Solutions to the time-independent nuclear Schrödinger 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.
Paoloni L., Maris A. (2021). Interplay of Rotational and Pseudorotational Motions in Flexible Cyclic Molecules. JOURNAL OF PHYSICAL CHEMISTRY. A, MOLECULES, SPECTROSCOPY, KINETICS, ENVIRONMENT, & GENERAL THEORY, 125(19), 4098-4113 [10.1021/acs.jpca.1c01472].
Interplay of Rotational and Pseudorotational Motions in Flexible Cyclic Molecules
Maris A.Ultimo
2021
Abstract
Solutions to the time-independent nuclear Schrödinger 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.File | Dimensione | Formato | |
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