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

Polyak, Iakov ORCID: https://orcid.org/0000-0002-2894-0657, Allan, Charlotte S. M. and Worth, Graham A. 2015. A complete description of tunnelling using direct quantum dynamics simulation: Salicylaldimine proton transfer. Journal of Chemical Physics 143 (8) , 084121. 10.1063/1.4929478

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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.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Institute of Physics
ISSN:	0021-9606
Date of Acceptance:	1 August 2015
Last Modified:	23 Oct 2022 13:21
URI:	https://orca.cardiff.ac.uk/id/eprint/110437

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