A complete description of tunnelling using direct quantum dynamics simulation: Salicylaldimine proton transfer

The Journal of Chemical Physics
Iakov PolyakGraham A Worth

Abstract

We demonstrate here conclusively that the variational multiconfiguration Gaussian (vMCG) method converges to the grid based full quantum dynamics multiconfiguration time-dependent Hartree result for a tunnelling problem in many dimensions, using the intramolecular proton transfer in salicylaldimine as a model system. The 13-dimensional model potential energy surface was obtained from Hartree Fock energies with the 6-31G* basis set and the expectation value of the flux operator along the transition mode was used as a benchmark characteristic. As well as showing excellent convergence of the vMCG method on the model surface using a local harmonic approximation and a moderate number of basis functions, we show that the direct dynamics version of the vMCG also performs very well, usually needs the same number of Gaussians to converge, and converges to exact results if those are obtained on an accurately fitted surface. Finally, we make an important observation that the width of the Gaussian basis functions must be chosen very carefully to obtain accurate results with the use of the frozen-width approximation.

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Citations

Apr 11, 2017·Physical Chemistry Chemical Physics : PCCP·T J Penfold
Jun 1, 2017·Journal of Chemical Theory and Computation·Maximilian A C Saller, Scott Habershon
Aug 30, 2019·Physical Chemistry Chemical Physics : PCCP·T NortheyT J Penfold
Apr 9, 2018·The Journal of Chemical Physics·Gareth W Richings, Scott Habershon
Feb 3, 2019·The Journal of Chemical Physics·Iakov PolyakPeter J Knowles
Apr 4, 2021·The Journal of Chemical Physics·Georgia ChristopoulouGraham A Worth
Feb 22, 2018·Chemical Reviews·Basile F E Curchod, Todd J Martínez
Feb 9, 2017·Journal of Chemical Theory and Computation·Barak HirshbergR Benny Gerber
Jun 17, 2020·Journal of Chemical Theory and Computation·Niels Kristian MadsenOve Christiansen
Jul 19, 2017·Journal of Chemical Theory and Computation·Gareth W Richings, Scott Habershon

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