Hilbert space multireference coupled cluster tailored by matrix product states.
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00580139" target="_blank" >RIV/61388955:_____/23:00580139 - isvavai.cz</a>
Nalezeny alternativní kódy
RIV/00216208:11310/23:10480047
Výsledek na webu
<a href="https://hdl.handle.net/11104/0348905" target="_blank" >https://hdl.handle.net/11104/0348905</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1063/5.0174461" target="_blank" >10.1063/5.0174461</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Hilbert space multireference coupled cluster tailored by matrix product states.
Popis výsledku v původním jazyce
In the past decade, the quantum chemical version of the density matrix renormalization group method has established itself as the method of choice for strongly correlated molecular systems. However, despite its favorable scaling, in practice, it is not suitable for computations of dynamic correlation. Several approaches to include that in post-DMRG methods exist, in our group, we focused on the tailored coupled cluster (TCC) approach. This method works well in many situations. However, in exactly degenerate cases (with two or more determinants of equal weight), it exhibits a bias toward the reference determinant representing the Fermi vacuum. Although sometimes it is possible to use a compensation scheme to avoid this bias for energy differences, it is certainly a drawback. In order to overcome this bias of the TCC method, we have developed a Hilbert-space multireference version of tailored CC, which can treat several determinants on an equal footing. We have implemented and compared the performance of three Hilbert-space multireference coupled cluster (MRCC) variants-the state universal one and the Brillouin-Wigner and Mukherjee's state specific ones. We have assessed these approaches on the cyclobutadiene and tetramethyleneethane molecules, which are both diradicals with exactly degenerate determinants at a certain geometry. We have also investigated the sensitivity of the results on the orbital rotation of the highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) pair, as it is well known that Hilbert-space MRCC methods are not invariant to such transformations.
Název v anglickém jazyce
Hilbert space multireference coupled cluster tailored by matrix product states.
Popis výsledku anglicky
In the past decade, the quantum chemical version of the density matrix renormalization group method has established itself as the method of choice for strongly correlated molecular systems. However, despite its favorable scaling, in practice, it is not suitable for computations of dynamic correlation. Several approaches to include that in post-DMRG methods exist, in our group, we focused on the tailored coupled cluster (TCC) approach. This method works well in many situations. However, in exactly degenerate cases (with two or more determinants of equal weight), it exhibits a bias toward the reference determinant representing the Fermi vacuum. Although sometimes it is possible to use a compensation scheme to avoid this bias for energy differences, it is certainly a drawback. In order to overcome this bias of the TCC method, we have developed a Hilbert-space multireference version of tailored CC, which can treat several determinants on an equal footing. We have implemented and compared the performance of three Hilbert-space multireference coupled cluster (MRCC) variants-the state universal one and the Brillouin-Wigner and Mukherjee's state specific ones. We have assessed these approaches on the cyclobutadiene and tetramethyleneethane molecules, which are both diradicals with exactly degenerate determinants at a certain geometry. We have also investigated the sensitivity of the results on the orbital rotation of the highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) pair, as it is well known that Hilbert-space MRCC methods are not invariant to such transformations.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10403 - Physical chemistry
Návaznosti výsledku
Projekt
Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.
Návaznosti
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Ostatní
Rok uplatnění
2023
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Journal of Chemical Physics
ISSN
0021-9606
e-ISSN
1089-7690
Svazek periodika
159
Číslo periodika v rámci svazku
22
Stát vydavatele periodika
US - Spojené státy americké
Počet stran výsledku
14
Strana od-do
224115
Kód UT WoS článku
001126141400006
EID výsledku v databázi Scopus
2-s2.0-85179772948