Diode laser measurements of CD{sub 3} quantum yields and internal energy for the dissociation of dimethyl sulfoxide-d{sub 6}

Journal Article · Wed Jan 01 04:00:00 EST 1997 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.473232· OSTI ID:435132

Rudolph, R N; North, S W; Hall, G E; Sears, T J ^[1]

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1. Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000 (United States)

Infrared diode laser absorption spectroscopy has been used to measure the CD{sub 3} radical photoproducts formed in the 193 and 222 nm photodissociation of dimethyl sulfoxide-d{sub 6}. Quantum yields of CD{sub 3} have been determined to be 1.4{plus_minus}0.1 at 193 nm and 1.2{plus_minus}0.2 at 222 nm, compared to 2.0 for acetone-d{sub 6} at 193 nm. An analysis of transient waveforms reflecting the vibrational relaxation and radical recombination kinetics also yields an estimate of the nascent CD{sub 3} vibrational energy content by determining the fraction of total CD{sub 3} initially produced in the vibrationless state. The nascent CD{sub 3} population in the vibrational ground state decreases in order for the following photodissociation systems: CD{sub 3}I at 248 nm, DMSO-d{sub 6} at 193 and 222 nm and acetone-d{sub 6} at 193 nm. The DMSO results are in good agreement with recent photofragment translational spectroscopy results and support a stepwise mechanism for the dissociation of DMSO at both wavelengths. {copyright} {ital 1997 American Institute of Physics.}

• Research Organization: Brookhaven National Laboratory
• DOE Contract Number: AC02-76CH00016
• OSTI ID: 435132
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 106; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
66 PHYSICS
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
ACETONE
CARBON COMPOUNDS
CHEMICAL BONDS
CHEMICAL REACTION YIELD
DEUTERIUM COMPOUNDS
DISSOCIATION
DMSO
INFRARED SPECTRA
LASERS
PHOTON-MOLECULE COLLISIONS
RADICALS
REACTION KINETICS
VIBRATIONAL STATES