Publication Abstracts

Green 1988

Green, S., 1988: Effect of nuclear hyperfine structure on microwave spectral pressure broadening. J. Chem. Phys., 88, 7331-7336, doi:10.1063/1.454344.

The spectral pressure broadening formalism of Ben-Reuven [Phys. Rev. 145, 7 (1966)] is applied to rotational transitions of a closed-shell linear molecule with nuclear quadrupole hyperfine structure (hfs) due to a nucleus of spin I. If, as expected, nuclear spin does not affect molecular collision dynamics, generalized pressure broadening cross sections can be expressed in terms of the spin-free collisional S matrices. For the three hfs components of the lowest j=0-1 rotational transition, the line shape is a simple sum of three noninterfering Lorentzians each of which has the same width and shift as would be expected in the absence of nuclear spin. For higher rotational transitions, however, the line shape is no longer so simple; in general, each hfs component is described by a different width and shift, and collisions transfer intensity among them. Numerical results for HCN broadened by He atoms are presented using both the accurate close coupling (CC) collision formalism and also the infinite order sudden (IOS) approximation. For the case that broadening is very large compared with the hfs splittings it is shown (numerically, within the IOS approximation) that the line shape is nearly (but not exactly, except for j=0-1 as noted above) a Lorentzian with the same width as would be expected in the absenc of nuclear spin.

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BibTeX Citation

  author={Green, S.},
  title={Effect of nuclear hyperfine structure on microwave spectral pressure broadening},
  journal={Journal of Chemical Physics},

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RIS Citation

ID  - gr02200i
AU  - Green, S.
PY  - 1988
TI  - Effect of nuclear hyperfine structure on microwave spectral pressure broadening
JA  - J. Chem. Phys.
JO  - Journal of Chemical Physics
VL  - 88
SP  - 7331
EP  - 7336
DO  - 10.1063/1.454344
ER  -

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