Direct Observation of the Transition-State Region in the Photodissociation of CH3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy

Andrew R Attar; Aditi Bhattacherjee; Stephen R Leone

doi:10.1021/acs.jpclett.5b02489

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Direct Observation of the Transition-State Region in the Photodissociation of CH3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy

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Direct Observation of the Transition-State Region in the Photodissociation of CH3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy

Andrew R Attar, Aditi Bhattacherjee and Stephen R Leone

The journal of physical chemistry letters, Vol.6(24), pp.5072-5077

12/17/2015

DOI: 10.1021/acs.jpclett.5b02489

PMID: 26636176

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Abstract

Femtosecond extreme ultraviolet (XUV) pulses produced by high harmonic generation are used to probe the transition-state region in the 266 nm photodissociation of CH3I by the real-time evolution of core-to-valence transitions near the iodine N-edge at 45-60 eV. During C-I bond breaking, new core-to-valence electronic states appear in the spectra, which decay concomitantly with the rise of the atomic iodine resonances of I((2)P3/2) and I*((2)P1/2). The short-lived features are assigned to repulsive valence-excited transition-state regions of (3)Q0 and (1)Q1, which can connect to transient core-excited states via promotion of 4d(I) core electrons. A simplified one-electron transition picture is described that accurately predicts the relative energies of the transient states observed. The transition-state resonances reach a maximum at ∼40 fs and decay to complete C-I dissociation in ∼90 fs, representing the shortest-lived chemical transition state observed by core-level, XUV, or X-ray spectroscopy.

XUV absorption spectroscopy

transition state

photodissociation

Details

Title: Subtitle: Direct Observation of the Transition-State Region in the Photodissociation of CH3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy
Creators: Andrew R Attar - Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States
Aditi Bhattacherjee - Chemical Sciences Division, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States
Stephen R Leone - Department of Physics, University of California , Berkeley, California 94720, United States
Resource Type: Journal article
Publication Details: The journal of physical chemistry letters, Vol.6(24), pp.5072-5077
DOI: 10.1021/acs.jpclett.5b02489
PMID: 26636176
NLM abbreviation: J Phys Chem Lett
ISSN: 1948-7185
eISSN: 1948-7185
Grant note: DOI: 10.13039/100006151, name: Basic Energy Sciences, award: DE-AC02-05CH11231; DOI: 10.13039/100006235, name: Lawrence Berkely National Laboratory
Language: English
Date published: 12/17/2015
Academic Unit: Chemistry
Record Identifier: 9984216566502771

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