Effect of semi-empirical parameters on the triplet energy levels and triplet–triplet transition in benzene

✍ Scribed by A. B. Sannigrahi

• Publisher: John Wiley and Sons
• Year: 1971
• Tongue: English
• Weight: 395 KB
• Volume: 5
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560050303

✦ Synopsis

Abstract

Triplet energy levels and triplet–triplet transition in benzene have been calculated semi‐empirically by considering CI up to and including doubly excited configurations and using various values of the core resonance and electron repulsion integrals. The usual method of calibrating β (core resonance integral) from one of the observed transitions in the semi‐empirical methods is critically examined with respect to the triplet levels of this molecule. Semi‐empirical parameters are found to have a pronounced effect on the energy of the triplets and the triplet–triplet transitions; but the intensities of such transitions are quite insensitive to the choice of such parameters.

Numerical results show several ^3^B~1u~ → ^3^E~2g~ transitions of various intensities. Out of these, the transitions which correspond energetically to the observed triplet–triplet bands are found to have low intensity. Some strong triplet–triplet bands are predicted in the far ultra violet region.