Abstract
In the ultrafast photodissociation of Cr(CO)(6), Cr(CO)(5) is formed within 50 fs. Initially in an excited state, a Jahn-Teller (E circle times e) conical intersection is believed to then act as an efficient decay funnel to the ground state. Here, we present a Hamiltonian representing the first three electronic states of Cr(CO)(5), obtained by fitting the linear vibronic coupling model to calculations using a complete active space self-consistent field (CASSCF) wave-function. The intersection is in fact found to involve ((E circle plus A) circle times e) pseudo-Jahn-Teller coupling, with the singly degenerate state playing an important role. The results of wave-packet dynamics using the multi-configuration time-dependent Hartree (MCTDH) method show that this model is consistent with the experimental data.
Original language | English |
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Pages (from-to) | 1095-1105 |
Number of pages | 11 |
Journal | Molecular Physics |
Volume | 104 |
Issue number | 5-7 |
DOIs | |
Publication status | Published - 2006 |
Keywords
- Cr(CO)(5)
- photodissociation
- Jahn-Teller conical intersection
- wavepacket dynamics
- MOLECULAR-DYNAMICS
- PROPAGATING WAVEPACKETS
- ORGANIC-PHOTOCHEMISTRY
- METAL HEXACARBONYLS
- BORN-OPPENHEIMER
- APPROXIMATION
- FRAMEWORK
- SPECTRA
- CR