SAC and SAC-CI calculations of excitation and circular dichroism spectra of straight-chain and cyclic dichalcogens

Junji Seino, Yasushi Honda, Masahiko Hada, Hiroshi Nakatsuji

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Accurate quantum-chemical calculations of the excitation energies and the rotatory strengths of dichalcogens R-Ch-Ch-R (Ch = S, Se, Te) were carried out with the symmetry adapted cluster (SAC) and SAC-configuration interaction (CI) methods. A series of straight-chain molecules (dihydrogen dichalcogenide, dimethyl dichalcogenide, and (+)-bis(2-methylbutyl) dichalcogenide) and one cyclic molecule (2,3-(R,R)-dichalcogenadecalin) were adopted for comparative analysis. The calculated excitation and circular dichroism (CD) spectra were in good agreement with experimental ones (Laur, P. H. A. In Proceedings of the Third International Symposium on Organic Selenium and Tellurium Compounds; Cagniant, D., Kirsch, G., Eds.; Universite de Metz: Metz, 1979; pp 219-299) within 0.3 eV. The fitting CD spectra also reasonably reproduced the experimental ones. In all the molecules adopted, the first and second lowest bands were assigned to the n-σ*(Ch-Ch) transition and the third and fourth lowest bands to the n-σ*(Ch-R) transition. The first and second lowest bands apparently depended on the R-Ch-Ch-R dihedral angle, suggesting that the orbital energies of two σ*(Ch-Ch) change with the R-Ch-Ch-R dihedral angle. This calculated trend agrees with two empirical rules: the C2 rule and the quadrant rule.

Original languageEnglish
Pages (from-to)10053-10062
Number of pages10
JournalJournal of Physical Chemistry A
Volume110
Issue number33
DOIs
Publication statusPublished - 2006 Aug 24
Externally publishedYes

Fingerprint

Dichroism
configuration interaction
dichroism
Dihedral angle
Molecules
dihedral angle
Tellurium compounds
Selenium compounds
tellurium compounds
symmetry
selenium compounds
excitation
molecules
Excitation energy
quadrants
congressional reports
trends
orbitals
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

SAC and SAC-CI calculations of excitation and circular dichroism spectra of straight-chain and cyclic dichalcogens. / Seino, Junji; Honda, Yasushi; Hada, Masahiko; Nakatsuji, Hiroshi.

In: Journal of Physical Chemistry A, Vol. 110, No. 33, 24.08.2006, p. 10053-10062.

Research output: Contribution to journalArticle

Seino, Junji ; Honda, Yasushi ; Hada, Masahiko ; Nakatsuji, Hiroshi. / SAC and SAC-CI calculations of excitation and circular dichroism spectra of straight-chain and cyclic dichalcogens. In: Journal of Physical Chemistry A. 2006 ; Vol. 110, No. 33. pp. 10053-10062.
@article{e3211ece9ec34b0eab030942a37f1972,
title = "SAC and SAC-CI calculations of excitation and circular dichroism spectra of straight-chain and cyclic dichalcogens",
abstract = "Accurate quantum-chemical calculations of the excitation energies and the rotatory strengths of dichalcogens R-Ch-Ch-R (Ch = S, Se, Te) were carried out with the symmetry adapted cluster (SAC) and SAC-configuration interaction (CI) methods. A series of straight-chain molecules (dihydrogen dichalcogenide, dimethyl dichalcogenide, and (+)-bis(2-methylbutyl) dichalcogenide) and one cyclic molecule (2,3-(R,R)-dichalcogenadecalin) were adopted for comparative analysis. The calculated excitation and circular dichroism (CD) spectra were in good agreement with experimental ones (Laur, P. H. A. In Proceedings of the Third International Symposium on Organic Selenium and Tellurium Compounds; Cagniant, D., Kirsch, G., Eds.; Universite de Metz: Metz, 1979; pp 219-299) within 0.3 eV. The fitting CD spectra also reasonably reproduced the experimental ones. In all the molecules adopted, the first and second lowest bands were assigned to the n-σ*(Ch-Ch) transition and the third and fourth lowest bands to the n-σ*(Ch-R) transition. The first and second lowest bands apparently depended on the R-Ch-Ch-R dihedral angle, suggesting that the orbital energies of two σ*(Ch-Ch) change with the R-Ch-Ch-R dihedral angle. This calculated trend agrees with two empirical rules: the C2 rule and the quadrant rule.",
author = "Junji Seino and Yasushi Honda and Masahiko Hada and Hiroshi Nakatsuji",
year = "2006",
month = "8",
day = "24",
doi = "10.1021/jp0627271",
language = "English",
volume = "110",
pages = "10053--10062",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "33",

