Full Dimensional (15D) Quantum-Dynamical Simulation of the Protonated Water-Dimer II: Infrared Spectrum and Vibrational Dynamics.

Oriol Vendrell (1) , Fabien Gatti (2) , H.-D. Meyer

1 Theoretische Chemie Universität Heidelberg
2 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

The infrared absorption spectrum of the protonated water dimer (H5O+ 2 ) is simulated in full dimensionality (15D) in the spectral range 0–4000 cm−1. The calculations are performed using the Multiconfiguration Time-Dependent Hartree (MCTDH) method for propagation of wavepackets. All the fundamentals and several overtones of the vibrational motion are computed. The spectrum of H5O+ 2 is shaped to a large extent by couplings of the proton-transfer motion to large amplitude fluxional motions of the water molecules, water bending and water-water stretch motions. These couplings are identified and discussed, and the corresponding spectral lines assigned. The large couplings featured by H5O+ 2 do not hinder, however, a description of the vibrational motion based on well defined modes of vibration, in terms of which the spectral lines are assigned. Compar- ison of our results to recent experiments and calculations on the system is given. The reported MCTDH spectrum is in very good agreement to the recently measured spectrum by Hammer et. al. [JCP, 122, 244301, (2005)].

Domaines: Chimie théorique et/ou physique

Oriol Vendrell, Fabien Gatti, H.-D. Meyer. Full Dimensional (15D) Quantum-Dynamical Simulation of the Protonated Water-Dimer II: Infrared Spectrum and Vibrational Dynamics.. Journal of Chemical Physics, 2007, 127 (18), pp.184303. ⟨10.1063/1.2787596⟩. ⟨hal-00171333⟩