Jump to main content
Jump to site search

Issue 48, 2010
Previous Article Next Article

Controlling the mechanism of fulvene S1/S0 decay: switching off the stepwise population transfer

Author affiliations

Abstract

Direct quantum dynamics simulations were performed to model the radiationless decay of the first excited state S1 of fulvene. The full space of thirty normal mode nuclear coordinates was explicitly considered. By default, ultrafast internal conversion takes place centred on the higher-energy planar region of the S1/S0 conical intersection seam, giving the stepwise population transfer characteristic of a sloped surface crossing, and leading back to the ground state reactant. Two possible schemes for controlling whether stepwise population transfer occurs or not—either altering the initial geometry distribution or the initial momentum composition of the photo-excited wavepacket—were explored. In both cases, decay was successfully induced to occur in the lower-energy twisted/peaked region of the crossing seam, switching off the stepwise population transfer. This absence of re-crossing is a direct consequence of the change in the position on the intersection at which decay occurs (our target for control), and its consequences should provide an experimentally observable fingerprint of this system.

Graphical abstract: Controlling the mechanism of fulvene S1/S0 decay: switching off the stepwise population transfer

Back to tab navigation

Supplementary files

Publication details

The article was received on 08 Sep 2010, accepted on 29 Oct 2010 and first published on 16 Nov 2010


Article type: Paper
DOI: 10.1039/C0CP01757D
Citation: Phys. Chem. Chem. Phys., 2010,12, 15725-15733

  •   Request permissions

    Controlling the mechanism of fulvene S1/S0 decay: switching off the stepwise population transfer

    D. Mendive-Tapia, B. Lasorne, G. A. Worth, M. J. Bearpark and M. A. Robb, Phys. Chem. Chem. Phys., 2010, 12, 15725
    DOI: 10.1039/C0CP01757D

Search articles by author

Spotlight

Advertisements