Simulation of photoelectron spectra with anharmonicity fully included: Application to the X 2A2<--X 1A1 band of furan

Sean Bonness; Bernard Kirtman; Miquel Huix; Angel J Sanchez; Josep M Luis

doi:10.1063/1.2210479

Simulation of photoelectron spectra with anharmonicity fully included: Application to the X 2A2<--X 1A1 band of furan

J Chem Phys. 2006 Jul 7;125(1):014311. doi: 10.1063/1.2210479.

Authors

Sean Bonness¹, Bernard Kirtman, Miquel Huix, Angel J Sanchez, Josep M Luis

Affiliation

¹ Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106, USA.

PMID: 16863302
DOI: 10.1063/1.2210479

Abstract

Using a new unconventional procedure for calculating Franck-Condon factors with anharmonicity fully included the X 2A2<--X 1A1 band in the photoelectron spectrum of furan (and deuterated furan) was simulated at the second-order perturbation theory level. All 21 vibrational modes were considered but, in the end, only 4 are required to accurately reproduce the spectrum. Except for our own recent work on ethylene such calculations have been previously limited to tri- or tetraatomic molecules. Most of the effect of anharmonicity is accounted for in first order, although second-order corrections to the vibrational frequencies are important. Based on these simulations we were able to improve upon and extend previous assignments as well as suggest further measurements.