Toward Accurate Post-Born-Oppenheimer Molecular Simulations on Quantum Computers: An Adaptive Variational Eigensolver with Nuclear-Electronic Frozen Natural Orbitals
Artikel i vetenskaplig tidskrift, 2023
Nuclear quantum effects such as zero-point energy and hydrogen tunneling play a central role in many biological and chemical processes. The nuclear-electronic orbital (NEO) approach captures these effects by treating selected nuclei quantum mechanically on the same footing as electrons. On classical computers, the resources required for an exact solution of NEO-based models grow exponentially with system size. By contrast, quantum computers offer a means of solving this problem with polynomial scaling. However, due to the limitations of current quantum devices, NEO simulations are confined to the smallest systems described by minimal basis sets, whereas realistic simulations beyond the Born-Oppenheimer approximation require more sophisticated basis sets. For this purpose, we herein extend a hardware-efficient ADAPT-VQE method to the NEO framework in the frozen natural orbital (FNO) basis. We demonstrate on H2 and D2 molecules that the NEO-FNO-ADAPT-VQE method reduces the CNOT count by several orders of magnitude relative to the NEO unitary coupled cluster method with singles and doubles while maintaining the desired accuracy. This extreme reduction in the CNOT gate count is sufficient to permit practical computations employing the NEO method─an important step toward accurate simulations involving nonclassical nuclei and non-Born-Oppenheimer effects on near-term quantum devices. We further show that the method can capture isotope effects, and we demonstrate that inclusion of correlation energy systematically improves the prediction of difference in the zero-point energy (ΔZPE) between isotopes.
Författare
Anton Nykänen
Algorithmiq
Aaron Miller
Algorithmiq
Trinity College Dublin
Walter Talarico
Algorithmiq
Aalto-Yliopisto
Stefan Knecht
Eidgenössische Technische Hochschule Zürich (ETH)
Algorithmiq
Arseny Kovyrshin
AstraZeneca AB
Mårten Skogh
Chalmers, Kemi och kemiteknik, Kemi och biokemi
AstraZeneca AB
Lars Tornberg
AstraZeneca AB
Anders Broo
AstraZeneca AB
Stefano Mensa
Science and Technology Facilities Council (STFC)
Benjamin C.B. Symons
Science and Technology Facilities Council (STFC)
Emre Sahin
Science and Technology Facilities Council (STFC)
Jason Crain
University of Oxford
IBM
Ivano Tavernelli
IBM
Fabijan Pavošević
Algorithmiq
Journal of Chemical Theory and Computation
1549-9618 (ISSN) 1549-9626 (eISSN)
Vol. 19 24 9269-9277Wallenberg Centre for Quantum Technology (WACQT)
Knut och Alice Wallenbergs Stiftelse (KAW 2017.0449, KAW2021.0009, KAW2022.0006), 2018-01-01 -- 2030-03-31.
Ämneskategorier (SSIF 2011)
Beräkningsmatematik
Teoretisk kemi
Datavetenskap (datalogi)
DOI
10.1021/acs.jctc.3c01091
PubMed
38081802