Automated Exploration of Photolytic Channels of HCOOH: Conformational Memory via Excited-State Roaming.
To elucidate the photodissociation mechanism of HCOOH, we systematically explored reaction pathways starting from the first excited singlet state (S1) by using automated reaction path search methods. All critical points, that is, minima, transition states, minimum energy conical intersections, and minima on seam of crossing, for the S0, T1, and S1 potential energy surfaces (PESs) obtained in the present search were optimized at the CASPT2 level. The structure list obtained by the search explained all experimentally reported photolytic channels. A new mechanism for the previously suggested but unexplained conformational memory in the 193 nm photolysis is proposed, which involves two steps: partial dissociation and succeeding roaming of one of H atoms on the S1 PES, followed by intramolecular recombination on the S0 PES after radiationless transition through a conical intersection at a partially dissociated geometry. This is partially similar to the excited-state roaming recently discovered for the NO3 radical.
†Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
Satoshi
S
Maeda
†Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo 060-0810, Japan.
Tetsuya
T
Taketsugu
‡Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103, Japan.|§Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, United States.
Keiji
K
Morokuma
automated reaction path search; conformational memory; excited-state roaming; formic acid; photolysis; reaction path; roaming