Collect. Czech. Chem. Commun. 1993, 58, 2458-2473

Thermodynamic Functions of Pendular Molecules

Břetislav Friedrich and Dudley R. Herschbach

Department of Chemistry, Harvard University, 12 Oxford St. Cambridge, MA 02138, U.S.A.


External electric or magnetic fields can hybridize rotational states of individual dipolar molecules and thus create pendular states whose field-dependent eigenproperties differ qualitatively from those of a rotor or an oscilator. The pendular eigenfunctions are directional, so the molecular axis id oriented. Here we use quantum statistical mechanics to evaluate ensamble properties of the pendular states. For linear molecules, the partition function and the averages that determine the thermodynamic functions can be specified by two reduced variables involving the dipole moment, field strength, rotational constant, and temperature. We examine a simple approximation due to Pitzer that employs the classical partition function with quantum corrections. This provides explicit analytic formulas which permit thermodynamic properties to be evaluated to good accuracy without computing energy levels. As applications we evaluate the high-field average orientation of the molecular dipoles and field-induced shifts of chemical equilibria.