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Title: Signatures of a Conical Intersection in Adiabatic Dissociation on the Ground Electronic State

Abstract

Conical intersections are known to cause nonadiabatic transitions, but their effects on adiabatic dynamics are often ignored. Using the overtone-induced dissociation of the hydroxymethyl radical as an example, we demonstrate that ground-state O–H bond rupture is significantly affected by a conical intersection with an electronically excited state along the dissociation path, despite the much lower energy of the dissociating state than that of the conical intersection. In addition to lifetime differences, the geometric phase leads to a different H2CO rotational state distribution compared with that obtained using the standard single-state adiabatic model, which constitutes a signature of the conical intersection.

Authors:
 [1];  [2];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States
  2. Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States
  3. Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China, Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026, China
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1419595
Alternate Identifier(s):
OSTI ID: 1508610
Grant/Contract Number:  
SC0015997
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 140 Journal Issue: 6; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Xie, Changjian, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, and Guo, Hua. Signatures of a Conical Intersection in Adiabatic Dissociation on the Ground Electronic State. United States: N. p., 2018. Web. doi:10.1021/jacs.7b11489.
Xie, Changjian, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, & Guo, Hua. Signatures of a Conical Intersection in Adiabatic Dissociation on the Ground Electronic State. United States. doi:10.1021/jacs.7b11489.
Xie, Changjian, Malbon, Christopher L., Yarkony, David R., Xie, Daiqian, and Guo, Hua. Mon . "Signatures of a Conical Intersection in Adiabatic Dissociation on the Ground Electronic State". United States. doi:10.1021/jacs.7b11489.
@article{osti_1419595,
title = {Signatures of a Conical Intersection in Adiabatic Dissociation on the Ground Electronic State},
author = {Xie, Changjian and Malbon, Christopher L. and Yarkony, David R. and Xie, Daiqian and Guo, Hua},
abstractNote = {Conical intersections are known to cause nonadiabatic transitions, but their effects on adiabatic dynamics are often ignored. Using the overtone-induced dissociation of the hydroxymethyl radical as an example, we demonstrate that ground-state O–H bond rupture is significantly affected by a conical intersection with an electronically excited state along the dissociation path, despite the much lower energy of the dissociating state than that of the conical intersection. In addition to lifetime differences, the geometric phase leads to a different H2CO rotational state distribution compared with that obtained using the standard single-state adiabatic model, which constitutes a signature of the conical intersection.},
doi = {10.1021/jacs.7b11489},
journal = {Journal of the American Chemical Society},
number = 6,
volume = 140,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/jacs.7b11489

Citation Metrics:
Cited by: 13 works
Citation information provided by
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Figures / Tables:

Figure 1 Figure 1: Adiabatic potential energy surfaces (PESs) of the two lowest electronic states of CH2OH as a function of the R and ϕ coordinates with r = 1.436 Å, θ = 136.9°. The coordinates used in the four-dimensional (4D) model are shown in inset and defined below.

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Works referencing / citing this record:

Exploring Norrish type I and type II reactions: an ab initio mechanistic study highlighting singlet-state mediated chemistry
journal, January 2019

  • Marchetti, Barbara; Karsili, Tolga N. V.; Ashfold, Michael N. R.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 26
  • DOI: 10.1039/c8cp07292b

When the exact factorization meets conical intersections...
journal, July 2018


Exploring Norrish type I and type II reactions: an ab initio mechanistic study highlighting singlet-state mediated chemistry
journal, January 2019

  • Marchetti, Barbara; Karsili, Tolga N. V.; Ashfold, Michael N. R.
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 26
  • DOI: 10.1039/c8cp07292b

When the exact factorization meets conical intersections...
journal, July 2018


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.