d-orbital participation in bonding in thiophene

Comparison of CNDO/2 and ab initio results

G. Náray-Szabó, M. R. Peterson

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

We have compared CNDO/2 and ab initio STO-3G calculations for furan and thiophene with and without the inclusion of 3d-orbitals on oxygen and on sulphur. Comparison of localized molecular orbitals indicates that d-orbital participation is over-estimated within the CNDO/2 approximation, although trends are reflected correctly. Enhanced aromaticity of thiophene compared to furan is primarily due to the delocalization of C2C3 π-bonds to the vacant d-orbitals of sulphur. On the other hand, d-orbitals are unimportant in describing σ-bonds. Energies of canonical molecular orbitals, as obtained with the CNDO/2 and ab initio STO-3G* methods and divided into separate σ and π groups, run parallel with each other within both groups.

Original languageEnglish
Pages (from-to)249-255
Number of pages7
JournalJournal of Molecular Structure: THEOCHEM
Volume85
Issue number3-4
DOIs
Publication statusPublished - 1981

Fingerprint

Thiophenes
Molecular orbitals
Thiophene
thiophenes
Sulfur
orbitals
furans
molecular orbitals
sulfur
Oxygen
inclusions
trends
furan
oxygen
approximation
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics
  • Materials Science (miscellaneous)
  • Spectroscopy
  • Organic Chemistry
  • Structural Biology

Cite this

d-orbital participation in bonding in thiophene : Comparison of CNDO/2 and ab initio results. / Náray-Szabó, G.; Peterson, M. R.

In: Journal of Molecular Structure: THEOCHEM, Vol. 85, No. 3-4, 1981, p. 249-255.

Research output: Contribution to journalArticle

@article{de21de4abcf44723a9517440e0b226ec,
title = "d-orbital participation in bonding in thiophene: Comparison of CNDO/2 and ab initio results",
abstract = "We have compared CNDO/2 and ab initio STO-3G calculations for furan and thiophene with and without the inclusion of 3d-orbitals on oxygen and on sulphur. Comparison of localized molecular orbitals indicates that d-orbital participation is over-estimated within the CNDO/2 approximation, although trends are reflected correctly. Enhanced aromaticity of thiophene compared to furan is primarily due to the delocalization of C2C3 π-bonds to the vacant d-orbitals of sulphur. On the other hand, d-orbitals are unimportant in describing σ-bonds. Energies of canonical molecular orbitals, as obtained with the CNDO/2 and ab initio STO-3G* methods and divided into separate σ and π groups, run parallel with each other within both groups.",
author = "G. N{\'a}ray-Szab{\'o} and Peterson, {M. R.}",
year = "1981",
doi = "10.1016/0166-1280(81)85023-3",
language = "English",
volume = "85",
pages = "249--255",
journal = "Computational and Theoretical Chemistry",
issn = "2210-271X",
publisher = "Elsevier BV",
number = "3-4",

}

TY - JOUR

T1 - d-orbital participation in bonding in thiophene

T2 - Comparison of CNDO/2 and ab initio results

AU - Náray-Szabó, G.

AU - Peterson, M. R.

PY - 1981

Y1 - 1981

N2 - We have compared CNDO/2 and ab initio STO-3G calculations for furan and thiophene with and without the inclusion of 3d-orbitals on oxygen and on sulphur. Comparison of localized molecular orbitals indicates that d-orbital participation is over-estimated within the CNDO/2 approximation, although trends are reflected correctly. Enhanced aromaticity of thiophene compared to furan is primarily due to the delocalization of C2C3 π-bonds to the vacant d-orbitals of sulphur. On the other hand, d-orbitals are unimportant in describing σ-bonds. Energies of canonical molecular orbitals, as obtained with the CNDO/2 and ab initio STO-3G* methods and divided into separate σ and π groups, run parallel with each other within both groups.

AB - We have compared CNDO/2 and ab initio STO-3G calculations for furan and thiophene with and without the inclusion of 3d-orbitals on oxygen and on sulphur. Comparison of localized molecular orbitals indicates that d-orbital participation is over-estimated within the CNDO/2 approximation, although trends are reflected correctly. Enhanced aromaticity of thiophene compared to furan is primarily due to the delocalization of C2C3 π-bonds to the vacant d-orbitals of sulphur. On the other hand, d-orbitals are unimportant in describing σ-bonds. Energies of canonical molecular orbitals, as obtained with the CNDO/2 and ab initio STO-3G* methods and divided into separate σ and π groups, run parallel with each other within both groups.

UR - http://www.scopus.com/inward/record.url?scp=49049149969&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=49049149969&partnerID=8YFLogxK

U2 - 10.1016/0166-1280(81)85023-3

DO - 10.1016/0166-1280(81)85023-3

M3 - Article

VL - 85

SP - 249

EP - 255

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

IS - 3-4

ER -