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

Sibaev, Marat, Polyak, Iakov, Manby, Frederick R. and Knowles, Peter J. 2020. Molecular second-quantized Hamiltonian: electron correlation and non-adiabatic coupling treated on an equal footing. 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
Publisher: American Institute of Physics
ISSN: 0021-9606
Date of First Compliant Deposit: 24 September 2020
Date of Acceptance: 1 September 2020
Last Modified: 15 Jul 2021 01:21
URI: http://orca.cardiff.ac.uk/id/eprint/135080

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