Diatomic sulfur: Low lying bound molecular electronic states of S 2

William C. Swope*, Yuan-Pern Lee, Henry F. Schaefer

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

70 Scopus citations

Abstract

We present here the results of self-consistent field (SCF) and configuration interaction (CI) type calculations on thirteen low-lying electronic states of diatomic sulfur. The basis set was one of double zeta quality augmented with polarization functions. The CI space for each electronic state consisted of all configurations constructed from single and double excitations of electrons from the valence orbitals of the Hartree-Fock configuration. There are several significant findings of this study. First, we report the discovery of a previously unobserved and bound 1Π u state which lies approximately 37000 cm-1 above the ground state. This state dissociates to two ground state sulfur atoms. Second, we provide new predictions of excitation energies and properties for the three states e 1Πg, c 1Σu -, and B″3Πu. These states were suspected or known to be bound, but experimentally determined properties were uncertain. Finally, we find that systematic application of a formula of Davidson, which estimates the contribution of unlinked energy terms in a singles and doubles CI calculation, leads to improved predictions of excitation energies.

Original languageEnglish
Pages (from-to)947-953
Number of pages7
JournalThe Journal of chemical physics
Volume70
Issue number2
DOIs
StatePublished - 15 Jan 1979

Fingerprint

Dive into the research topics of 'Diatomic sulfur: Low lying bound molecular electronic states of S <sub>2</sub>'. Together they form a unique fingerprint.

Cite this