Dynamical hydrogen atom tunneling in dichlorotropolone: A combined quantum, semiclassical, and classical study

Abstract

Based on the Cartesian Reaction Surface framework we construct a four-dimensional potential for the tropolone derivative 3,7-dichlorotropolone, a molecule with an intramolecular O-H...O hydrogen bond. The reduced configuration space involves the in-plane hydrogen atom coordinates, a symmetric O-O vibrational mode, and an antisymmetric mode related to deformations of the seven-membered ring. The system is characterized in terms of quantum mechanical computations of the low-lying eigenstates as well as a classical and semiclassical analysis of spectra obtained via Fourier transforming autocorrelation functions. For the semiclassical analysis we utilize the amplitude-free correlation function method [K. Hotta and K. Takatsuka, J. Phys. A 36, 4785 (2003)]. Our results demonstrate substantial anharmonic couplings leading to highly correlated wave functions even at moderate energies. Furthermore, the importance of dynamical tunneling in tropolone is suggested since many low-lying states--including the ground state--lie above the classical saddle point but nevertheless appear as split pairs.