Transformation-Free Generation of a Quasi-Diabatic Representation from the State-Average Orbital-Optimized Variational Quantum Eigensolver

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61989100%3A27740%2F25%3A10257792" target="_blank" >RIV/61989100:27740/25:10257792 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jctc.5c00327" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jctc.5c00327</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.5c00327" target="_blank" >10.1021/acs.jctc.5c00327</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Transformation-Free Generation of a Quasi-Diabatic Representation from the State-Average Orbital-Optimized Variational Quantum Eigensolver

Popis výsledku v původním jazyce

In the present work, we examine how the recent quantum-computing algorithm known as the state-average orbital-optimized variational quantum eigensolver (SA-OO-VQE), viewed within the context of quantum chemistry as a type of multiconfiguration self-consistent field (MCSCF) electronic-structure approach, exhibits a propensity to produce an ab initio quasi-diabatic representation “for free” if considered as a least-transformed block-diagonalization procedure, as alluded to in our previous work (Yalouz, S. et al. J. Chem. Theory Comput. 2022, 18, 776−794) and thoroughly assessed herein. To this end, we introduce intrinsic and residual descriptors of diabaticity and re-explore the definition and linear-algebra properties, as well as their consequences on the vibronic nonadiabatic couplings, of an optimal diabatic representation within this context and how much one may deviate from it. Such considerations are illustrated numerically in the prototypical case of formaldimine, which presents a well-known conical intersection between its ground and first-excited singlet electronic states.

Název v anglickém jazyce

Transformation-Free Generation of a Quasi-Diabatic Representation from the State-Average Orbital-Optimized Variational Quantum Eigensolver

Popis výsledku anglicky

In the present work, we examine how the recent quantum-computing algorithm known as the state-average orbital-optimized variational quantum eigensolver (SA-OO-VQE), viewed within the context of quantum chemistry as a type of multiconfiguration self-consistent field (MCSCF) electronic-structure approach, exhibits a propensity to produce an ab initio quasi-diabatic representation “for free” if considered as a least-transformed block-diagonalization procedure, as alluded to in our previous work (Yalouz, S. et al. J. Chem. Theory Comput. 2022, 18, 776−794) and thoroughly assessed herein. To this end, we introduce intrinsic and residual descriptors of diabaticity and re-explore the definition and linear-algebra properties, as well as their consequences on the vibronic nonadiabatic couplings, of an optimal diabatic representation within this context and how much one may deviate from it. Such considerations are illustrated numerically in the prototypical case of formaldimine, which presents a well-known conical intersection between its ground and first-excited singlet electronic states.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

—

Rok uplatnění

2025

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

1549-9626

Svazek periodika

21

Číslo periodika v rámci svazku

11

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

24

Strana od-do

"5457–5480"

Kód UT WoS článku

001494666600001

EID výsledku v databázi Scopus

2-s2.0-105006611325