Wavepacket dynamics study of Cr(CO)(5) after formation by photodissociation: relaxation through an (E circle plus A) circle times e Jahn-Teller conical intersection

G A Worth, G Welch, M J Paterson, Martin Paterson

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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 languageEnglish
Pages (from-to)1095-1105
Number of pages11
JournalMolecular Physics
Volume104
Issue number5-7
DOIs
Publication statusPublished - 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

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