Conformationally controlled chemistry: Excited-state dynamics dictate ground-state reaction

Myung Hwa Kim, Lei Shen, Hongli Tao, Todd J. Martinez, Arthur G. Suits

Research output: Contribution to journalArticlepeer-review

90 Scopus citations

Abstract

Ion imaging reveals distinct photodissociation dynamics for propanal cations initially prepared in either the cis or gauche conformation, even though these isomers differ only slightly in energy and face a small interconversion barrier. The product kinetic energy distributions for the hydrogen atom elimination channels are bimodal, and the two peaks are readily assigned to propanoyl cation or hydroxyallyl cation coproducts. Ab initio multiple spawning dynamical calculations suggest that distinct ultrafast dynamics in the excited state deposit each conformer in isolated regions of the ground-state potential energy surface, and, from these distinct regions, conformer interconversion does not effectively compete with dissociation.

Original languageEnglish
Pages (from-to)1561-1565
Number of pages5
JournalScience
Volume315
Issue number5818
DOIs
StatePublished - 16 Mar 2007

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