Zombie cats on the quantum–classical frontier: Wigner–Moyal and semiclassical limit dynamics of quantum coherence in molecules

• Published in: The Journal of chemical physics 2023-11, Vol.159 (20)
• Main Authors: Green, Austin T., Martens, Craig C.
• Format: Article
• Language: English
• Subjects: Cats; Coherence; Electron states; Evolution; Quantum mechanics; Quantum phenomena; Quantum theory; Representations; Wave packets
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0177421

In this paper, we investigate the time evolution of quantum coherence—the off-diagonal elements of the density matrix of a multistate quantum system—from the perspective of the Wigner–Moyal formalism. This approach provides an exact phase space representation of quantum mechanics. We consider the coherent evolution of nuclear wavepackets in a molecule with two electronic states. For harmonic potentials, the problem is analytically soluble for both a fully quantum mechanical description and a semiclassical description. We highlight the serious deficiencies of the semiclassical treatment of coherence for general systems and illustrate how even qualitative accuracy requires higher order terms in the Moyal expansion to be included. The model provides an experimentally relevant example of a molecular Schrödinger’s cat state. The alive and dead cats of the exact two-state quantum evolution collapse into a “zombie” cat in the semiclassical limit—an averaged behavior, neither alive nor dead, leading to significant errors. The inclusion of the Moyal correction restores a faithful simultaneously alive and dead representation of the cat that is experimentally observable.