Exploring Systematic Discrepancies in DFT Calculations of Chlorine Nuclear Quadrupole Couplings

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00476090" target="_blank" >RIV/61388963:_____/17:00476090 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.jpca.7b02810" target="_blank" >http://dx.doi.org/10.1021/acs.jpca.7b02810</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.7b02810" target="_blank" >10.1021/acs.jpca.7b02810</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Exploring Systematic Discrepancies in DFT Calculations of Chlorine Nuclear Quadrupole Couplings

Popis výsledku v původním jazyce

Previous studies have revealed significant discrepancies between density functional theory (DFT)-calculated and experimental nuclear quadrupolar coupling constants (CQ) for chlorine atoms, particularly in ionic solids. Various aspects of the computations are systematically investigated here, including the choice of the DFT functional, basis set convergence, and geometry optimization protocol. The effects of fast (fs) time-scale dynamics are probed using molecular dynamics (MD) and nuclear quantum effects (NQEs) are considered using path-integral MD calculations. It is shown that the functional choice is the most important factor related to improving the accuracy of the quadrupolar coupling calculations, and that functionals beyond the generalized gradient approximation (GGA) level, such as hybrid and meta-GGA functionals, are required for good correlations with experiment. The influence of molecular dynamics and NQEs is less important than the functional choice in the studied systems. A method which involves scaling the calculated quadrupolar coupling constant is proposed here, its application leads to good agreement with experimental data.

Název v anglickém jazyce

Exploring Systematic Discrepancies in DFT Calculations of Chlorine Nuclear Quadrupole Couplings

Popis výsledku anglicky

Previous studies have revealed significant discrepancies between density functional theory (DFT)-calculated and experimental nuclear quadrupolar coupling constants (CQ) for chlorine atoms, particularly in ionic solids. Various aspects of the computations are systematically investigated here, including the choice of the DFT functional, basis set convergence, and geometry optimization protocol. The effects of fast (fs) time-scale dynamics are probed using molecular dynamics (MD) and nuclear quantum effects (NQEs) are considered using path-integral MD calculations. It is shown that the functional choice is the most important factor related to improving the accuracy of the quadrupolar coupling calculations, and that functionals beyond the generalized gradient approximation (GGA) level, such as hybrid and meta-GGA functionals, are required for good correlations with experiment. The influence of molecular dynamics and NQEs is less important than the functional choice in the studied systems. A method which involves scaling the calculated quadrupolar coupling constant is proposed here, its application leads to good agreement with experimental data.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA15-11223S" target="_blank" >GA15-11223S: Vodíkové vazby a nukleární kvantová delokalizace studované pomocí NMR spektroskopie a teoretických výpočtů</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 Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

121

Číslo periodika v rámci svazku

21

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

11

Strana od-do

4103-4113

Kód UT WoS článku

000402775000006

EID výsledku v databázi Scopus

2-s2.0-85021681019