Time-resolved detection of reaction products in the infrared laser chemistry of sulfoxides:C2H4SO, (CH3)2SO, (CD3)2SO

Heike Gross; Yabai He; Martin Quack; Alex Schmid; Georg Seyfang

doi:10.1016/0009-2614(93)85429-R

Time-resolved detection of reaction products in the infrared laser chemistry of sulfoxides:C2H4SO, (CH3)2SO, (CD3)2SO

Heike Gross^*, Yabai He, Martin Quack, Alex Schmid, Georg Seyfang

^*Corresponding author for this work

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

15 Citations (Scopus)

Abstract

The first observations of the infrared laser chemical reaction of organic sulfoxides after IR multiphoton excitation of the SO infrared chromophore (with large band strength G=2.0 pm² in (CH₃)₂SO) with pulsed CO₂ laser radiation are reported. The collisionless IR photochemical primary products are shown to be C₂H₄ and SO (³Σ^-) for C₂ H₄SO, and CH₃ and (³Σ^-) SO (via CH₃SO) for (CH₃)₂SO by means of time-resolved laser spectroscopic observation of C₂H₄, SO, and CD₃. Effective laser chemical rate constants k_I(st)=1.2 cm² J^-1 for C₂H₄SO (9R32) and 0.06 cm² J^-1 for (CH₃)₂SO (9R32) are obtained from static yield measurements as well as unimolecular decay constants k≈10⁷ to 10⁸ s^-1 (for C₂H₄SO) after excitation above threshold and laser probing of C₂H₄ and SO. A nonlinear intensity dependence of k(st) is reported for C₂H₄SO and nanosecond intramolecular relaxation for (CH₃)₂SO.

Original language	English
Pages (from-to)	122-130
Number of pages	9
Journal	Chemical Physics Letters
Volume	213
Issue number	1-2
DOIs	https://doi.org/10.1016/0009-2614(93)85429-R
Publication status	Published - 1 Oct 1993
Externally published	Yes

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title = "Time-resolved detection of reaction products in the infrared laser chemistry of sulfoxides:C2H4SO, (CH3)2SO, (CD3)2SO",

abstract = "The first observations of the infrared laser chemical reaction of organic sulfoxides after IR multiphoton excitation of the SO infrared chromophore (with large band strength G=2.0 pm2 in (CH3)2SO) with pulsed CO2 laser radiation are reported. The collisionless IR photochemical primary products are shown to be C2H4 and SO (3Σ-) for C2 H4SO, and CH3 and (3Σ-) SO (via CH3SO) for (CH3)2SO by means of time-resolved laser spectroscopic observation of C2H4, SO, and CD3. Effective laser chemical rate constants kI(st)=1.2 cm2 J-1 for C2H4SO (9R32) and 0.06 cm2 J-1 for (CH3)2SO (9R32) are obtained from static yield measurements as well as unimolecular decay constants k≈107 to 108 s-1 (for C2H4SO) after excitation above threshold and laser probing of C2H4 and SO. A nonlinear intensity dependence of k(st) is reported for C2H4SO and nanosecond intramolecular relaxation for (CH3)2SO.",

author = "Heike Gross and Yabai He and Martin Quack and Alex Schmid and Georg Seyfang",

year = "1993",

month = oct,

day = "1",

doi = "10.1016/0009-2614(93)85429-R",

language = "English",

volume = "213",

pages = "122--130",

journal = "Chemical Physics Letters",

issn = "0009-2614",

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number = "1-2",

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T1 - Time-resolved detection of reaction products in the infrared laser chemistry of sulfoxides:C2H4SO, (CH3)2SO, (CD3)2SO

AU - Gross, Heike

AU - He, Yabai

AU - Quack, Martin

AU - Schmid, Alex

AU - Seyfang, Georg

PY - 1993/10/1

Y1 - 1993/10/1

N2 - The first observations of the infrared laser chemical reaction of organic sulfoxides after IR multiphoton excitation of the SO infrared chromophore (with large band strength G=2.0 pm2 in (CH3)2SO) with pulsed CO2 laser radiation are reported. The collisionless IR photochemical primary products are shown to be C2H4 and SO (3Σ-) for C2 H4SO, and CH3 and (3Σ-) SO (via CH3SO) for (CH3)2SO by means of time-resolved laser spectroscopic observation of C2H4, SO, and CD3. Effective laser chemical rate constants kI(st)=1.2 cm2 J-1 for C2H4SO (9R32) and 0.06 cm2 J-1 for (CH3)2SO (9R32) are obtained from static yield measurements as well as unimolecular decay constants k≈107 to 108 s-1 (for C2H4SO) after excitation above threshold and laser probing of C2H4 and SO. A nonlinear intensity dependence of k(st) is reported for C2H4SO and nanosecond intramolecular relaxation for (CH3)2SO.

AB - The first observations of the infrared laser chemical reaction of organic sulfoxides after IR multiphoton excitation of the SO infrared chromophore (with large band strength G=2.0 pm2 in (CH3)2SO) with pulsed CO2 laser radiation are reported. The collisionless IR photochemical primary products are shown to be C2H4 and SO (3Σ-) for C2 H4SO, and CH3 and (3Σ-) SO (via CH3SO) for (CH3)2SO by means of time-resolved laser spectroscopic observation of C2H4, SO, and CD3. Effective laser chemical rate constants kI(st)=1.2 cm2 J-1 for C2H4SO (9R32) and 0.06 cm2 J-1 for (CH3)2SO (9R32) are obtained from static yield measurements as well as unimolecular decay constants k≈107 to 108 s-1 (for C2H4SO) after excitation above threshold and laser probing of C2H4 and SO. A nonlinear intensity dependence of k(st) is reported for C2H4SO and nanosecond intramolecular relaxation for (CH3)2SO.

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DO - 10.1016/0009-2614(93)85429-R

M3 - Article

AN - SCOPUS:0000837240

SN - 0009-2614

VL - 213

SP - 122

EP - 130

JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-2

ER -

Time-resolved detection of reaction products in the infrared laser chemistry of sulfoxides:C2H4SO, (CH3)2SO, (CD3)2SO

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