Interplay of Rotational and Pseudorotational Motions in Flexible Cyclic Molecules.

Solutions to the time-independent nuclear Schrodinger equation associated with the pseudorotational motion of three flexible cyclic molecules are presented and discussed. Structural relaxations related to the pseudorotational motion are described as functions of a pseudorotation angle ϕ which is formulated according to the definition of ring-puckering coordinates originally proposed by Cremer and Pople ( J. Am. Chem. Soc. 1975, 97 (6), 1354-1358). In order to take into account the interplay between pseudorotational and rotational motions, the rovibrational Hamiltonian matrices are formulated for the rotational quantum numbers J = 0 and J = 1. The rovibrational Hamiltonian matrices are constructed and diagonalized using a Python program developed by the authors. Suitable algorithms for (i) the construction of one-dimensional cuts of potential energy surfaces along the pseudorotation angle ϕ and (ii) the assignment of the vibrorotational wave functions (which are needed for the automatic calculation of rotational transition energies J = 0 → J = 1) are described and discussed.