Issue 25, 2012

The photo-dissociation of the pyrrole–ammonia complex—the role of hydrogen bonding in Rydberg states photochemistry

Abstract

The photochemistry of the pyrrole–ammonia cluster is analyzed theoretically. Whereas in neat pyrrole the dominant photochemical reaction is H-atom cleavage, recent experiments show that in pyrrole–ammonia clusters the major reaction is H-transfer to form the NH4 radical (solvated by ammonia molecules in the case of large clusters) and the pyrrolyl radical. A mechanism involving the hydrogen-bonded Rydberg state is offered to account for these results and verified computationally. Two minima are located on the lowest excited singlet PES. Both of them are Rydberg states, one leads to the formation of NH4 and pyrrolyl radicals, the other is connected to the πσ* state through a relatively high barrier, leading to a 3-body dissociation reaction to form a pyrrolyl radical, ammonia and an H-atom. The former is the energetically and statistically preferred one.

Graphical abstract: The photo-dissociation of the pyrrole–ammonia complex—the role of hydrogen bonding in Rydberg states photochemistry

Supplementary files

Article information

Article type
Paper
Submitted
04 Dec 2011
Accepted
23 Jan 2012
First published
23 Jan 2012

Phys. Chem. Chem. Phys., 2012,14, 8836-8841

The photo-dissociation of the pyrrole–ammonia complex—the role of hydrogen bonding in Rydberg states photochemistry

S. Zilberg, A. Kahan and Y. Haas, Phys. Chem. Chem. Phys., 2012, 14, 8836 DOI: 10.1039/C2CP23849G

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