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Title: Direct Observation of the Transition-State Region in the Photodissociation of CH 3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy

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 CH 3I 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( 2P 3/2) and I*( 2P 1/2). The short-lived features are assigned to repulsive valence-excited transition-state regions of 3Q 0 and 1Q 1, 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.

Authors:
 [1];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1229692
Alternate Identifier(s):
OSTI ID: 1532172
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 6; Journal Issue: 24; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Attar, Andrew R., Bhattacherjee, Aditi, and Leone, Stephen R. Direct Observation of the Transition-State Region in the Photodissociation of CH3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy. United States: N. p., 2015. Web. doi:10.1021/acs.jpclett.5b02489.
Attar, Andrew R., Bhattacherjee, Aditi, & Leone, Stephen R. Direct Observation of the Transition-State Region in the Photodissociation of CH3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy. United States. doi:10.1021/acs.jpclett.5b02489.
Attar, Andrew R., Bhattacherjee, Aditi, and Leone, Stephen R. Fri . "Direct Observation of the Transition-State Region in the Photodissociation of CH3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy". United States. doi:10.1021/acs.jpclett.5b02489.
@article{osti_1229692,
title = {Direct Observation of the Transition-State Region in the Photodissociation of CH3I by Femtosecond Extreme Ultraviolet Transient Absorption Spectroscopy},
author = {Attar, Andrew R. and Bhattacherjee, Aditi and Leone, Stephen R.},
abstractNote = {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(2P3/2) and I*(2P1/2). The short-lived features are assigned to repulsive valence-excited transition-state regions of 3Q0 and 1Q1, 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.},
doi = {10.1021/acs.jpclett.5b02489},
journal = {Journal of Physical Chemistry Letters},
number = 24,
volume = 6,
place = {United States},
year = {2015},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acs.jpclett.5b02489

Citation Metrics:
Cited by: 13 works
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