Photodissociation dynamics of gas-phase BrICl- and IBr2- anions

Andrei M Sanov, Todd Sanford, Laurie J. Butler, Jiri Vala, Ronnie Kosloff, W. Carl Lineberger

Research output: Contribution to journalArticle

17 Citations (Scopus)

Abstract

This work is the first study of mixed trihalide anions in the gas phase. We report the photochemistry and photodissociation dynamics of BrICl- and IBr2- anions near 400 nm. For BrICl-, two major photodissociation channels yielding IBr- and ICl- products are observed. The photodissociation of IBr2- yields primarily IBr- anion products. No BrCl- and Br2- fragments are formed from BrICl- and IBr2-, respectively, and the parent anions are ascribed linear [Br-I-Cl]- and [Br-I-Br]- structures, in agreement with ab initio calculations. The IBr- and ICl- products are produced in highly vibrationally excited states. We observe fragment vibrational coherence in femtosecond pump-probe measurements by probing nascent IBr- via its photodissociation to I- + Br. The IBr- vibrational periods observed in the photodissociation of BrICl- correspond to excitations of ∼80% of the IBr- dissociation energy (Do). In IBr2- dissociation, the average vibrational excitation of IBr- is 84-91% of Do. The high degrees of vibrational excitation raise questions about the effect of the proximity to the dissociation threshold on the dynamics of coherent wave packets. We analyze these dynamics analytically and by means of wave packet simulations and observe smearing of expected wave packet revivals.

Original languageEnglish (US)
Pages (from-to)10244-10254
Number of pages11
JournalJournal of Physical Chemistry A
Volume103
Issue number49
StatePublished - Dec 9 1999

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Photodissociation
photodissociation
Anions
Wave packets
Gases
vapor phases
anions
wave packets
dissociation
excitation
products
fragments
Photochemical reactions
Excited states
photochemical reactions
proximity
Pumps
pumps
thresholds
probes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Sanov, A. M., Sanford, T., Butler, L. J., Vala, J., Kosloff, R., & Lineberger, W. C. (1999). Photodissociation dynamics of gas-phase BrICl- and IBr2- anions. Journal of Physical Chemistry A, 103(49), 10244-10254.

Photodissociation dynamics of gas-phase BrICl- and IBr2- anions. / Sanov, Andrei M; Sanford, Todd; Butler, Laurie J.; Vala, Jiri; Kosloff, Ronnie; Lineberger, W. Carl.

In: Journal of Physical Chemistry A, Vol. 103, No. 49, 09.12.1999, p. 10244-10254.

Research output: Contribution to journalArticle

Sanov, AM, Sanford, T, Butler, LJ, Vala, J, Kosloff, R & Lineberger, WC 1999, 'Photodissociation dynamics of gas-phase BrICl- and IBr2- anions', Journal of Physical Chemistry A, vol. 103, no. 49, pp. 10244-10254.
Sanov AM, Sanford T, Butler LJ, Vala J, Kosloff R, Lineberger WC. Photodissociation dynamics of gas-phase BrICl- and IBr2- anions. Journal of Physical Chemistry A. 1999 Dec 9;103(49):10244-10254.
Sanov, Andrei M ; Sanford, Todd ; Butler, Laurie J. ; Vala, Jiri ; Kosloff, Ronnie ; Lineberger, W. Carl. / Photodissociation dynamics of gas-phase BrICl- and IBr2- anions. In: Journal of Physical Chemistry A. 1999 ; Vol. 103, No. 49. pp. 10244-10254.
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