}

TY - JOUR

T1 - SAC and SAC-CI calculations of excitation and circular dichroism spectra of straight-chain and cyclic dichalcogens

AU - Seino, Junji

AU - Honda, Yasushi

AU - Hada, Masahiko

AU - Nakatsuji, Hiroshi

PY - 2006/8/24

Y1 - 2006/8/24

N2 - Accurate quantum-chemical calculations of the excitation energies and the rotatory strengths of dichalcogens R-Ch-Ch-R (Ch = S, Se, Te) were carried out with the symmetry adapted cluster (SAC) and SAC-configuration interaction (CI) methods. A series of straight-chain molecules (dihydrogen dichalcogenide, dimethyl dichalcogenide, and (+)-bis(2-methylbutyl) dichalcogenide) and one cyclic molecule (2,3-(R,R)-dichalcogenadecalin) were adopted for comparative analysis. The calculated excitation and circular dichroism (CD) spectra were in good agreement with experimental ones (Laur, P. H. A. In Proceedings of the Third International Symposium on Organic Selenium and Tellurium Compounds; Cagniant, D., Kirsch, G., Eds.; Universite de Metz: Metz, 1979; pp 219-299) within 0.3 eV. The fitting CD spectra also reasonably reproduced the experimental ones. In all the molecules adopted, the first and second lowest bands were assigned to the n-σ*(Ch-Ch) transition and the third and fourth lowest bands to the n-σ*(Ch-R) transition. The first and second lowest bands apparently depended on the R-Ch-Ch-R dihedral angle, suggesting that the orbital energies of two σ*(Ch-Ch) change with the R-Ch-Ch-R dihedral angle. This calculated trend agrees with two empirical rules: the C2 rule and the quadrant rule.

AB - Accurate quantum-chemical calculations of the excitation energies and the rotatory strengths of dichalcogens R-Ch-Ch-R (Ch = S, Se, Te) were carried out with the symmetry adapted cluster (SAC) and SAC-configuration interaction (CI) methods. A series of straight-chain molecules (dihydrogen dichalcogenide, dimethyl dichalcogenide, and (+)-bis(2-methylbutyl) dichalcogenide) and one cyclic molecule (2,3-(R,R)-dichalcogenadecalin) were adopted for comparative analysis. The calculated excitation and circular dichroism (CD) spectra were in good agreement with experimental ones (Laur, P. H. A. In Proceedings of the Third International Symposium on Organic Selenium and Tellurium Compounds; Cagniant, D., Kirsch, G., Eds.; Universite de Metz: Metz, 1979; pp 219-299) within 0.3 eV. The fitting CD spectra also reasonably reproduced the experimental ones. In all the molecules adopted, the first and second lowest bands were assigned to the n-σ*(Ch-Ch) transition and the third and fourth lowest bands to the n-σ*(Ch-R) transition. The first and second lowest bands apparently depended on the R-Ch-Ch-R dihedral angle, suggesting that the orbital energies of two σ*(Ch-Ch) change with the R-Ch-Ch-R dihedral angle. This calculated trend agrees with two empirical rules: the C2 rule and the quadrant rule.

UR - http://www.scopus.com/inward/record.url?scp=33748525537&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33748525537&partnerID=8YFLogxK

U2 - 10.1021/jp0627271

DO - 10.1021/jp0627271

M3 - Article

C2 - 16913679

AN - SCOPUS:33748525537

VL - 110

SP - 10053

EP - 10062

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 33

ER -