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Abstract

Electronic structure calculations of atoms and molecules are considered to be a promising application for quantum computers. Two key algorithms, the quantum phase estimation (QPE) and the variational quantum eigensolver (VQE), have been extensively studied. The condition that the energy of a dimer consisting of two monomers separated by a large distance should be equal to twice the energy of a monomer, known as size consistency, is essential in quantum chemical calculations. Recently, we reported that the size consistency condition can be violated by Trotterization in the unitary coupled cluster singles and doubles (UCCSD) ansatz in VQE when employing molecular orbitals delocalized to the dimer (K. Sugisaki {\it et al.}, {\it J. Comput. Chem.}, published online; \href{https://doi.org/10.1002/jcc.27438}{DOI:10.1002/jcc.27438}). It is well known that the full configuration interaction (full-CI) energy is invariant to arbitrary rotations of molecular orbitals, and therefore the QPE-based full-CI should theoretically satisfy the size consistency. However, Trotterization of the time evolution operator can break the size consistency conditions. In this work, we investigated whether the size consistency can be maintained with Trotterization of the time evolution operator in QPE-based full-CI calculations. Our numerical simulations revealed that size consistency in QPE-based full-CI is not automatically violated by using molecular orbitals delocalized to the dimer, but employing an appropriate Trotter decomposition condition is crucial to maintain size consistency. We also report on the acceleration of QPE simulations through the sequential addition of ancillary qubits.

Details

1009240
Title
Does the full configuration interaction method based on quantum phase estimation with Trotter decomposition satisfy the size consistency condition?
Publication title
arXiv.org; Ithaca
Publication year
2024
Publication date
Aug 8, 2024
Section
Quantum Physics
Publisher
Cornell University Library, arXiv.org
Source
arXiv.org
Place of publication
Ithaca
Country of publication
United States
University/institution
Cornell University Library arXiv.org
e-ISSN
2331-8422
Source type
Working Paper
Language of publication
English
Document type
Working Paper
Publication history
 
 
Online publication date
2024-09-26
Milestone dates
2024-06-14 (Submission v1); 2024-06-17 (Submission v2); 2024-08-08 (Submission v3)
Publication history
 
 
   First posting date
26 Sep 2024
ProQuest document ID
3069346026
Document URL
https://www.proquest.com/working-papers/does-full-configuration-interaction-method-based/docview/3069346026/se-2?accountid=208611
Full text outside of ProQuest
Copyright
© 2024. This work is published under http://arxiv.org/licenses/nonexclusive-distrib/1.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.
Last updated
2024-09-27
Database
ProQuest One Academic