and electron correlation studies on structures and harmonic in-plane force fields of ethylene, trans 1,3-butadiene, and all-trans 1,3,5-hexatriene

P. Szalay, A. Karpfen, H. Lischka

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53 Citations (Scopus)

Abstract

Equilibrium structures and in-plane harmonic force fields of ethylene, trans 1,3-butadiene, and all-trans 1,3,5-hexatriene were investigated with the aid of ab initio Hartree-Fock (SCF) calculations applying basis sets of DZ+P and TZ+P quality. The most interesting parts of the force fields, namely those involving stretching vibrations of the conjugated carbon backbone, were subsequently reevaluated including electron correlation at the coupled pair functional (CPF) level. We demonstrate that electron correlation has a significant influence not only on the degree of bond alternation in the ground state equilibrium structure but simultaneously leads to an increase in absolute value of all off-diagonal stretch-stretch coupling constants within the carbon backbone.

Original languageEnglish
Pages (from-to)3530-3538
Number of pages9
JournalThe Journal of Chemical Physics
Volume87
Issue number6
Publication statusPublished - 1987

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Electron correlations
butadiene
field theory (physics)
self consistent fields
ethylene
Carbon
harmonics
carbon
alternations
Ground state
Stretching
electrons
vibration
ground state
1,3,5-hexatriene
1,3-butadiene

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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abstract = "Equilibrium structures and in-plane harmonic force fields of ethylene, trans 1,3-butadiene, and all-trans 1,3,5-hexatriene were investigated with the aid of ab initio Hartree-Fock (SCF) calculations applying basis sets of DZ+P and TZ+P quality. The most interesting parts of the force fields, namely those involving stretching vibrations of the conjugated carbon backbone, were subsequently reevaluated including electron correlation at the coupled pair functional (CPF) level. We demonstrate that electron correlation has a significant influence not only on the degree of bond alternation in the ground state equilibrium structure but simultaneously leads to an increase in absolute value of all off-diagonal stretch-stretch coupling constants within the carbon backbone.",
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T1 - SCF and electron correlation studies on structures and harmonic in-plane force fields of ethylene, trans 1,3-butadiene, and all-trans 1,3,5-hexatriene

AU - Szalay, P.

AU - Karpfen, A.

AU - Lischka, H.

PY - 1987

Y1 - 1987

N2 - Equilibrium structures and in-plane harmonic force fields of ethylene, trans 1,3-butadiene, and all-trans 1,3,5-hexatriene were investigated with the aid of ab initio Hartree-Fock (SCF) calculations applying basis sets of DZ+P and TZ+P quality. The most interesting parts of the force fields, namely those involving stretching vibrations of the conjugated carbon backbone, were subsequently reevaluated including electron correlation at the coupled pair functional (CPF) level. We demonstrate that electron correlation has a significant influence not only on the degree of bond alternation in the ground state equilibrium structure but simultaneously leads to an increase in absolute value of all off-diagonal stretch-stretch coupling constants within the carbon backbone.

AB - Equilibrium structures and in-plane harmonic force fields of ethylene, trans 1,3-butadiene, and all-trans 1,3,5-hexatriene were investigated with the aid of ab initio Hartree-Fock (SCF) calculations applying basis sets of DZ+P and TZ+P quality. The most interesting parts of the force fields, namely those involving stretching vibrations of the conjugated carbon backbone, were subsequently reevaluated including electron correlation at the coupled pair functional (CPF) level. We demonstrate that electron correlation has a significant influence not only on the degree of bond alternation in the ground state equilibrium structure but simultaneously leads to an increase in absolute value of all off-diagonal stretch-stretch coupling constants within the carbon backbone.

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