LINEWIDTHS AND SHIFTS OF THE FUNDAMENTAL VIBRATION-ROTATION BAND OF HF AND HCL BROADENED BY $N_{2}, O_{2}$ AND AIR

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1986

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Ohio State University

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The linewidths and shifts of the fundamental vibration-rotation band of HF-X and HCL-X systems $(X = N_{2}, O_{2}, Air)$ have been calculated at $202^{\circ}$ and $296^{\circ} K$, using the Kolb-Grime-Baranger theory. The calculations include isotropic effects to all orders, use of realistic trajectories (as a modification of straight line trajectories) and explicit velocity averaging. It is found that the major contribution to the linewidths and shift arise from dipole-quadrupole, quadrupole-quadrupole, and vibrationally dependent isotropic dispersion forces. Due to the reduction of the dipole-quadrupole and quadrupole-quadrupole contributions with increasing $|m|$, the widths decrease, with a leveling off at high $|m|$ values, where the dispersion forces dominate. A comparison between the calculated and $measured^{1}$ widths and shifts, which shows good overall agreement, will be given.

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$^{1}$ A. S. Pine and J. P. Looney, this session. Address: Department of Physics, The Pennsylvania State University, University Park, PA 16802
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