Collision-induced absorption spectra of binary mixtures of H2 with D2 and Ar and of pure HD

Thesis (Ph.D.)--Memorial University of Newfoundland, 1993. Physics Bibliography: leaves 123-126 In the present research project a systematic study of the collision-induced infrared absorption (CIA) spectra of the binary mixtures of H2 - D2 in the region of the double fundamental vibrations of H2 and...

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Bibliographic Details
Main Author: Hsieh, Chang-Tsang William, 1943-
Other Authors: Memorial University of Newfoundland. Dept. of Physics
Format: Thesis
Language:English
Published: 1992
Subjects:
Online Access:http://collections.mun.ca/cdm/ref/collection/theses3/id/28415
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Summary:Thesis (Ph.D.)--Memorial University of Newfoundland, 1993. Physics Bibliography: leaves 123-126 In the present research project a systematic study of the collision-induced infrared absorption (CIA) spectra of the binary mixtures of H2 - D2 in the region of the double fundamental vibrations of H2 and D2 and H2 - Ar in the fundamental band of H2, and of pure HD in its fundamental and first overtone regions was undertaken. The experiments were carried out with a 2.0 m high-pressure low-temperature transmission-type absorption cell at 77, 201 and 296 K at total gas densities up to 550 amagat. Infrared prism and grating spectrometers equipped with a microprocessor-controlled stepping motor were used to record the spectra. Alt the experimental results obtained represent first-time observations in collision-induced absorption. -- Collision-induced infrared absorption spectra of the double transitions of H2 (ν = 1―0) and D2 (ν = 1―0) have been observed at 77 and 201 K in the spectral region 7000-8000 cm-1 for total gas densities up to 550 amagat with a partial gas density ratio of 1:1 of H2 and D2. The observed spectra are interpreted in terms of the transitions, Q1(J) of H2 + Q1{J) of D2, Q1(J) of H2 + S1(J) of D2, S1(J) of H2- Q1(J) of D2, and S1(J) of H2 + S1(J) of D2 for J=0 and 1 for H2 and J=0, 1, and 2 for D2. Analysis of the experimental absorption profiles was carried out using appropriate lineshape functions. The absorption coefficients, lineshape parameters, etc., are obtained from the analysis. -- Collision-induced enhancement absorption spectra of the fundamental band of H2 in H2 - At mixtures were recorded at room temperature for a base density of 72 amagat of H2 for several partial densities of Ar up to 440 amagat. Hexadecapole-induced U transitions, U1(l), U1(2), Q1(0) + U0(1), and Q1(1) +r U0(1) have been identified in the spectral region 5400-6200 cm-1. A "cage" model has been proposed to account for the double transitions of H2 – H2 in the H2 - Ar enhancement spectra. From the analysis of the absorption profiles, the lineshape parameters and the absorption coefficients have been determined. -- The collision-induced absorption spectrum of the first overtone band of H D in the pure gas was observed at 77 K for gas densities up to 320 amagat. In addition to the allowed transitions P2(l), R2(0), and R2(1), the CIA transitions Q2(J) + Qn(J), Q1(J) + Q1(J)+ Q2(J) + S0(J), S2(J) + Q0(J), Qt(J) + S1(J), S2(J) + S0(J), and Si(J) + S1(J) have been observed. An analysis of the observed absorption profiles has been completed. It is found that the isotropic overlap induction mechanism does not contribute to the intensity of the band and that negative contribution to the intensity of the band comes from the mixed term (2√3λ32exp[-(R -α))Þ32| < < νJ |α | v’j’ >< vJ | Q | v’J’> (R/α0)-4. The fundamental band of HD has been investigated at 77 K for gas densities in the range 40-310 amagat. For the first time the collision-induced transitions of the type T1(1) + Qo(J), Q1(J)+T0(1), U1(0) + Q0(J), Q1(J) + U0(0), V1(0) + Q0(J), and Q1(J) +V0(0) for HD have been identified. Here T, U, and V transitions correspond to AJ-3, 4, and 5, respectively.