Toward more accurate adiabatic connection approach for multireference wavefunctions

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00568898" target="_blank" >RIV/61388955:_____/23:00568898 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11320/23:10475778

Výsledek na webu

<a href="https://hdl.handle.net/11104/0340176" target="_blank" >https://hdl.handle.net/11104/0340176</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0131448" target="_blank" >10.1063/5.0131448</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Toward more accurate adiabatic connection approach for multireference wavefunctions

Popis výsledku v původním jazyce

A multiconfigurational adiabatic connection (AC) formalism is an attractive approach to compute the dynamic correlation within the complete active space self-consistent field and density matrix renormalization group (DMRG) models. Practical realizations of AC have been based on two approximations: (i) fixing one- and two-electron reduced density matrices (1- and 2-RDMs) at the zero-coupling constant limit and (ii) extended random phase approximation (ERPA). This work investigates the effect of removing the ´´fixed-RDM´´approximation in AC. The analysis is carried out for two electronic Hamiltonian partitionings: the group product function- and the Dyall Hamiltonians. Exact reference AC integrands are generated from the DMRG full configuration interaction solver. Two AC models are investigated, employing either exact 1- and 2-RDMs or their second-order expansions in the coupling constant in the ERPA equations. Calculations for model molecules indicate that lifting the fixed-RDM approximation is a viable way toward improving the accuracy of existing AC approximations.

Název v anglickém jazyce

Toward more accurate adiabatic connection approach for multireference wavefunctions

Popis výsledku anglicky

A multiconfigurational adiabatic connection (AC) formalism is an attractive approach to compute the dynamic correlation within the complete active space self-consistent field and density matrix renormalization group (DMRG) models. Practical realizations of AC have been based on two approximations: (i) fixing one- and two-electron reduced density matrices (1- and 2-RDMs) at the zero-coupling constant limit and (ii) extended random phase approximation (ERPA). This work investigates the effect of removing the ´´fixed-RDM´´approximation in AC. The analysis is carried out for two electronic Hamiltonian partitionings: the group product function- and the Dyall Hamiltonians. Exact reference AC integrands are generated from the DMRG full configuration interaction solver. Two AC models are investigated, employing either exact 1- and 2-RDMs or their second-order expansions in the coupling constant in the ERPA equations. Calculations for model molecules indicate that lifting the fixed-RDM approximation is a viable way toward improving the accuracy of existing AC approximations.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GF23-04302L" target="_blank" >GF23-04302L: Efektivní výpočetní metody pro velké molekuly založené na renormalizační grupě matice hustoty</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Svazek periodika

158

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

054105

Kód UT WoS článku

000925327200001

EID výsledku v databázi Scopus

2-s2.0-85147543623