This paper is part of a special issue dedicated to Professor J. C. (Tito) Scaiano on the occasion of his 60th birthday.
Ultraviolet Absorption Spectra of Substituted Phenols: A Computational Study†
Article first published online: 30 APR 2007
Photochemistry and Photobiology
Volume 82, Issue 1, pages 324–331, January 2006
How to Cite
Zhang, L., Peslherbe, G. H. and Muchall, H. M. (2006), Ultraviolet Absorption Spectra of Substituted Phenols: A Computational Study. Photochemistry and Photobiology, 82: 324–331. doi: 10.1562/2005-07-08-RA-605
- Issue published online: 30 APR 2007
- Article first published online: 30 APR 2007
- Received 8 July 2005; accepted 9 November 2005; published online 28 November 2005
Vertical excitation energies for electronic transitions from the ground state to the first two excited states of phenol, mono- and disubstituted methoxyphenols and methyl-substituted phenols have been characterized with the Time-Dependent Density Functional Theory (TD-DFT), the Complete Active Space Self-Consistent Field method (CASSCF) and the Coupled Cluster with Single and Double Excitations Equation-of-Motion approach (CCSD-EOM) to simulate and interpret experimental ultraviolet absorption spectra. While CASSCF excitation energies for the first two transitions either are grossly overestimated or exhibit a weak correlation with experimental data, both TD-DFT and CCSD-EOM perform very well, reproducing the spectral shifts of both the primary band and secondary band observed upon substitution. The conformational dependence of the calculated excitation energies is generally smaller than the shifts caused by substitution.