Vibrational relaxation and infrared spectra of O sub 3 and OCS in cryogenic liquid solutions

Journal Article · Thu Sep 05 04:00:00 EDT 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100171a013· OSTI ID:5225895

Zittel, P F ^[1]

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1. Aerospace Corp., Los Angeles, CA (United States)

A laser-induced fluorescence method has been used to measure vibrational relaxation times for OCS and O{sub 3} in cryogenic liquid solutions. A CO{sub 2} laser was used to pump the 2{nu}{sub 2} vibrational level of OCS dilute in various solvents, and fluorescence was observed from the {nu}{sub 1} and {nu}{sub 2} vibrational levels of OCS by Ar(l) at 84.4 K. Probabilities are also given for Kr(l) at 116.8 K and for Xe(l) at 162.0 K. Relaxation of OCS by O{sub 2} was studied in mixtures of O{sub 2} in Ar(l), where the probabilities for relaxation of the {nu}{sub 1} and {nu}{sub 2} levels of OCS by O{sub 2} at 84.4 K were found to be 2.6{sup +1.1}{sub {minus}0.7} {times} 10{sup {minus}6} and (1.1 {+-} 0.2) {times} 10{sup {minus}6} respectively. Following CO{sub 2} laser excitation of the {nu}{sub 3} vibrational level of O{sub 3} dilute in the different solvents, fluorescence was observed from the {nu}{sub 2} level. A lower limit of {approximately}1 {times} 10{sup {minus}6} was determined for the relaxation probability per collision of the equilibrated {nu}{sub 1} and {nu}{sub 2} stretching levels of O{sub 3} by each of the four collision partners. The probabilities are given for relaxation of O{sub 3}({nu}{sub 2}) by Ar(l) at 84.4 K, Kr(l) at 116.8 K, Xe(l) at 162.0 K, and O{sub 2}(dilute in Ar(l)) at 84.4 K. A comparison is made between the relaxation rates measured in the liquid phase at cryogenic temperatures and rates measured in the gas phase at room temperature, using the isolated binary collision model and energy-transfer theory. Fourier transform spectra were recorded for OCS and O{sub 3} in Ar(l), Kr(l), and Xe(l) solutions at the aforementioned temperatures and in O{sub 2}(l) at 78.6 K. Band centers, half-widths, and strengths are given for eight vibrational bands of {sup 16}O{sup 12}C{sup 32}S and six bands of {sup 16}O{sub 3} in the spectral range of 500-3,500 cm{sup {minus}1}.

• OSTI ID: 5225895
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 95:18; ISSN 0022-3654; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ARGON
CARBON COMPOUNDS
CARBON OXYSULFIDE
COLLISIONS
CRYOGENIC FLUIDS
DATA
DIPOLE MOMENTS
EIGENVALUES
ELECTROMAGNETIC RADIATION
ELEMENTS
EMISSION SPECTROSCOPY
ENERGY LEVELS
EXCITED STATES
EXPERIMENTAL DATA
FLUIDS
FLUORESCENCE SPECTROSCOPY
FOURIER ANALYSIS
GASES
INFORMATION
INFRARED SPECTRA
KINETICS
KRYPTON
LASER RADIATION
MOLECULE COLLISIONS
MOLECULE-MOLECULE COLLISIONS
NONMETALS
NUMERICAL DATA
OZONE
RADIATIONS
RARE GASES
RELAXATION TIME
SPECTRA
SPECTROSCOPY
SULFUR COMPOUNDS
TEMPERATURE EFFECTS
TEMPERATURE RANGE
TEMPERATURE RANGE 0065-0273 K
VIBRATIONAL STATES
XENON