The Collision Broadening of Spectral Lines

Abstract

The shape of a collision-broadened spectral line depends on the assumptions made about the collision processes involved. If the collision cross section varies inversely as the relative speed of the colliding molecules, the half-width to the half-power points and to the points of steepest slope should be 1/27T1' and 1/(2";3)7T1' respectively, where l' is the mean interval between line-broadening collisions. It is shown that, in a gas of "hard-sphere" molecules, the shape of the line is modified and the above half-widths are reduced by' 6·4 and 9·7% respectively. While it is not suggested that gas molecules behave entirely as hard spheres, it is suggested that some deviations from the Van Vleck-Weisskopf-Lorentz shape may occur, and that it may be possible to detect these deviations experimentally