Photochemistry of the water dimer: Time-dependent quantum wave-packet description of the dynamics at the S1-S conical intersection
- 6 October 2009
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 131 (13), 134307
- https://doi.org/10.1063/1.3226568
Abstract
The photoinduced electron-driven proton-transfer dynamics of the water-dimer system has been investigated by time-dependent quantum wave-packet calculations. The main nuclear degrees of freedom driving the system from the Frank-Condon region to the S-0-S-1 conical intersection are the distance between the oxygen atoms and the displacement of the hydrogen atom from the oxygen-oxygen bond center. Two important coupling modes have been investigated: Rotation of the H-donating water dangling proton and asymmetric stretching of the H-accepting water dangling protons' OaH bonds. Potential energy surfaces of the ground and lowest excited electronic states have been constructed on the basis of ab initio calculations. The time-dependent quantum wave-packet propagation has been employed within the (2 + 1)-dimensional systems for the description of the nonadiabatic dynamics of water dimer. The effects of the initial vibrational state of the system on the electronic population transfer and dissociation dynamics are presented. To approximate the photochemical behavior of water dimer in bulk water, we add a boundary condition into the (2 + 1)-dimensional systems to simulate the existence of water bulk. The results provide insight into the mechanisms of excited state deactivation of the water-dimer system in gas phase and in bulk water through the electron-driven proton-transfer process. (C) 2009 American Institute of Physics. [doi:10.1063/1.3226568]Keywords
This publication has 44 references indexed in Scilit:
- Excited state properties of liquid waterJournal of Physics: Condensed Matter, 2008
- Photoexcitation and Photoionization Dynamics of Water PhotolysisThe Journal of Physical Chemistry A, 2008
- Stretching of hydrogen-bonded OH in the lowest singlet excited electronic state of water dimerThe Journal of Chemical Physics, 2006
- Excited electronic states of small water clustersThe Journal of Chemical Physics, 2005
- Ultraviolet Spectroscopy of Large Water Clusters: Model and Calculations for (H2O)n, forn= 8, 11, 20, 40, and 50The Journal of Physical Chemistry A, 2004
- Ultraviolet spectroscopy of water clusters: Excited electronic states and absorption line shapes of (H2O)n, n=2–6The Journal of Chemical Physics, 1998
- State resolved photodissociation of vibrationally excited water: Rotations, stretching vibrations, and relative cross sectionsThe Journal of Chemical Physics, 1991
- Photodissociation processes of water vapor below and above the ionization potentialThe Journal of Chemical Physics, 1985
- A b i n i t i o calculation of the first order interaction energy in excited dimers. The H2O–H2O and H2O–Ne dimersThe Journal of Chemical Physics, 1979
- The Rydberg Nature And Assignments Of Excited States Of The Water MoleculeChemical Physics Letters, 1974