Photofragmentation dynamics of ICN-(CO2)n clusters following visible excitation

Joshua P. Martin, Amanda S. Case, Quanli Gu, Joshua P. Darr, Anne B. McCoy, W. Carl Lineberger

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Abstract

Photodissociation of ICN-(CO2)n, n = 0-18, with 500-nm excitation is investigated using a dual time-of-flight mass spectrometer. Photoabsorption to the 2Π1/2 state is detected using ionic-photoproduct action spectroscopy; the maximum absorption occurs around 490 nm. Ionic-photoproduct distributions were determined for ICN-(CO2)n at 500 nm. Following photodissociation of bare ICN- via 430-650 nm excitation, a small fraction of CN- is produced, suggesting that nonadiabatic effects play a role in the photodissociation of this simple anion. Electronic structure calculations, carried out at the MR-SO-CISD level of theory, were used to evaluate the potential-energy surfaces for the ground and excited states of ICN-. Analysis of the electronic structure supports the presence of nonadiabatic effects in the photodissociation dynamics. For n ≥ 2, the major ionic photoproduct has a mass corresponding to either partially solvated CN - or partially solvated [NCCO2]-.

Original languageEnglish (US)
Article number064315
JournalJournal of Chemical Physics
Volume139
Issue number6
DOIs
StatePublished - Aug 14 2013

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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