Simulation of photoelectron spectra with anharmonicity fully included:: Application to the (X)over-tilde2A2←(X)over-tilde1A1 band of furan

被引:19
作者
Bonness, Sean
Kirtman, Bernard
Huix, Miquel
Sanchez, Angel J.
Luis, Josep M. [1 ]
机构
[1] Univ Girona, Inst Computat Chem, Girona 17071, Catalonia, Spain
[2] Univ Girona, Dept Chem, Girona 17071, Catalonia, Spain
[3] Univ Calif Santa Barbara, Dept Chem & Biochem, Santa Barbara, CA 93106 USA
关键词
D O I
10.1063/1.2210479
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Using a new unconventional procedure for calculating Franck-Condon factors with anharmonicity fully included the (A) over tilde (2)A(2)<-(X) over tilde (1)A(1) 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. (c) 2006 American Institute of Physics.
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页数:12
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