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

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

Research output: Contribution to journalArticle

10 Citations (Scopus)

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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Photodissociation
photodissociation
excitation
Electronic structure
electronic structure
Potential energy surfaces
Mass spectrometers
photoabsorption
Excited states
Ground state
mass spectrometers
Anions
potential energy
Spectroscopy
anions
ground state
spectroscopy

ASJC Scopus subject areas

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

Cite this

Photofragmentation dynamics of ICN-(CO2)n clusters following visible excitation. / Martin, Joshua P.; Case, Amanda S.; Gu, Quanli; Darr, Joshua Paul; McCoy, Anne B.; Lineberger, W. Carl.

In: Journal of Chemical Physics, Vol. 139, No. 6, 064315, 14.08.2013.

Research output: Contribution to journalArticle

Martin, Joshua P. ; Case, Amanda S. ; Gu, Quanli ; Darr, Joshua Paul ; McCoy, Anne B. ; Lineberger, W. Carl. / Photofragmentation dynamics of ICN-(CO2)n clusters following visible excitation. In: Journal of Chemical Physics. 2013 ; Vol. 139, No. 6.
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