On the kinetic mechanism of reactions of hydroxyl radical with CHF 2CH3 - N F n (n = 1-3)

Yue Meng Ji; Ze Sheng Li; Jing Yao Liu

doi:10.1007/s00214-007-0260-3

On the kinetic mechanism of reactions of hydroxyl radical with CHF ₂CH_{3 - N} F _n (n = 1-3)

Yue Meng Ji, Ze Sheng Li^*, Jing Yao Liu

^*Corresponding author for this work

Jilin University

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

6 Citations (Scopus)

Abstract

The potential energy surfaces of the reactions CHF₂CH _{3 - n} F _n (n = 1-3) + OH were investigated by MPWB1K and BMC-CCSD (single-point) methods. Furthermore, with the aid of canonical variational transition state theory including the small-curvature tunneling correction, the rate constants of the title reactions were calculated over a wide temperature range of 220-1,500 K. Agreement between the CVT/SCT rate constants and the experimental values is good. Our results show that the order of rate constants is CHF₂CH₂F + OH > CHF ₂CHF₂ + OH > CHF₂CF₃ + OH. For reaction CHF₂CH₂F + OH, the 1-H-abstraction channel dominates the reaction at the whole temperature, while 2-H-abstraction channel appears to be competitive with the increase of temperature.

Original language	English
Pages (from-to)	315-323
Number of pages	9
Journal	Theoretical Chemistry Accounts
Volume	118
Issue number	2
DOIs	https://doi.org/10.1007/s00214-007-0260-3
Publication status	Published - Aug 2007
Externally published	Yes

Access to Document

10.1007/s00214-007-0260-3

Cite this

Ji, Y. M., Li, Z. S., & Liu, J. Y. (2007). On the kinetic mechanism of reactions of hydroxyl radical with CHF ₂CH_{3 - N} F _n (n = 1-3). Theoretical Chemistry Accounts, 118(2), 315-323. https://doi.org/10.1007/s00214-007-0260-3

@article{6a6ebce924ca400d8f888f09b679c6ae,

title = "On the kinetic mechanism of reactions of hydroxyl radical with CHF 2CH3 - N F n (n = 1-3)",

abstract = "The potential energy surfaces of the reactions CHF2CH 3 - n F n (n = 1-3) + OH were investigated by MPWB1K and BMC-CCSD (single-point) methods. Furthermore, with the aid of canonical variational transition state theory including the small-curvature tunneling correction, the rate constants of the title reactions were calculated over a wide temperature range of 220-1,500 K. Agreement between the CVT/SCT rate constants and the experimental values is good. Our results show that the order of rate constants is CHF2CH2F + OH > CHF 2CHF2 + OH > CHF2CF3 + OH. For reaction CHF2CH2F + OH, the 1-H-abstraction channel dominates the reaction at the whole temperature, while 2-H-abstraction channel appears to be competitive with the increase of temperature.",

author = "Ji, {Yue Meng} and Li, {Ze Sheng} and Liu, {Jing Yao}",

year = "2007",

month = aug,

doi = "10.1007/s00214-007-0260-3",

language = "English",

volume = "118",

pages = "315--323",

journal = "Theoretical Chemistry Accounts",

issn = "1432-881X",

publisher = "Springer New York",

number = "2",

}

TY - JOUR

T1 - On the kinetic mechanism of reactions of hydroxyl radical with CHF 2CH3 - N F n (n = 1-3)

AU - Ji, Yue Meng

AU - Li, Ze Sheng

AU - Liu, Jing Yao

PY - 2007/8

Y1 - 2007/8

N2 - The potential energy surfaces of the reactions CHF2CH 3 - n F n (n = 1-3) + OH were investigated by MPWB1K and BMC-CCSD (single-point) methods. Furthermore, with the aid of canonical variational transition state theory including the small-curvature tunneling correction, the rate constants of the title reactions were calculated over a wide temperature range of 220-1,500 K. Agreement between the CVT/SCT rate constants and the experimental values is good. Our results show that the order of rate constants is CHF2CH2F + OH > CHF 2CHF2 + OH > CHF2CF3 + OH. For reaction CHF2CH2F + OH, the 1-H-abstraction channel dominates the reaction at the whole temperature, while 2-H-abstraction channel appears to be competitive with the increase of temperature.

AB - The potential energy surfaces of the reactions CHF2CH 3 - n F n (n = 1-3) + OH were investigated by MPWB1K and BMC-CCSD (single-point) methods. Furthermore, with the aid of canonical variational transition state theory including the small-curvature tunneling correction, the rate constants of the title reactions were calculated over a wide temperature range of 220-1,500 K. Agreement between the CVT/SCT rate constants and the experimental values is good. Our results show that the order of rate constants is CHF2CH2F + OH > CHF 2CHF2 + OH > CHF2CF3 + OH. For reaction CHF2CH2F + OH, the 1-H-abstraction channel dominates the reaction at the whole temperature, while 2-H-abstraction channel appears to be competitive with the increase of temperature.

UR - http://www.scopus.com/inward/record.url?scp=34547184395&partnerID=8YFLogxK

U2 - 10.1007/s00214-007-0260-3

DO - 10.1007/s00214-007-0260-3

M3 - Article

AN - SCOPUS:34547184395

SN - 1432-881X

VL - 118

SP - 315

EP - 323

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

IS - 2

ER -

On the kinetic mechanism of reactions of hydroxyl radical with CHF ₂CH_{3 - N} F _n (n = 1-3)

Abstract

Access to Document

Other files and links

Fingerprint

Cite this