title: Constrained molecular vibration-rotation Hamiltonians: contravariant metric tensor.
abstract: Here, I present a practical recipe for obtaining contravariant vibration-rotation metric tensors, and thus the kinetic energy operators, when some degrees of freedom are constrained rigidly. An element of the contravariant metric tensor is obtained as a sum of dot products of contravariant measuring vectors, which are obtained from their unconstrained counterparts by adding a frozen mode correction. The present method applies in principle for any choice of shape coordinates and a body-frame for which the contravariant measuring vectors can be evaluated. In contrast to the existing methods, the present method does not involve evaluation of covariant metric tensors, matrix inversions, chain rules of derivation, or numerical differentiation. It is applied in the sequel paper [L. Partanen, J. Pesonen, E. Sjöholm, and L. Halonen, J. Chem. Phys. 139, 144311 (2013)] to study the effects of several different approximations to the kinetic energy operator, when the two large-amplitude OH-torsional motions in H2SO4 are of interest.
authors.affiliation: Department of Chemistry, University of Helsinki, P.O. Box 55 (A. I. Virtasen aukio 1), Helsinki FIN-00014, Finland.
authors.forename: Janne
authors.initials: J
authors.lastname: Pesonen