Kinetic study for the unimolecular dissociation of CF3H: RRKM and PST calculations on an ab initio potential energy surface

Dong Nam Shin; Yong Sim Yoo; Chul Woong Park; Jae Won Hahn; Kihyung Song

doi:10.1016/0009-2614(96)00691-4

Kinetic study for the unimolecular dissociation of CF₃H: RRKM and PST calculations on an ab initio potential energy surface

Dong Nam Shin, Yong Sim Yoo, Chul Woong Park, Jae Won Hahn, Kihyung Song

Department of Mechanical Engineering

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

5 Citations (Scopus)

Abstract

Unimolecular dissociations of CF₃H into (1) CF₂(¹A₁) + HF, (2) CF₃ + H and (3) CF₂H + F were studied by means of RRKM and PST calculations on an ab initio potential energy surface. Activation energies for the three channels (1), (2) and (3) are 73.95, 108.20 and 130.02 kcal/mol at G2 level, respectively. RRKM and PST calculations show that the reaction rate for channel (1) is significantly faster than that for channel (2) at low energy. As the internal energy increases, channel (2) becomes important and, at energies greater than 7.0 eV, competes with channel (1). These results are consistent with recent experimental observations.

Original language	English
Pages (from-to)	613-619
Number of pages	7
Journal	Chemical Physics Letters
Volume	258
Issue number	5-6
DOIs	https://doi.org/10.1016/0009-2614(96)00691-4
Publication status	Published - 1996 Aug 23

Bibliographical note

Funding Information:
DNS gratefullya cknowledgetsh e financial support for the post-doctorafle llowshipfrom Korea Sciencea ndE ngineeringFo undationT.h is work was supportedb y the Ministry of Science and Technology.

All Science Journal Classification (ASJC) codes

Physics and Astronomy(all)
Physical and Theoretical Chemistry

Access to Document

10.1016/0009-2614(96)00691-4

Cite this

@article{593002ed7ac0413294a712ab0342d3a8,

title = "Kinetic study for the unimolecular dissociation of CF3H: RRKM and PST calculations on an ab initio potential energy surface",

abstract = "Unimolecular dissociations of CF3H into (1) CF2(1A1) + HF, (2) CF3 + H and (3) CF2H + F were studied by means of RRKM and PST calculations on an ab initio potential energy surface. Activation energies for the three channels (1), (2) and (3) are 73.95, 108.20 and 130.02 kcal/mol at G2 level, respectively. RRKM and PST calculations show that the reaction rate for channel (1) is significantly faster than that for channel (2) at low energy. As the internal energy increases, channel (2) becomes important and, at energies greater than 7.0 eV, competes with channel (1). These results are consistent with recent experimental observations.",

author = "Shin, {Dong Nam} and Yoo, {Yong Sim} and Park, {Chul Woong} and Hahn, {Jae Won} and Kihyung Song",

note = "Funding Information: DNS gratefullya cknowledgetsh e financial support for the post-doctorafle llowshipfrom Korea Sciencea ndE ngineeringFo undationT.h is work was supportedb y the Ministry of Science and Technology.",

year = "1996",

month = aug,

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doi = "10.1016/0009-2614(96)00691-4",

language = "English",

volume = "258",

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journal = "Chemical Physics Letters",

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T1 - Kinetic study for the unimolecular dissociation of CF3H

T2 - RRKM and PST calculations on an ab initio potential energy surface

AU - Shin, Dong Nam

AU - Yoo, Yong Sim

AU - Park, Chul Woong

AU - Hahn, Jae Won

AU - Song, Kihyung

N1 - Funding Information: DNS gratefullya cknowledgetsh e financial support for the post-doctorafle llowshipfrom Korea Sciencea ndE ngineeringFo undationT.h is work was supportedb y the Ministry of Science and Technology.

PY - 1996/8/23

Y1 - 1996/8/23

N2 - Unimolecular dissociations of CF3H into (1) CF2(1A1) + HF, (2) CF3 + H and (3) CF2H + F were studied by means of RRKM and PST calculations on an ab initio potential energy surface. Activation energies for the three channels (1), (2) and (3) are 73.95, 108.20 and 130.02 kcal/mol at G2 level, respectively. RRKM and PST calculations show that the reaction rate for channel (1) is significantly faster than that for channel (2) at low energy. As the internal energy increases, channel (2) becomes important and, at energies greater than 7.0 eV, competes with channel (1). These results are consistent with recent experimental observations.

AB - Unimolecular dissociations of CF3H into (1) CF2(1A1) + HF, (2) CF3 + H and (3) CF2H + F were studied by means of RRKM and PST calculations on an ab initio potential energy surface. Activation energies for the three channels (1), (2) and (3) are 73.95, 108.20 and 130.02 kcal/mol at G2 level, respectively. RRKM and PST calculations show that the reaction rate for channel (1) is significantly faster than that for channel (2) at low energy. As the internal energy increases, channel (2) becomes important and, at energies greater than 7.0 eV, competes with channel (1). These results are consistent with recent experimental observations.

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