title: Vibrational Quantum Decoherence in Liquid Water.
abstract: Traditional descriptions of vibrational energy transfer consider a quantum oscillator interacting with a classical environment. However, a major limitation of this simplified description is the neglect of quantum decoherence induced by the different interactions between two distinct quantum states and their environment, which can strongly affect the predicted energy-transfer rate and vibrational spectra. Here, we use quantum-classical molecular dynamics simulations to determine the vibrational quantum decoherence time for an OH stretch vibration in liquid heavy water. We show that coherence is lost on a sub-100 fs time scale due to the different responses of the first shell neighbors to the ground and excited OH vibrational states. This ultrafast decoherence induces a strong homogeneous contribution to the linear infrared spectrum and suggests that resonant vibrational energy transfer in H2O may be more incoherent than previously thought.
authors.affiliation: École Normale Supérieure-PSL Research University, Département de Chimie, Sorbonne Universités - UPMC, Univ Paris 06, CNRS UMR 8640 PASTEUR , 24 rue Lhomond, 75005 Paris, France.
authors.forename: Tatsuya
authors.initials: T
authors.lastname: Joutsuka
authors.affiliation: Department of Chemistry, University of Kansas , Lawrence, Kansas 66045, United States.
authors.forename: Ward H
authors.initials: WH
authors.lastname: Thompson
authors.affiliation: École Normale Supérieure-PSL Research University, Département de Chimie, Sorbonne Universités - UPMC, Univ Paris 06, CNRS UMR 8640 PASTEUR , 24 rue Lhomond, 75005 Paris, France.
authors.forename: Damien
authors.initials: D
authors.lastname: Laage
mesh_terms: D056004:Molecular Dynamics Simulation; D011789:Quantum Theory; D014732:Vibration; D014867:Water / Q000737:chemistry*
chemical_list: D014867:Water