title: On the origin dependence of the angle made by the electric and magnetic vibrational transition dipole moment vectors.
abstract: The concept of robustness of rotational strengths of vibrational modes in a VCD spectrum has been introduced as an aid in assignment of the absolute configuration with the help of the VCD spectrum. The criteria for robustness have been based on the distribution around 90° of the angles ξ(i) between electric and magnetic transition dipoles of all the modes i of a molecule. The angles ξ(i) (not, of course, the rotational strengths) are, however, dependent on the choice of origin. The derived criteria are for the center of mass chosen as the origin of the coordinate system. We stress in this note that application of the derived criteria assumes that excessive translation of the coordinate origin is not applied. Although the ξ(i) angles are not very sensitive to the position of the origin, very small displacements (a few Å) are not a problem, excessive translation of the origin does have considerable effect on the ξ(i) angles. In this note we quantify this effect and demonstrate how the distribution of ξ(i) angles is affected. Although it is possible to recalibrate the robustness criteria for the angles for a specific (large) displacement, we recommend that such displacement simply be avoided. It is to be noted that some modeling software does yield output with excessively displaced coordinate origin; this should be checked and corrected.
authors.affiliation: Theoretical Chemistry, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands. v.p.nicu@vu.nl
authors.forename: Valentin Paul
authors.initials: VP
authors.lastname: Nicu
authors.forename: Evert Jan
authors.initials: EJ
authors.lastname: Baerends