title: Temperature dependence of the optical rotation in six bicyclic organic molecules calculated by vibrational averaging.
abstract: The vibrational corrections and the temperature dependence of the specific rotation of six rigid organic molecules (alpha-pinene, beta-pinene, cis-pinane, camphene, camphor, and fenchone) were calculated at three wavelengths using hybrid time-dependent density functional theory (TDDFT). A technique for calculating the temperature dependence of the vibrational average of a molecular property has been applied to obtain the specific rotation of the molecules as a function of temperature. For cases in which accurate equilibrium optical rotations can be obtained as a "base value," and for which there is little effect from solvation, accurate predictions of the trends in the temperature-dependence of the specific rotations can be calculated. For other cases, the method can be used to extract purely vibrational contributions to the overall temperature dependence of optical rotation.
authors.affiliation: Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, USA.
authors.forename: Brendan C
authors.initials: BC
authors.lastname: Mort
authors.forename: Jochen
authors.initials: J
authors.lastname: Autschbach