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Title: Barrierless association of CF 2 and dissociation of C 2F 4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

Abstract

Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C 2F 4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. In conclusion, our computed dissociation rate constants agree well with the recent experimental measurements.

Authors:
 [1];  [1]; ORCiD logo [2]
  1. Beijing Univ. of Chemical Technology, Beijing (People's Republic of China); Univ. of Minnesota, Minneapolis, MN (United States)
  2. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States); Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1465484
Grant/Contract Number:  
FG02-86ER13579; SC0015997
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 113; Journal Issue: 48; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bond dissociation; barrierless reaction; variable-reaction-coordinate variational transition-state theory; falloff; system-specific quantum RRK theory

Citation Formats

Bao, Junwei Lucas, Zhang, Xin, and Truhlar, Donald G. Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory. United States: N. p., 2016. Web. doi:10.1073/pnas.1616208113.
Bao, Junwei Lucas, Zhang, Xin, & Truhlar, Donald G. Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory. United States. doi:10.1073/pnas.1616208113.
Bao, Junwei Lucas, Zhang, Xin, and Truhlar, Donald G. Thu . "Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory". United States. doi:10.1073/pnas.1616208113. https://www.osti.gov/servlets/purl/1465484.
@article{osti_1465484,
title = {Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory},
author = {Bao, Junwei Lucas and Zhang, Xin and Truhlar, Donald G.},
abstractNote = {Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. In conclusion, our computed dissociation rate constants agree well with the recent experimental measurements.},
doi = {10.1073/pnas.1616208113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 48,
volume = 113,
place = {United States},
year = {Thu Nov 10 00:00:00 EST 2016},
month = {Thu Nov 10 00:00:00 EST 2016}
}

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Cited by: 3 works
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Works referenced in this record:

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006

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