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Issue 7, 2014
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Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate

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Abstract

The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged “reactivity funnel” of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states.

Graphical abstract: Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate

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Publication details

The article was received on 05 Sep 2013, accepted on 07 Nov 2013 and first published on 11 Nov 2013


Article type: Paper
DOI: 10.1039/C3CP53792G
Phys. Chem. Chem. Phys., 2014,16, 2854-2865

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    Roads leading to roam. Role of triple fragmentation and of conical intersections in photochemical reactions: experiments and theory on methyl formate

    P. Tsai, M. Chao, T. Kasai, K. Lin, A. Lombardi, F. Palazzetti and V. Aquilanti, Phys. Chem. Chem. Phys., 2014, 16, 2854
    DOI: 10.1039/C3CP53792G

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