The Intricate Case of Tetramethyleneethane: A Full Configuration Interaction Quantum Monte Carlo Benchmark and Multireference Coupled Cluster Studies

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F18%3A10439851" target="_blank" >RIV/00216208:11320/18:10439851 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388955:_____/18:00489863

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=8uJfb9By0y" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=8uJfb9By0y</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.8b00022" target="_blank" >10.1021/acs.jctc.8b00022</a>

Jazyk výsledku

angličtina

Název v původním jazyce

The Intricate Case of Tetramethyleneethane: A Full Configuration Interaction Quantum Monte Carlo Benchmark and Multireference Coupled Cluster Studies

Popis výsledku v původním jazyce

We have performed a full configuration interaction (FCI) quality benchmark calculation for the tetramethyleneethane molecule in the cc-pVTZ basis set employing a subset of complete active space second order perturbation theory, CASPT2(6,6), natural orbitals for the FCI quantum Monte Carlo calculation. The results are in an excellent agreement with the previous large scale diffusion Monte Carlo calculations by Pozun et al. and available experimental results. Our computations verified that there is a maximum on the potential energy surface (PES) of the ground singlet state ((1)A) 45 degrees torsional angle, and the corresponding vertical singlet triplet energy gap is 0.01 eV. We have employed this benchmark for the assessment of the accuracy of Mukherjee&apos;s coupled clusters with up to triple excitations (MkCCSDT) and CCSD tailored by the density matrix renormalization group method (DMRG). Multireference MkCCSDT with CAS(2,2) model space, though giving good values for the singlet-triplet energy gap, is not able to properly describe the shape of the multireference singlet PES. Similarly, DMRG(24,25) is not able to correctly capture the shape of the singlet surface, due to the missing dynamic correlation. On the other hand, the DMRG-tailored CCSD method describes the shape of the ground singlet state with excellent accuracy but for the correct ordering requires computation of the zero-spin-projection component of the triplet state (B-3(1)).

Název v anglickém jazyce

The Intricate Case of Tetramethyleneethane: A Full Configuration Interaction Quantum Monte Carlo Benchmark and Multireference Coupled Cluster Studies

Popis výsledku anglicky

We have performed a full configuration interaction (FCI) quality benchmark calculation for the tetramethyleneethane molecule in the cc-pVTZ basis set employing a subset of complete active space second order perturbation theory, CASPT2(6,6), natural orbitals for the FCI quantum Monte Carlo calculation. The results are in an excellent agreement with the previous large scale diffusion Monte Carlo calculations by Pozun et al. and available experimental results. Our computations verified that there is a maximum on the potential energy surface (PES) of the ground singlet state ((1)A) 45 degrees torsional angle, and the corresponding vertical singlet triplet energy gap is 0.01 eV. We have employed this benchmark for the assessment of the accuracy of Mukherjee&apos;s coupled clusters with up to triple excitations (MkCCSDT) and CCSD tailored by the density matrix renormalization group method (DMRG). Multireference MkCCSDT with CAS(2,2) model space, though giving good values for the singlet-triplet energy gap, is not able to properly describe the shape of the multireference singlet PES. Similarly, DMRG(24,25) is not able to correctly capture the shape of the singlet surface, due to the missing dynamic correlation. On the other hand, the DMRG-tailored CCSD method describes the shape of the ground singlet state with excellent accuracy but for the correct ordering requires computation of the zero-spin-projection component of the triplet state (B-3(1)).

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

—

Návaznosti

S - Specificky vyzkum na vysokych skolach<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Theory and Computation

ISSN

1549-9618

e-ISSN

—

Svazek periodika

14

Číslo periodika v rámci svazku

5

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

2439-2445

Kód UT WoS článku

000431926500014

EID výsledku v databázi Scopus

2-s2.0-85046755028