Correlation of optical activity and nonlinear polarizability

This paper describes recent experiments in which optical sum frequency generation has been observed in liquids. The mechanism of coherent optical sum frequency generation in systems of randomly oriented molecules is closely related to that of optical activity, and the symmetry selection rules for the two processes are the same. The effect is observed experimentally in d- and l-optical isomers, for example, but vanishes in a racemic mixture. Details of the measurement of the nonlinear polarizability of optically active liquids are presented. The mechanism of sum frequency generation is explained in terms of the one-electron and the coupled-oscillator models of optical activity, and it is proposed that the ratio of the nonlinear polarizability to the optical rotatory power provides information in assessing the relative role of the two models.