Multistate Complete-Active-Space Second-Order Perturbation Theory Based on Density Matrix Renormalization Group Reference States
Identifikátory výsledku
Kód výsledku v IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00480940" target="_blank" >RIV/61388963:_____/17:00480940 - isvavai.cz</a>
Výsledek na webu
<a href="http://pubs.acs.org/doi/full/10.1021/acs.jctc.7b00735" target="_blank" >http://pubs.acs.org/doi/full/10.1021/acs.jctc.7b00735</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jctc.7b00735" target="_blank" >10.1021/acs.jctc.7b00735</a>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Multistate Complete-Active-Space Second-Order Perturbation Theory Based on Density Matrix Renormalization Group Reference States
Popis výsledku v původním jazyce
We present the development of the multistate multireference second-order perturbation theory (CASPT2) with multiroot references, which are described using the density matrix renormalization group (DMRG) method to handle a large active space. The multistate first-order wave functions are expanded into the internally contracted (IC) basis of the single-state single-reference (SS-SR) scheme, which is shown to be the most feasible variant to use DMRG references. The feasibility of the SS-SR scheme comes from two factors: first, it formally does not require the fourth-order transition reduced density matrix (TRDM) and second, the computational complexity scales linearly with the number of the reference states. The extended multistate (XMS) treatment is further incorporated, giving suited treatment of the zeroth-order Hamiltonian despite the fact that the SS-SR based IC basis is not invariant with respect to the XMS rotation. In addition, the state-specific fourth-order reduced density matrix (RDM) is eliminated in an approximate fashion using the cumulant reconstruction formula, as also done in the previous state-specific DMRG-cu(4)-CASPT2 approach. The resultant method, referred to as DMRG-cu(4)-XMS-CASPT2, uses the RDMs and TRDMs of up to third-order provided by the DMRG calculation. The multistate potential energy curves of the photoisomerization of diarylethene derivatives with CAS(26e,24o) are presented to illustrate the applicability of our theoretical approach.
Název v anglickém jazyce
Multistate Complete-Active-Space Second-Order Perturbation Theory Based on Density Matrix Renormalization Group Reference States
Popis výsledku anglicky
We present the development of the multistate multireference second-order perturbation theory (CASPT2) with multiroot references, which are described using the density matrix renormalization group (DMRG) method to handle a large active space. The multistate first-order wave functions are expanded into the internally contracted (IC) basis of the single-state single-reference (SS-SR) scheme, which is shown to be the most feasible variant to use DMRG references. The feasibility of the SS-SR scheme comes from two factors: first, it formally does not require the fourth-order transition reduced density matrix (TRDM) and second, the computational complexity scales linearly with the number of the reference states. The extended multistate (XMS) treatment is further incorporated, giving suited treatment of the zeroth-order Hamiltonian despite the fact that the SS-SR based IC basis is not invariant with respect to the XMS rotation. In addition, the state-specific fourth-order reduced density matrix (RDM) is eliminated in an approximate fashion using the cumulant reconstruction formula, as also done in the previous state-specific DMRG-cu(4)-CASPT2 approach. The resultant method, referred to as DMRG-cu(4)-XMS-CASPT2, uses the RDMs and TRDMs of up to third-order provided by the DMRG calculation. The multistate potential energy curves of the photoisomerization of diarylethene derivatives with CAS(26e,24o) are presented to illustrate the applicability of our theoretical approach.
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
<a href="/cs/project/GA15-19143S" target="_blank" >GA15-19143S: Singletové štěpení</a><br>
Návaznosti
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Ostatní
Rok uplatnění
2017
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 Theory and Computation
ISSN
1549-9618
e-ISSN
—
Svazek periodika
13
Číslo periodika v rámci svazku
10
Stát vydavatele periodika
US - Spojené státy americké
Počet stran výsledku
12
Strana od-do
4829-4840
Kód UT WoS článku
000412965700019
EID výsledku v databázi Scopus
2-s2.0-85031039381