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 - Nov 1981

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Fingerprint Dive into the research topics of 'd-orbital participation in bonding in thiophene: Comparison of CNDO/2 and ab initio results'. Together they form a unique fingerprint.

  • Cite this