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Yandell MA, King SB, Neumark DM. Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer. J Chem Phys. 2014;140(18):184317doi: 10.1063/1.4875021.
Yandell, M. A., King, S. B., & Neumark, D. M. (2014). Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer. The Journal of chemical physics, 140(18), 184317. https://doi.org/10.1063/1.4875021
Yandell, Margaret A, et al. "Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer." The Journal of chemical physics vol. 140,18 (2014): 184317. doi: https://doi.org/10.1063/1.4875021
Yandell MA, King SB, Neumark DM. Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer. J Chem Phys. 2014 May 14;140(18):184317. doi: 10.1063/1.4875021. PMID: 24832280.
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J Chem Phys. 2014 May 14;140(18):184317. doi: 10.1063/1.4875021.

Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer.

The Journal of chemical physics

Margaret A Yandell, Sarah B King, Daniel M Neumark

Affiliations

  1. Department of Chemistry, University of California, Berkeley, California 94720, USA.

PMID: 24832280 DOI: 10.1063/1.4875021

Abstract

Decay dynamics of nascent dipole bound states of acetonitrile and nitromethane are examined using time-resolved photoelectron imaging of iodide-acetonitrile (I(-)·CH3CN) and iodide-nitromethane (I(-)·CH3NO2) complexes. Dipole-bound anions are created by UV-initiated electron transfer to the molecule of interest from the associated iodide ion at energies just below the vertical detachment energy of the halide-molecule complex. The acetonitrile anion is observed to decay biexponentially with time constants in the range of 4-900 ps. In contrast, the dipole bound state of nitromethane decays rapidly over 400 fs to form the valence bound anion. The nitromethane valence anion species then decays biexponentially with time constants of 2 ps and 1200 ps. The biexponential decay dynamics in acetonitrile are interpreted as iodine atom loss and autodetachment from the excited dipole-bound anion, followed by slower autodetachment of the relaxed metastable ion, while the dynamics of the nitromethane system suggest that a dipole-bound anion to valence anion transition proceeds via intramolecular vibrational energy redistribution to nitro group modes in the vicinity of the iodine atom.

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