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Complex adiabatic connection: A hidden non-Hermitian path from ground to excited states.

Accepted version
Peer-reviewed

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Type

Article

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Authors

Burton, Hugh GA 
Thom, Alex JW 
Loos, Pierre-François 

Abstract

Processes related to electronically excited states are central in many areas of science; however, accurately determining excited-state energies remains a major challenge in theoretical chemistry. Recently, higher energy stationary states of non-linear methods have themselves been proposed as approximations to excited states, although the general understanding of the nature of these solutions remains surprisingly limited. In this letter, we present an entirely novel approach for exploring and obtaining excited stationary states by exploiting the properties of non-Hermitian Hamiltonians. Our key idea centres on performing analytic continuations of conventional quantum chemistry methods. Considering Hartree-Fock theory as an example, we analytically continue the electron-electron interaction to expose a hidden connectivity of multiple solutions across the complex plane, revealing a close resemblance between Coulson-Fischer points and non-Hermitian degeneracies. Finally, we demonstrate how a ground-state wave function can be morphed naturally into an excited-state wave function by constructing a well-defined complex adiabatic connection.

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Keywords

physics.chem-ph, physics.chem-ph

Journal Title

J Chem Phys

Conference Name

Journal ISSN

0021-9606
1089-7690

Volume Title

150

Publisher

AIP Publishing