Surface hopping simulation of vibrational predissociation of methanol dimer

Title Surface hopping simulation of vibrational predissociation of methanol dimer
Publication Type Journal Article
Year of Publication 2012
Authors Jiang RM, Sibert EL
Journal Journal of Chemical Physics
Volume 136
Date Published Jun
Type of Article Article
ISBN Number 0021-9606
Accession Number WOS:000305268500004
Keywords alcohol oligomers, collective probabilities algorithm, electronic-transitions, energy relaxation, hydrogen-bond breaking, hydroxyl stretch, molecular-dynamics, nonadiabatic dynamics, organic compounds, predissociation, SCF calculations, tunnelling, vibrational states, proton-transfer reactions, quantum, rber rb, 1982, journal of chemical physics, v77, p3022, transitions
Abstract The mixed quantum-classical surface hopping method is applied to the vibrational predissociation of methanol dimer, and the results are compared to more exact quantum calculations. Utilizing the vibrational SCF basis, the predissociation problem is cast into a curve crossing problem between dissociative and quasibound surfaces with different vibrational character. The varied features of the dissociative surfaces, arising from the large amplitude OH torsion, generate rich predissociation dynamics. The fewest switches surface hopping algorithm of Tully [J. Chem. Phys. 93, 1061 (1990)] is applied to both diabatic and adiabatic representations. The comparison affords new insight into the criterion for selecting the suitable representation. The adiabatic method’s difficulty with low energy trajectories is highlighted. In the normal crossing case, the diabatic calculations yield good results, albeit showing its limitation in situations where tunneling is important. The quadratic scaling of the rates on coupling strength is confirmed. An interesting resonance behavior is identified and is dealt with using a simple decoherence scheme. For low lying dissociative surfaces that do not cross the quasibound surface, the diabatic method tends to overestimate the predissociation rate whereas the adiabatic method is qualitatively correct. Analysis reveals the major culprits involve Rabi-like oscillation, treatment of classically forbidden hops, and overcoherence. Improvements of the surface hopping results are achieved by adopting a few changes to the original surface hopping algorithms. (C) 2012 American Institute of Physics. []
Short Title J. Chem. Phys.
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