Empirical D3 Dispersion as a Replacement for ab lnitio Dispersion Terms in Density Functional Theory-Based Symmetry-Adapted Perturbation Theory

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00475333" target="_blank" >RIV/61388963:_____/17:00475333 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989592:15310/17:73584585

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.jctc.6b01198" target="_blank" >http://dx.doi.org/10.1021/acs.jctc.6b01198</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jctc.6b01198" target="_blank" >10.1021/acs.jctc.6b01198</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Empirical D3 Dispersion as a Replacement for ab lnitio Dispersion Terms in Density Functional Theory-Based Symmetry-Adapted Perturbation Theory

Popis výsledku v původním jazyce

In density functional theory-based symmetry-adapted perturbation theory (DFT-SAPT) interaction energy calculations, the most demanding step is the calculation of the London dispersion term. For this bottleneck to be avoided and DFT-SAPT to be made applicable to larger systems, the ab initio dispersion terms can be replaced by one calculated empirically at an almost negligible cost (J Phys. Chem. A 2011, 115, 11321-11330). We present an update of this approach that improves accuracy and makes the method applicable to a wider range of systems. It is based on Grimme's D3 dispersion correction for DFT, where the damping function is changed to one suitable for the calculation of the complete dispersion energy. The best results have been achieved with the Tang-Toennies damping function. It has been parametrized on the S66X8 data set for which we report density fitting DFT-SAPT/aug-cc-pVTZ interaction energy decomposition. The method has been validated on a diverse set of noncovalent systems including difficult cases such as very compact noncovalent complexes of charge-transfer type. The root-mean-square errors in the complete test set are 0.73 and 0.42 kcal mol(-1) when charge-transfer complexes are excluded. The proposed empirical dispersion terms can also be used outside the DFT-SAPT framework, e.g., for the estimation of the amount of dispersion in a calculation where only the total interaction energy is known.

Název v anglickém jazyce

Empirical D3 Dispersion as a Replacement for ab lnitio Dispersion Terms in Density Functional Theory-Based Symmetry-Adapted Perturbation Theory

Popis výsledku anglicky

In density functional theory-based symmetry-adapted perturbation theory (DFT-SAPT) interaction energy calculations, the most demanding step is the calculation of the London dispersion term. For this bottleneck to be avoided and DFT-SAPT to be made applicable to larger systems, the ab initio dispersion terms can be replaced by one calculated empirically at an almost negligible cost (J Phys. Chem. A 2011, 115, 11321-11330). We present an update of this approach that improves accuracy and makes the method applicable to a wider range of systems. It is based on Grimme's D3 dispersion correction for DFT, where the damping function is changed to one suitable for the calculation of the complete dispersion energy. The best results have been achieved with the Tang-Toennies damping function. It has been parametrized on the S66X8 data set for which we report density fitting DFT-SAPT/aug-cc-pVTZ interaction energy decomposition. The method has been validated on a diverse set of noncovalent systems including difficult cases such as very compact noncovalent complexes of charge-transfer type. The root-mean-square errors in the complete test set are 0.73 and 0.42 kcal mol(-1) when charge-transfer complexes are excluded. The proposed empirical dispersion terms can also be used outside the DFT-SAPT framework, e.g., for the estimation of the amount of dispersion in a calculation where only the total interaction energy is known.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GJ16-11321Y" target="_blank" >GJ16-11321Y: Rychlý kvantově-mechanický model pro popis nekovalentních interakcí ce velkých molekulárních systémech</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2017

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

13

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

1638-1646

Kód UT WoS článku

000399264200015

EID výsledku v databázi Scopus

2-s2.0-85017514864