Molecular second-quantized Hamiltonian: electron correlation and non-adiabatic coupling treated on an equal footing

Sibaev, Marat, Polyak, Iakov ORCID: https://orcid.org/0000-0002-2894-0657, Manby, Frederick R. and Knowles, Peter J. ORCID: https://orcid.org/0000-0003-4657-6331 2020. Molecular second-quantized Hamiltonian: electron correlation and non-adiabatic coupling treated on an equal footing. The Journal of Chemical Physics 153 (12) , 124102. 10.1063/5.0018930

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Abstract

We introduce a new theoretical and computational framework for treating molecular quantum mechanics without the Born–Oppenheimer approximation. The molecular wavefunction is represented in a tensor-product space of electronic and vibrational basis functions, with electronic basis chosen to reproduce the mean-field electronic structure at all geometries. We show how to transform the Hamiltonian to a fully second-quantized form with creation/annihilation operators for electronic and vibrational quantum particles, paving the way for polynomial-scaling approximations to the tensor-product space formalism. In addition, we make a proof-of-principle application of the new Ansatz to the vibronic spectrum of C2.

Item Type:	Article
Date Type:	Published Online
Status:	Published
Schools:	Chemistry Advanced Research Computing @ Cardiff (ARCCA)
Publisher:	American Institute of Physics
ISSN:	0021-9606
Date of First Compliant Deposit:	24 September 2020
Date of Acceptance:	1 September 2020
Last Modified:	06 Nov 2023 13:59
URI:	https://orca.cardiff.ac.uk/id/eprint/135080

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