1974 ◽  
Vol 52 (12) ◽  
pp. 1082-1089 ◽  
Author(s):  
A. R. W. McKellar ◽  
H. L. Welsh

Spectra due to the Van der Waals complex (H2)2 have been obtained with greatly improved resolution, and analogous spectra of (D2)2 and H2–D2 have been observed. The experiments were conducted with an absorption path of 110 m in a multiple traversal cell at temperatures between 16 and 21 K. The spectra are manifested as fine structure accompanying the single and double H2 (or D2) transitions in the hydrogen (or deuterium) collision induced fundamental band. The observed structure for (H2)2 and H2–D2 can be unambiguously assigned to rotational transitions of the complex governed by the selection rule Δl = ± 1, ± 3, where l is the rotational quantum number of the complex. A detailed analysis must include anisotropic force effects, and is not given here. The spectrum of (D2)2 is complicated, not only by anisotropic force effects, but also by mutual perturbations between the rotational levels of the upper states of corresponding single and double D2 transitions; for this reason, the assignments suggested are somewhat uncertain. An interesting intensity alternation apparent in part of the (D2)2 spectrum is explained as a simple effect of nuclear spin statistics in the pseudodiatomic molecule (D2)2.


1979 ◽  
Vol 57 (8) ◽  
pp. 1081-1089 ◽  
Author(s):  
Arieh Rosenberg ◽  
Joel Susskind

A general expression is derived for the integrated intensity of rotational transitions in the vibronic ground state of tetrahedral molecules, taking into account the nuclear spin statistics. It is shown that the ratio of this expression to previously published spin-free integrated intensities depends only on the tensor character N of the operator driving the transition, the appropriate rotational quantum numbers J and J′, and the nuclear spin IB of the identical nuclei. Tables are given for N = 3, 4 and J ≤ 50 which enable the calculation of integrated intensities for octopole and hexadecapole collision induced dipole moment transitions, centrifugal distortion induced dipole moment transitions, and centrifugal distortion induced anisotropic polarizability tensor Raman transitions. It is shown that the relative error of the spin-free integrated intensity calculation is proportional to (2IB + 1)−2.


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