The valence electronic excited states of Fe2(CO)9 have been studied using the time-dependent density functional theory (TDDFT). Both tribridged D3h and monobridged C2V structures have been considered, and the structure of selected low-lying singlet and triplet excited states have been optimized on the basis of the TDDFT analytical gradient. Optimized excited-state geometries are used to obtain an insight into certain aspects of the Fe2- (CO)9 photochemistry. The Fe2(CO)9 (D3h) first triplet and second singlet excited states are unbound with respect to dibridged Fe2(CO)8 + CO, and the first two monobridged Fe2(CO)9 (C2V) singlet states are unbound with respect to the Fe(CO)5 + Fe(CO)4 dissociation. These results are discussed in light of the experimental data available
Bertini, L., Greco, C., DE GIOIA, L., Fantucci, P. (2006). Time-Dependent Density Functional Theory Study of Fe2(CO)9 Low-Lying Electronic Excited States. JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY, 110(47), 12900-12907 [10.1021/jp0646022].
Time-Dependent Density Functional Theory Study of Fe2(CO)9 Low-Lying Electronic Excited States
BERTINI, LUCA;GRECO, CLAUDIO;DE GIOIA, LUCA;FANTUCCI, PIERCARLO
2006
Abstract
The valence electronic excited states of Fe2(CO)9 have been studied using the time-dependent density functional theory (TDDFT). Both tribridged D3h and monobridged C2V structures have been considered, and the structure of selected low-lying singlet and triplet excited states have been optimized on the basis of the TDDFT analytical gradient. Optimized excited-state geometries are used to obtain an insight into certain aspects of the Fe2- (CO)9 photochemistry. The Fe2(CO)9 (D3h) first triplet and second singlet excited states are unbound with respect to dibridged Fe2(CO)8 + CO, and the first two monobridged Fe2(CO)9 (C2V) singlet states are unbound with respect to the Fe(CO)5 + Fe(CO)4 dissociation. These results are discussed in light of the experimental data available
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