Water Dimer under Electric Fields: An Ab Initio Investigation up to Quantum Accuracy

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00587754" target="_blank" >RIV/61388955:_____/24:00587754 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jpca.4c01553?src=getftr" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpca.4c01553?src=getftr</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.4c01553" target="_blank" >10.1021/acs.jpca.4c01553</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Water Dimer under Electric Fields: An Ab Initio Investigation up to Quantum Accuracy

Popis výsledku v původním jazyce

It is well-established that strong electric fields (EFs) can align water dipoles, partially order the H-bond network of liquid water, and induce water splitting and proton transfers. To illuminate the fundamental behavior of water under external EFs, we present the first benchmark, to the best of our knowledge, of DFT calculations of the water dimer exposed to intense EFs against coupled cluster calculations. The analyses of the vibrational Stark effect and electron density provide a consistent picture of the intermolecular charge transfer effects driven along the H-bond by the increasing applied field at all theory levels. However, our findings prove that at extreme field regimes (1-2 V/A) DFT calculations significantly exaggerate by 10-30% the field-induced strengthening of the H-bond, both within the GGA, hybrid GGA, and hybrid meta-GGA approximations. Notably, a linear correlation emerges between the vibrational Stark effect on OH stretching and H-bond strengthening: a 1 kcal mol-1 increase corresponds to an 80 cm-1 red-shift in OH stretching frequency.

Název v anglickém jazyce

Water Dimer under Electric Fields: An Ab Initio Investigation up to Quantum Accuracy

Popis výsledku anglicky

It is well-established that strong electric fields (EFs) can align water dipoles, partially order the H-bond network of liquid water, and induce water splitting and proton transfers. To illuminate the fundamental behavior of water under external EFs, we present the first benchmark, to the best of our knowledge, of DFT calculations of the water dimer exposed to intense EFs against coupled cluster calculations. The analyses of the vibrational Stark effect and electron density provide a consistent picture of the intermolecular charge transfer effects driven along the H-bond by the increasing applied field at all theory levels. However, our findings prove that at extreme field regimes (1-2 V/A) DFT calculations significantly exaggerate by 10-30% the field-induced strengthening of the H-bond, both within the GGA, hybrid GGA, and hybrid meta-GGA approximations. Notably, a linear correlation emerges between the vibrational Stark effect on OH stretching and H-bond strengthening: a 1 kcal mol-1 increase corresponds to an 80 cm-1 red-shift in OH stretching frequency.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

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

1520-5215

Svazek periodika

128

Číslo periodika v rámci svazku

28

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

5490-5499

Kód UT WoS článku

001268366500001

EID výsledku v databázi Scopus

2-s2.0-85198140850