Temporally stable rotational coherent states for molecular simulations. II. Symmetric rotor case

Following our preceding work on spherical and linear rotors [C. Stopera and J. A. Morales, J. Chem. Phys. 152, 134112 (2020)], we reformulate an earlier rotational coherent state (CS) set to obtain a temporally stable (TS) CS set for symmetric rotors. Being TS, the new CSs remain within its own set during dynamics by evolving exclusively through their parameters. The TS CS set is now appropriate to reconstruct quantum rotational properties from classical-mechanics simulations of chemical reactions. Following literature precedents, we enforce temporal stability by incorporating action-angle-related phase factors into two parameters of the original CS set. Proofs and final expressions of the symmetric-rotor CS turn out more intricate than those of its spherical-rotor counterpart. We demonstrate and examine the key properties of the new CS set: continuity, resolution of unity, temporal stability, action identity, minimum uncertainty relationships, and quasi-classical behavior. Regarding the last property, we demonstrate that the body-fixed z-component of the CS angular momentum average evolves exactly as its classical counterpart, and that the x- and y-components display an astonishing analogy with their classical counterparts in terms of functional form, precession angular velocities, amplitudes, and phases. We elucidate some of these properties via computer simulations of a rotating benzene molecule represented with the CS set. We discuss the utilization of this CS set to reconstruct quantum rotational properties of symmetric-rotor molecules from classical-mechanics simulations. The new CS set is appropriate to establish quantum-classical connections for rotational properties in chemical dynamics, statistical mechanics, spectroscopy, nuclear physics, and quantum computing. Published under an exclusive license by AIP Publishing.

Automated summary

In this work, we have improved an earlier rotational coherent state (CS) set to obtain a temporally stable (TS) CS set for symmetric rotors, which is applicable for reconstructing quantum rotational properties from classical-mechanics simulations. By incorporating action-angle-related phase factors into two parameters of the original CS set, we have achieved temporal stability. Computer simulations of a rotating benzene molecule represented with the CS set demonstrate key properties of the new set and its potential applications in various fields.