Structure, vibrational spectra, and IR intensities of polyenes from ab initio SCF calculations

H. O. Villar, Michel Dupuis, J. D. Watts, G. J B Hurst, E. Clementi

Research output: Contribution to journalArticle

70 Citations (Scopus)

Abstract

Ab initio SCF calculations are presented which deal with the structure of polyenes, as model systems for polyacetylene (PA). We used a double zeta quality basis set, and determined the structure of clusters up to C22H 24 as well as the vibrational spectra of clusters up to C 12H14, including infrared intensities. All of these data are analyzed by comparing with experimental information available on polyacetylene and previous theoretical studies. Specifically, we identified the vibrational modes corresponding to the observed absorption bands of PA. We comment on controversial points such as the relative contributions of internal coordinates to these modes, on the magnitude of interaction force constants, and also on the effect of light polarization on the absorption of some vibrational modes. We establish that the inclusion of polarization function in the basis set does not lead to significant changes in structural or energetic properties. Convergence of the cluster properties toward the 1D polymer properties was also tested with ab initio crystal orbital calculations.

Original languageEnglish
Pages (from-to)1003-1009
Number of pages7
JournalJournal of Chemical Physics
Volume88
Issue number2
Publication statusPublished - 1988

Fingerprint

Polyacetylenes
Polyenes
polyacetylene
Vibrational spectra
vibrational spectra
self consistent fields
vibration mode
Orbital calculations
polarization
Light polarization
Absorption spectra
Polymers
inclusions
Polarization
Infrared radiation
absorption spectra
orbitals
Crystals
polymers
crystals

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Villar, H. O., Dupuis, M., Watts, J. D., Hurst, G. J. B., & Clementi, E. (1988). Structure, vibrational spectra, and IR intensities of polyenes from ab initio SCF calculations. Journal of Chemical Physics, 88(2), 1003-1009.

Structure, vibrational spectra, and IR intensities of polyenes from ab initio SCF calculations. / Villar, H. O.; Dupuis, Michel; Watts, J. D.; Hurst, G. J B; Clementi, E.

In: Journal of Chemical Physics, Vol. 88, No. 2, 1988, p. 1003-1009.

Research output: Contribution to journalArticle

Villar, HO, Dupuis, M, Watts, JD, Hurst, GJB & Clementi, E 1988, 'Structure, vibrational spectra, and IR intensities of polyenes from ab initio SCF calculations', Journal of Chemical Physics, vol. 88, no. 2, pp. 1003-1009.
Villar, H. O. ; Dupuis, Michel ; Watts, J. D. ; Hurst, G. J B ; Clementi, E. / Structure, vibrational spectra, and IR intensities of polyenes from ab initio SCF calculations. In: Journal of Chemical Physics. 1988 ; Vol. 88, No. 2. pp. 1003-1009.
@article{0734d183bdc54ee6a8b31217b2029dbf,
title = "Structure, vibrational spectra, and IR intensities of polyenes from ab initio SCF calculations",
abstract = "Ab initio SCF calculations are presented which deal with the structure of polyenes, as model systems for polyacetylene (PA). We used a double zeta quality basis set, and determined the structure of clusters up to C22H 24 as well as the vibrational spectra of clusters up to C 12H14, including infrared intensities. All of these data are analyzed by comparing with experimental information available on polyacetylene and previous theoretical studies. Specifically, we identified the vibrational modes corresponding to the observed absorption bands of PA. We comment on controversial points such as the relative contributions of internal coordinates to these modes, on the magnitude of interaction force constants, and also on the effect of light polarization on the absorption of some vibrational modes. We establish that the inclusion of polarization function in the basis set does not lead to significant changes in structural or energetic properties. Convergence of the cluster properties toward the 1D polymer properties was also tested with ab initio crystal orbital calculations.",
author = "Villar, {H. O.} and Michel Dupuis and Watts, {J. D.} and Hurst, {G. J B} and E. Clementi",
year = "1988",
language = "English",
volume = "88",
pages = "1003--1009",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "2",

}

TY - JOUR

T1 - Structure, vibrational spectra, and IR intensities of polyenes from ab initio SCF calculations

AU - Villar, H. O.

AU - Dupuis, Michel

AU - Watts, J. D.

AU - Hurst, G. J B

AU - Clementi, E.

PY - 1988

Y1 - 1988

N2 - Ab initio SCF calculations are presented which deal with the structure of polyenes, as model systems for polyacetylene (PA). We used a double zeta quality basis set, and determined the structure of clusters up to C22H 24 as well as the vibrational spectra of clusters up to C 12H14, including infrared intensities. All of these data are analyzed by comparing with experimental information available on polyacetylene and previous theoretical studies. Specifically, we identified the vibrational modes corresponding to the observed absorption bands of PA. We comment on controversial points such as the relative contributions of internal coordinates to these modes, on the magnitude of interaction force constants, and also on the effect of light polarization on the absorption of some vibrational modes. We establish that the inclusion of polarization function in the basis set does not lead to significant changes in structural or energetic properties. Convergence of the cluster properties toward the 1D polymer properties was also tested with ab initio crystal orbital calculations.

AB - Ab initio SCF calculations are presented which deal with the structure of polyenes, as model systems for polyacetylene (PA). We used a double zeta quality basis set, and determined the structure of clusters up to C22H 24 as well as the vibrational spectra of clusters up to C 12H14, including infrared intensities. All of these data are analyzed by comparing with experimental information available on polyacetylene and previous theoretical studies. Specifically, we identified the vibrational modes corresponding to the observed absorption bands of PA. We comment on controversial points such as the relative contributions of internal coordinates to these modes, on the magnitude of interaction force constants, and also on the effect of light polarization on the absorption of some vibrational modes. We establish that the inclusion of polarization function in the basis set does not lead to significant changes in structural or energetic properties. Convergence of the cluster properties toward the 1D polymer properties was also tested with ab initio crystal orbital calculations.

UR - http://www.scopus.com/inward/record.url?scp=36549097020&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=36549097020&partnerID=8YFLogxK

M3 - Article

VL - 88

SP - 1003

EP - 1009

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 2

ER -