Gold(I)-N-heterocyclic carbene hydration process; ab initio, DFT, and QM/MM molecular dynamics study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F25%3A10511316" target="_blank" >RIV/00216208:11320/25:10511316 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216224:14310/25:00141478

Výsledek na webu

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

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/5.0268731" target="_blank" >10.1063/5.0268731</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Gold(I)-N-heterocyclic carbene hydration process; ab initio, DFT, and QM/MM molecular dynamics study

Popis výsledku v původním jazyce

This study investigates the hydration reaction of a gold(I)-N-heterocyclic carbene [Au(I)-NHC] complex at both the quantum mechanical (QM) level and combined Quantum Mechanics/Molecular Mechanics (QM/MM) MD simulations. The main goals are to analyze the differences between implicit (PCM) and explicit solvation models and to compare the advantages and disadvantages of both approaches. Regarding the QM part, the B97D3 and B3PW91 functionals are combined with double-zeta basis sets and the C-PCM/UFF implicit solvation model and compared with the CCSD(T)/TZP computational level supplemented with the C-PCM (COSMO/Klamt radii) or D-PCM/scaled-UAKS solvation model. In addition, reaction force and reaction electronic flux (REF) analyses are performed along the intrinsic reaction coordinate (IRC) determined at the B3PW91/6-31+G(d)/SDD/C-PCM/UFF computational model for deeper insights into the reaction mechanism. Despite relatively high endergonicity, the TS structure is quite close to the center of the reaction coordinate, contrary to the Hammond principle. In the QM/MM MD part of the study, the B97D3 computational setting from the previous part is used as a QM core, and several different explicit water solvation models are explored in the MM environment. The TIP3P water model is compared with the OPC, POL3, TIP4P, and SPCE ones. Nevertheless, they all lead to very low activation barriers and mild endergonicity. Both ΔG&lt;inf&gt;r&lt;/inf&gt; and ΔG&lt;inf&gt;a&lt;/inf&gt; energies are visibly reduced compared to QM values when PCM models are applied. Since partial charges of water atoms within the QM calculations are visibly smaller than point charges in all the explored force-field water models, a modified TIP3P (with partial charges close to DFT RESP values and a LJ parameter conserving the correct water density) is used. In this manner, the energy profile is closer to QM results (with ΔG&lt;inf&gt;a&lt;/inf&gt; = 8.2 and ΔG&lt;inf&gt;r&lt;/inf&gt; = 6.4 kcal mol&lt;sup&gt;-1&lt;/sup&gt;)-especially to the CCSD(T)/TZP/D-PCM/scaled-UAKS model (ΔG&lt;inf&gt;a&lt;/inf&gt; = 14.6 and ΔG&lt;inf&gt;r&lt;/inf&gt; = 9.1). Nevertheless, the hydration process is predicted to be endoergic in all explored models.

Název v anglickém jazyce

Gold(I)-N-heterocyclic carbene hydration process; ab initio, DFT, and QM/MM molecular dynamics study

Popis výsledku anglicky

This study investigates the hydration reaction of a gold(I)-N-heterocyclic carbene [Au(I)-NHC] complex at both the quantum mechanical (QM) level and combined Quantum Mechanics/Molecular Mechanics (QM/MM) MD simulations. The main goals are to analyze the differences between implicit (PCM) and explicit solvation models and to compare the advantages and disadvantages of both approaches. Regarding the QM part, the B97D3 and B3PW91 functionals are combined with double-zeta basis sets and the C-PCM/UFF implicit solvation model and compared with the CCSD(T)/TZP computational level supplemented with the C-PCM (COSMO/Klamt radii) or D-PCM/scaled-UAKS solvation model. In addition, reaction force and reaction electronic flux (REF) analyses are performed along the intrinsic reaction coordinate (IRC) determined at the B3PW91/6-31+G(d)/SDD/C-PCM/UFF computational model for deeper insights into the reaction mechanism. Despite relatively high endergonicity, the TS structure is quite close to the center of the reaction coordinate, contrary to the Hammond principle. In the QM/MM MD part of the study, the B97D3 computational setting from the previous part is used as a QM core, and several different explicit water solvation models are explored in the MM environment. The TIP3P water model is compared with the OPC, POL3, TIP4P, and SPCE ones. Nevertheless, they all lead to very low activation barriers and mild endergonicity. Both ΔG&lt;inf&gt;r&lt;/inf&gt; and ΔG&lt;inf&gt;a&lt;/inf&gt; energies are visibly reduced compared to QM values when PCM models are applied. Since partial charges of water atoms within the QM calculations are visibly smaller than point charges in all the explored force-field water models, a modified TIP3P (with partial charges close to DFT RESP values and a LJ parameter conserving the correct water density) is used. In this manner, the energy profile is closer to QM results (with ΔG&lt;inf&gt;a&lt;/inf&gt; = 8.2 and ΔG&lt;inf&gt;r&lt;/inf&gt; = 6.4 kcal mol&lt;sup&gt;-1&lt;/sup&gt;)-especially to the CCSD(T)/TZP/D-PCM/scaled-UAKS model (ΔG&lt;inf&gt;a&lt;/inf&gt; = 14.6 and ΔG&lt;inf&gt;r&lt;/inf&gt; = 9.1). Nevertheless, the hydration process is predicted to be endoergic in all explored models.

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

<a href="/cs/project/GA23-06909S" target="_blank" >GA23-06909S: Grand-kánonický popis chemických reakcí při konstantním pH.</a><br>

Návaznosti

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

Rok uplatnění

2025

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

1089-7690

Svazek periodika

162

Číslo periodika v rámci svazku

21

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

214301

Kód UT WoS článku

001506800700016

EID výsledku v databázi Scopus

2-s2.0-105007447116