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Title: Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol

Abstract

The fate of a photoexcited molecule is often strongly influencedby electronic degeneracies, such as conical intersections, which break the Born-Oppenheimer separation of electronic and nuclear motion. Detailed information concerning internal energy redistribution in a nonadiabatic process can beextracted from the product state distribution of a photofragment in photo-dissociation. Here, we focus on the nonadiabatic photodissociation of phenol and discuss the internal excitation of the phenoxyl fragment using both symmetry analysis and wave packet dynamics. It is shown that unique and general selection rules exist, which can be attributed to the geometric phase in the adiabatic representation. Further, our results provide a reinterpretation of the experimental data, shedding light on the importance of conical intersections on the product state distribution.

Authors:
 [1]; ORCiD logo [2];  [3]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [2]
  1. Univ. of New Mexico, Albuquerque, NM (United States); Northwest Univ., Shaanxi (China)
  2. Univ. of New Mexico, Albuquerque, NM (United States)
  3. Johns Hopkins Univ., Baltimore, MD (United States)
  4. Nanjing Univ. (China)
Publication Date:
Research Org.:
Johns Hopkins Univ., Baltimore, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1596358
Grant/Contract Number:  
SC0015997
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 11; Journal Issue: 1; 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

Xie, Changjian, Zhao, Bin, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, and Guo, Hua. Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.jpclett.9b03407.
Xie, Changjian, Zhao, Bin, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, & Guo, Hua. Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol. United States. https://doi.org/10.1021/acs.jpclett.9b03407
Xie, Changjian, Zhao, Bin, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, and Guo, Hua. Tue . "Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol". United States. https://doi.org/10.1021/acs.jpclett.9b03407. https://www.osti.gov/servlets/purl/1596358.
@article{osti_1596358,
title = {Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol},
author = {Xie, Changjian and Zhao, Bin and Malbon, Christopher L. and Yarkony, David R. and Xie, Daiqian and Guo, Hua},
abstractNote = {The fate of a photoexcited molecule is often strongly influencedby electronic degeneracies, such as conical intersections, which break the Born-Oppenheimer separation of electronic and nuclear motion. Detailed information concerning internal energy redistribution in a nonadiabatic process can beextracted from the product state distribution of a photofragment in photo-dissociation. Here, we focus on the nonadiabatic photodissociation of phenol and discuss the internal excitation of the phenoxyl fragment using both symmetry analysis and wave packet dynamics. It is shown that unique and general selection rules exist, which can be attributed to the geometric phase in the adiabatic representation. Further, our results provide a reinterpretation of the experimental data, shedding light on the importance of conical intersections on the product state distribution.},
doi = {10.1021/acs.jpclett.9b03407},
journal = {Journal of Physical Chemistry Letters},
number = 1,
volume = 11,
place = {United States},
year = {2019},
month = {12}
}

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