PMID- 38112507
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20231219
IS  - 1089-7690 (Electronic)
IS  - 0021-9606 (Linking)
VI  - 159
IP  - 23
DP  - 2023 Dec 21
TI  - An implicit electrolyte model for plane wave density functional theory exhibiting 
      nonlinear response and a nonlocal cavity definition.
LID - 234117 [pii]
LID - 10.1063/5.0176308 [doi]
AB  - We have developed and implemented an implicit electrolyte model in the Vienna Ab 
      initio Simulation Package (VASP) that includes nonlinear dielectric and ionic 
      responses as well as a nonlocal definition of the cavities defining the spatial 
      regions where these responses can occur. The implementation into the existing 
      VASPsol code is numerically efficient and exhibits robust convergence, requiring 
      computational effort only slightly higher than the original linear polarizable 
      continuum model. The nonlinear + nonlocal model is able to reproduce the 
      characteristic "double hump" shape observed experimentally for the differential 
      capacitance of an electrified metal interface while preventing "leakage" of the 
      electrolyte into regions of space too small to contain a single water molecule or 
      solvated ion. The model also gives a reasonable prediction of molecular solvation 
      free energies as well as the self-ionization free energy of water and the 
      absolute electron chemical potential of the standard hydrogen electrode. All of 
      this, combined with the additional ability to run constant potential density 
      functional theory calculations, should enable the routine computation of 
      activation barriers for electrocatalytic processes.
CI  - (c) 2023 Author(s). Published under an exclusive license by AIP Publishing.
FAU - Islam, S M Rezwanul
AU  - Islam SMR
AUID- ORCID: 0009-0006-5588-7149
AD  - Department of Chemical Engineering, Louisiana State University, Baton Rouge, 
      Louisiana 70803, USA.
FAU - Khezeli, Foroogh
AU  - Khezeli F
AD  - Department of Chemical Engineering, Louisiana State University, Baton Rouge, 
      Louisiana 70803, USA.
FAU - Ringe, Stefan
AU  - Ringe S
AUID- ORCID: 0000-0002-7804-1406
AD  - Department of Chemistry, Korea University, Seoul 02841, Republic of Korea.
FAU - Plaisance, Craig
AU  - Plaisance C
AUID- ORCID: 0000-0002-8490-6277
AD  - Department of Chemical Engineering, Louisiana State University, Baton Rouge, 
      Louisiana 70803, USA.
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Chem Phys
JT  - The Journal of chemical physics
JID - 0375360
SB  - IM
EDAT- 2023/12/19 19:53
MHDA- 2023/12/19 19:54
CRDT- 2023/12/19 09:33
PHST- 2023/09/12 00:00 [received]
PHST- 2023/11/15 00:00 [accepted]
PHST- 2023/12/19 19:54 [medline]
PHST- 2023/12/19 19:53 [pubmed]
PHST- 2023/12/19 09:33 [entrez]
AID - 2930317 [pii]
AID - 10.1063/5.0176308 [doi]
PST - ppublish
SO  - J Chem Phys. 2023 Dec 21;159(23):234117. doi: 10.1063/5.0176308.