Alteration of Cl spin-orbit branching ratios via photodissociation of pre-excited fundamental CH3 stretch of CH3CFCl2

A. Melchior; X. Chen; I. Bar; S. Rosenwaks

doi:10.1016/S0009-2614(99)01232-4

Alteration of Cl spin-orbit branching ratios via photodissociation of pre-excited fundamental CH₃ stretch of CH₃CFCl₂

A. Melchior, X. Chen, I. Bar, S. Rosenwaks

Department of Physics

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

19 Scopus citations

Abstract

The fundamental symmetric CH₃ stretch (ν₂) in the ground electronic state of CH₃CFCl₂ is efficiently prepared by stimulated Raman excitation. The excited molecules are photodissociated by ~235 nm photons that further tag Cl(²P_3/2) and Cl(²P_1/2) [Cl^*] photofragments via (2+1) resonantly enhanced multiphoton ionization. The yield of both photofragments increases as a result of pre-excitation, indicative of energy flow from the excited C-H to the C-Cl bond and hence a better Franck-Condon overlap between the components of the wavefunction along the C-Cl coordinate. The Cl^*/Cl branching ratio is 0.60±0.09 in ~235 nm photolysis of vibrationally excited molecules and 0.40±0.07 in that of vibrationless ground state CH₃CFCl₂.

Original language	English
Pages (from-to)	421-427
Number of pages	7
Journal	Chemical Physics Letters
Volume	315
Issue number	5-6
DOIs	https://doi.org/10.1016/S0009-2614(99)01232-4
State	Published - 31 Dec 1999

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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@article{511390e0f0234251a2a8e00c41c4d2be,

title = "Alteration of Cl spin-orbit branching ratios via photodissociation of pre-excited fundamental CH3 stretch of CH3CFCl2",

abstract = "The fundamental symmetric CH3 stretch (ν2) in the ground electronic state of CH3CFCl2 is efficiently prepared by stimulated Raman excitation. The excited molecules are photodissociated by ~235 nm photons that further tag Cl(2P3/2) and Cl(2P1/2) [Cl*] photofragments via (2+1) resonantly enhanced multiphoton ionization. The yield of both photofragments increases as a result of pre-excitation, indicative of energy flow from the excited C-H to the C-Cl bond and hence a better Franck-Condon overlap between the components of the wavefunction along the C-Cl coordinate. The Cl*/Cl branching ratio is 0.60±0.09 in ~235 nm photolysis of vibrationally excited molecules and 0.40±0.07 in that of vibrationless ground state CH3CFCl2.",

author = "A. Melchior and X. Chen and I. Bar and S. Rosenwaks",

note = "Funding Information: We are grateful to Prof. P.J. Dagdigian for useful discussions and for a critical reading of the manuscript. This research was supported by the United States–Israel Binational Foundation (BSF) under grant No. 96-00140, by the James Franck Binational German–Israeli Program in Laser-Matter Interaction and by the German–Israeli Foundation (GIF) under grant No. I 0537-098.05/97. A.M. thanks the Israeli Ministry of Science for a Levy Eshkol scholarship.",

year = "1999",

month = dec,

day = "31",

doi = "10.1016/S0009-2614(99)01232-4",

language = "English",

volume = "315",

pages = "421--427",

journal = "Chemical Physics Letters",

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T1 - Alteration of Cl spin-orbit branching ratios via photodissociation of pre-excited fundamental CH3 stretch of CH3CFCl2

AU - Melchior, A.

AU - Chen, X.

AU - Bar, I.

AU - Rosenwaks, S.

N1 - Funding Information: We are grateful to Prof. P.J. Dagdigian for useful discussions and for a critical reading of the manuscript. This research was supported by the United States–Israel Binational Foundation (BSF) under grant No. 96-00140, by the James Franck Binational German–Israeli Program in Laser-Matter Interaction and by the German–Israeli Foundation (GIF) under grant No. I 0537-098.05/97. A.M. thanks the Israeli Ministry of Science for a Levy Eshkol scholarship.

PY - 1999/12/31

Y1 - 1999/12/31

N2 - The fundamental symmetric CH3 stretch (ν2) in the ground electronic state of CH3CFCl2 is efficiently prepared by stimulated Raman excitation. The excited molecules are photodissociated by ~235 nm photons that further tag Cl(2P3/2) and Cl(2P1/2) [Cl*] photofragments via (2+1) resonantly enhanced multiphoton ionization. The yield of both photofragments increases as a result of pre-excitation, indicative of energy flow from the excited C-H to the C-Cl bond and hence a better Franck-Condon overlap between the components of the wavefunction along the C-Cl coordinate. The Cl*/Cl branching ratio is 0.60±0.09 in ~235 nm photolysis of vibrationally excited molecules and 0.40±0.07 in that of vibrationless ground state CH3CFCl2.

AB - The fundamental symmetric CH3 stretch (ν2) in the ground electronic state of CH3CFCl2 is efficiently prepared by stimulated Raman excitation. The excited molecules are photodissociated by ~235 nm photons that further tag Cl(2P3/2) and Cl(2P1/2) [Cl*] photofragments via (2+1) resonantly enhanced multiphoton ionization. The yield of both photofragments increases as a result of pre-excitation, indicative of energy flow from the excited C-H to the C-Cl bond and hence a better Franck-Condon overlap between the components of the wavefunction along the C-Cl coordinate. The Cl*/Cl branching ratio is 0.60±0.09 in ~235 nm photolysis of vibrationally excited molecules and 0.40±0.07 in that of vibrationless ground state CH3CFCl2.

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DO - 10.1016/S0009-2614(99)01232-4

M3 - Article

AN - SCOPUS:0001287798

SN - 0009-2614

VL - 315

SP - 421

EP - 427

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 5-6

ER -

Alteration of Cl spin-orbit branching ratios via photodissociation of pre-excited fundamental CH₃ stretch of CH₃CFCl₂

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