Using Koopmans' theorem for constructing basis sets: approaching high Rydberg excited states of lithium with a compact Gaussian basis

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F68378271%3A_____%2F23%3A00574593" target="_blank" >RIV/68378271:_____/23:00574593 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0345698" target="_blank" >https://hdl.handle.net/11104/0345698</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d2cp04633d" target="_blank" >10.1039/d2cp04633d</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Using Koopmans' theorem for constructing basis sets: approaching high Rydberg excited states of lithium with a compact Gaussian basis

Popis výsledku v původním jazyce

For accurate ab initio description of Rydberg excited states, this study suggests generating appropriate diffuse basis functions by cheap variational optimization of virtual orbitals of the corresponding ion core. By following this approach, dozens of converged correlated lithium Rydberg states, namely, all the states up to 24S, 25P, 14D, 16F and 16G, not yet achieved via other ab initio approaches, could be obtained at the EOM-CCSD level of theory with compact and mostly state-selective contracted Gaussian basis sets. Despite its small size and Gaussian character, the optimized basis leads to highly accurate excitation energies that differ merely in the order of meV from the reference state-of-the-art explicitly correlated Gaussian method and even surpass Full-CI results on the Slater basis by an order of magnitude.

Název v anglickém jazyce

Using Koopmans' theorem for constructing basis sets: approaching high Rydberg excited states of lithium with a compact Gaussian basis

Popis výsledku anglicky

For accurate ab initio description of Rydberg excited states, this study suggests generating appropriate diffuse basis functions by cheap variational optimization of virtual orbitals of the corresponding ion core. By following this approach, dozens of converged correlated lithium Rydberg states, namely, all the states up to 24S, 25P, 14D, 16F and 16G, not yet achieved via other ab initio approaches, could be obtained at the EOM-CCSD level of theory with compact and mostly state-selective contracted Gaussian basis sets. Despite its small size and Gaussian character, the optimized basis leads to highly accurate excitation energies that differ merely in the order of meV from the reference state-of-the-art explicitly correlated Gaussian method and even surpass Full-CI results on the Slater basis by an order of magnitude.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Projekt

<a href="/cs/project/GA20-21179S" target="_blank" >GA20-21179S: Studium nehermitovských degenerací (tzv. zvláštních bodů) v atomové fyzice prostřednictvím XUV laserových impulzů</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

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Svazek periodika

25

Číslo periodika v rámci svazku

30

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

20250-20258

Kód UT WoS článku

001031939000001

EID výsledku v databázi Scopus

2-s2.0-85166390412