2007/07/06 by Oriol Vendrell, Fabien Gatti, Hans‐Dieter Meyer +1 · 2 citations
Chemistry · Physics and Astronomy · #Laser-Matter Interactions and Applications #Spectroscopy and Laser Applications #Spectroscopy and Quantum Chemical Studies #physics.chem-ph
paper · pdf · doi:10.1063/1.2787596
published as J. Chem. Phys., 2007, 127, 184303-1 -- 184303-10 · 30 pages, 6 figures, submitted to J. Chem. Phys
arxiv created 2007/07/06 · openalex publication_date 2007/11/09 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
The infrared absorption spectrum of the protonated water dimer (H5O2+) is simulated in full dimensionality (15 dimensional) in the spectral range of 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 H5O2+ 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 are assigned. The large couplings featured by H5O2+ do not hinder, however, to describe the coupled vibrational motion by well defined simple types of vibration (stretching, bending; etc.) based on well defined modes of vibration, in terms of which the spectral lines are assigned. Comparison of our results to recent experiments and calculations on the system is given. The reported MCTDH IR spectrum is in very good agreement to the recently measured spectrum by Hammer et al. [J. Chem. Phys. 122, 244301 (2005)].