Theoretical study and rate constants calculation for the reactions X + CF 3CH 2OCF 3 (X = F, Cl, Br)

Hui Zhang; Yang Liu; Jing Yao Liu; Ze Sheng Li

doi:10.1002/jcc.22897

Theoretical study and rate constants calculation for the reactions X + CF ₃CH ₂OCF ₃ (X = F, Cl, Br)

Hui Zhang^*
, Yang Liu
, Jing Yao Liu
, Ze Sheng Li

^*Corresponding author for this work

School of Chemistry and Chemical Engineering

Harbin University of Science and Technology
Jilin University
Harbin Institute of Technology

Research output: Contribution to journal › Article › peer-review

5 Citations (Scopus)

Abstract

The multiple-channel reactions X + CF ₃CH ₂OCF ₃ (X = F, Cl, Br) are theoretically investigated. The minimum energy paths (MEP) are calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for major reaction channels are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200-2000 K. The theoretical three-parameter expressions for the three channels k _1a(T) = 1.24 × 10 ^-15T ^1.24exp(-304.81/T), k _2a(T) = 7.27 × 10 ^-15T ^0.37exp(-630.69/T), and k _3a(T) = 2.84 × 10 ^-19T ^2.51 exp(-2725.17/T) cm ³ molecule ^-1 s ^-1 are given. Our calculations indicate that hydrogen abstraction channel is only feasible channel due to the smaller barrier height among five channels considered.

Original language	English
Pages (from-to)	685-690
Number of pages	6
Journal	Journal of Computational Chemistry
Volume	33
Issue number	6
DOIs	https://doi.org/10.1002/jcc.22897
Publication status	Published - 5 Mar 2012

Keywords

gas-phase reaction
rate constants
transition state

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10.1002/jcc.22897

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@article{fc1bb0b290f9453a8e75ca95d922707d,

title = "Theoretical study and rate constants calculation for the reactions X + CF 3CH 2OCF 3 (X = F, Cl, Br)",

abstract = "The multiple-channel reactions X + CF 3CH 2OCF 3 (X = F, Cl, Br) are theoretically investigated. The minimum energy paths (MEP) are calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for major reaction channels are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200-2000 K. The theoretical three-parameter expressions for the three channels k 1a(T) = 1.24 × 10 -15T 1.24exp(-304.81/T), k 2a(T) = 7.27 × 10 -15T 0.37exp(-630.69/T), and k 3a(T) = 2.84 × 10 -19T 2.51 exp(-2725.17/T) cm 3 molecule -1 s -1 are given. Our calculations indicate that hydrogen abstraction channel is only feasible channel due to the smaller barrier height among five channels considered.",

keywords = "gas-phase reaction, rate constants, transition state",

author = "Hui Zhang and Yang Liu and Liu, \{Jing Yao\} and Li, \{Ze Sheng\}",

year = "2012",

month = mar,

day = "5",

doi = "10.1002/jcc.22897",

language = "English",

volume = "33",

pages = "685--690",

journal = "Journal of Computational Chemistry",

issn = "0192-8651",

publisher = "John Wiley \& Sons Inc.",

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TY - JOUR

T1 - Theoretical study and rate constants calculation for the reactions X + CF 3CH 2OCF 3 (X = F, Cl, Br)

AU - Zhang, Hui

AU - Liu, Yang

AU - Liu, Jing Yao

AU - Li, Ze Sheng

PY - 2012/3/5

Y1 - 2012/3/5

N2 - The multiple-channel reactions X + CF 3CH 2OCF 3 (X = F, Cl, Br) are theoretically investigated. The minimum energy paths (MEP) are calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for major reaction channels are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200-2000 K. The theoretical three-parameter expressions for the three channels k 1a(T) = 1.24 × 10 -15T 1.24exp(-304.81/T), k 2a(T) = 7.27 × 10 -15T 0.37exp(-630.69/T), and k 3a(T) = 2.84 × 10 -19T 2.51 exp(-2725.17/T) cm 3 molecule -1 s -1 are given. Our calculations indicate that hydrogen abstraction channel is only feasible channel due to the smaller barrier height among five channels considered.

AB - The multiple-channel reactions X + CF 3CH 2OCF 3 (X = F, Cl, Br) are theoretically investigated. The minimum energy paths (MEP) are calculated at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for major reaction channels are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 200-2000 K. The theoretical three-parameter expressions for the three channels k 1a(T) = 1.24 × 10 -15T 1.24exp(-304.81/T), k 2a(T) = 7.27 × 10 -15T 0.37exp(-630.69/T), and k 3a(T) = 2.84 × 10 -19T 2.51 exp(-2725.17/T) cm 3 molecule -1 s -1 are given. Our calculations indicate that hydrogen abstraction channel is only feasible channel due to the smaller barrier height among five channels considered.

KW - gas-phase reaction

KW - rate constants

KW - transition state

UR - https://www.scopus.com/pages/publications/84856704444

U2 - 10.1002/jcc.22897

DO - 10.1002/jcc.22897

M3 - Article

AN - SCOPUS:84856704444

SN - 0192-8651

VL - 33

SP - 685

EP - 690

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

IS - 6

ER -

Theoretical study and rate constants calculation for the reactions X + CF ₃CH ₂OCF ₃ (X = F, Cl, Br)

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