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Title: From ab Initio Potential Energy Surfaces to State-Resolved Reactivities: X + H 2O ↔ HX + OH [X = F, Cl, and O( 3P)] Reactions

Abstract

Here, we survey the recent advances in theoretical understanding of quantum state resolved dynamics, using the title reactions as examples. It is shown that the progress was made possible by major developments in two areas. First, an accurate analytical representation of many high-level ab initio points over a large configuration space can now be made with high fidelity and the necessary permutation symmetry. The resulting full-dimensional global potential energy surfaces enable dynamical calculations using either quasi-classical trajectory or more importantly quantum mechanical methods. The second advance is the development of accurate and efficient quantum dynamical methods, which are necessary for providing a reliable treatment of quantum effects in reaction dynamics such as tunneling, resonances, and zero-point energy. The powerful combination of the two advances has allowed us to achieve a quantitatively accurate characterization of the reaction dynamics, which unveiled rich dynamical features such as steric steering, strong mode specificity, and bond selectivity. The dependence of reactivity on reactant modes can be rationalized by the recently proposed sudden vector projection model, which attributes the mode specificity and bond selectivity to the coupling of reactant modes with the reaction coordinate at the relevant transition state. The deeper insights provided by these theoreticalmore » studies have advanced our understanding of reaction dynamics to a new level.« less

Authors:
 [1];  [2];  [2];  [3];  [2];  [4];  [2]
  1. Univ. of New Mexico, Albuquerque, NM (United States); Chongqing Univ., Chongqing (China)
  2. Univ. of New Mexico, Albuquerque, NM (United States)
  3. Sichuan Univ., Sichuan (China)
  4. Missouri Univ. of Science and Technology, Rolla, MO (United States)
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1179584
Alternate Identifier(s):
OSTI ID: 1454435
Grant/Contract Number:
SC0010616; FG02-05ER15694
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 119; Journal Issue: 20; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Jun, Jiang, Bin, Song, Hongwei, Ma, Jianyi, Zhao, Bin, Dawes, Richard, and Guo, Hua. From ab Initio Potential Energy Surfaces to State-Resolved Reactivities: X + H2O ↔ HX + OH [X = F, Cl, and O(3P)] Reactions. United States: N. p., 2015. Web. doi:10.1021/acs.jpca.5b02510.
Li, Jun, Jiang, Bin, Song, Hongwei, Ma, Jianyi, Zhao, Bin, Dawes, Richard, & Guo, Hua. From ab Initio Potential Energy Surfaces to State-Resolved Reactivities: X + H2O ↔ HX + OH [X = F, Cl, and O(3P)] Reactions. United States. doi:10.1021/acs.jpca.5b02510.
Li, Jun, Jiang, Bin, Song, Hongwei, Ma, Jianyi, Zhao, Bin, Dawes, Richard, and Guo, Hua. Fri . "From ab Initio Potential Energy Surfaces to State-Resolved Reactivities: X + H2O ↔ HX + OH [X = F, Cl, and O(3P)] Reactions". United States. doi:10.1021/acs.jpca.5b02510.
@article{osti_1179584,
title = {From ab Initio Potential Energy Surfaces to State-Resolved Reactivities: X + H2O ↔ HX + OH [X = F, Cl, and O(3P)] Reactions},
author = {Li, Jun and Jiang, Bin and Song, Hongwei and Ma, Jianyi and Zhao, Bin and Dawes, Richard and Guo, Hua},
abstractNote = {Here, we survey the recent advances in theoretical understanding of quantum state resolved dynamics, using the title reactions as examples. It is shown that the progress was made possible by major developments in two areas. First, an accurate analytical representation of many high-level ab initio points over a large configuration space can now be made with high fidelity and the necessary permutation symmetry. The resulting full-dimensional global potential energy surfaces enable dynamical calculations using either quasi-classical trajectory or more importantly quantum mechanical methods. The second advance is the development of accurate and efficient quantum dynamical methods, which are necessary for providing a reliable treatment of quantum effects in reaction dynamics such as tunneling, resonances, and zero-point energy. The powerful combination of the two advances has allowed us to achieve a quantitatively accurate characterization of the reaction dynamics, which unveiled rich dynamical features such as steric steering, strong mode specificity, and bond selectivity. The dependence of reactivity on reactant modes can be rationalized by the recently proposed sudden vector projection model, which attributes the mode specificity and bond selectivity to the coupling of reactant modes with the reaction coordinate at the relevant transition state. The deeper insights provided by these theoretical studies have advanced our understanding of reaction dynamics to a new level.},
doi = {10.1021/acs.jpca.5b02510},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 20,
volume = 119,
place = {United States},
year = {Fri Apr 17 00:00:00 EDT 2015},
month = {Fri Apr 17 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acs.jpca.5b02510

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Cited by: 44 works
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