Correcting Basis Set Incompleteness in Wave Function Correlation Energy by Dressing Electronic Hamiltonian with an Effective Short-Range Interaction

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F25%3A00637233" target="_blank" >RIV/61388955:_____/25:00637233 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0368999" target="_blank" >https://hdl.handle.net/11104/0368999</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpclett.5c01070" target="_blank" >10.1021/acs.jpclett.5c01070</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Correcting Basis Set Incompleteness in Wave Function Correlation Energy by Dressing Electronic Hamiltonian with an Effective Short-Range Interaction

Popis výsledku v původním jazyce

We propose a general approach to reducing basis set incompleteness error in electron correlation energy calculations. The correction is computed alongside the correlation energy in a single calculation by modifying the electron interaction operator with an effective short-range electron-electron interaction. Our approach is based on a local mapping between the Coulomb operator projected onto a finite basis and a long-range interaction represented by the error function with a local range-separated parameter, originally introduced by Giner et al. []. Unlike the basis set incompleteness error correction proposed in that work, our method does not rely on short-range correlation density functionals. As a numerical demonstration, we apply the method with complete active space wave functions. Correlation energies are computed using two distinct approaches: the linearized adiabatic connection (AC0) method and n-electron valence state second-order perturbation theory (NEVPT2). We obtain encouraging results for the relative energies of test molecules, with accuracy in a triple-zeta basis set comparable to or exceeding that of uncorrected AC0 or NEVPT2 energies in a quintuple-zeta basis set.

Název v anglickém jazyce

Correcting Basis Set Incompleteness in Wave Function Correlation Energy by Dressing Electronic Hamiltonian with an Effective Short-Range Interaction

Popis výsledku anglicky

We propose a general approach to reducing basis set incompleteness error in electron correlation energy calculations. The correction is computed alongside the correlation energy in a single calculation by modifying the electron interaction operator with an effective short-range electron-electron interaction. Our approach is based on a local mapping between the Coulomb operator projected onto a finite basis and a long-range interaction represented by the error function with a local range-separated parameter, originally introduced by Giner et al. []. Unlike the basis set incompleteness error correction proposed in that work, our method does not rely on short-range correlation density functionals. As a numerical demonstration, we apply the method with complete active space wave functions. Correlation energies are computed using two distinct approaches: the linearized adiabatic connection (AC0) method and n-electron valence state second-order perturbation theory (NEVPT2). We obtain encouraging results for the relative energies of test molecules, with accuracy in a triple-zeta basis set comparable to or exceeding that of uncorrected AC0 or NEVPT2 energies in a quintuple-zeta basis set.

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

2025

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

16

Číslo periodika v rámci svazku

25

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

6489-6499

Kód UT WoS článku

001517913300001

EID výsledku v databázi Scopus

2-s2.0-105008520533