Efficient Adiabatic Connection Approach for Strongly Correlated Systems: Application to Singlet–Triplet Gaps of Biradicals

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F22%3A00557671" target="_blank" >RIV/61388955:_____/22:00557671 - isvavai.cz</a>

Výsledek na webu

<a href="http://hdl.handle.net/11104/0331580" target="_blank" >http://hdl.handle.net/11104/0331580</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpclett.2c00993" target="_blank" >10.1021/acs.jpclett.2c00993</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Efficient Adiabatic Connection Approach for Strongly Correlated Systems: Application to Singlet–Triplet Gaps of Biradicals

Popis výsledku v původním jazyce

Strong electron correlation can be captured with multireference wave function methods, but an accurate description of the electronic structure requires accounting for the dynamic correlation, which they miss. In this work, a new approach for the correlation energy based on the adiabatic connection (AC) is proposed. The ACn method accounts for terms up to order n in the coupling constant, and it is size-consistent and free from instabilities. It employs the multireference random phase approximation and the Cholesky decomposition technique, leading to a computational cost growing with the fifth power of the system size. Because of the dependence on only one- and two-electron reduced density matrices, ACn is more efficient than existing ab initio multireference dynamic correlation methods. ACn affords excellent results for singlet–triplet gaps of challenging organic biradicals. The development presented in this work opens new perspectives for accurate calculations of systems with dozens of strongly correlated electrons.

Název v anglickém jazyce

Efficient Adiabatic Connection Approach for Strongly Correlated Systems: Application to Singlet–Triplet Gaps of Biradicals

Popis výsledku anglicky

Strong electron correlation can be captured with multireference wave function methods, but an accurate description of the electronic structure requires accounting for the dynamic correlation, which they miss. In this work, a new approach for the correlation energy based on the adiabatic connection (AC) is proposed. The ACn method accounts for terms up to order n in the coupling constant, and it is size-consistent and free from instabilities. It employs the multireference random phase approximation and the Cholesky decomposition technique, leading to a computational cost growing with the fifth power of the system size. Because of the dependence on only one- and two-electron reduced density matrices, ACn is more efficient than existing ab initio multireference dynamic correlation methods. ACn affords excellent results for singlet–triplet gaps of challenging organic biradicals. The development presented in this work opens new perspectives for accurate calculations of systems with dozens of strongly correlated electrons.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry Letters

ISSN

1948-7185

e-ISSN

—

Svazek periodika

13

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

4570-4578

Kód UT WoS článku

000806610000024

EID výsledku v databázi Scopus

2-s2.0-85131107208