Determination of barrier heights for proton exchange in small water, ammonia, and hydrogen fluoride clusters with G4(MP2)-type, MPn, and SCS-MPn procedures-a caveat

Amir Karton, Robert J. O'Reilly, Bun Chan, Leo Radom

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

Calculation of accurate water-water interaction energies is of fundamental importance in computational modeling of many biological and chemical phenomena. We have obtained benchmark barrier heights for proton-exchange reactions and complexation energies in water clusters (H 2O) n (n = 1-6) by means of the high-level W1-F12 procedure. We find that lower-cost composite procedures (e.g., G4(MP2) and G4(MP2)-6X), as well as MP2 and SCS-MP2, exhibit surprisingly poor performance for the barrier heights of reactions involving multiple proton exchanges. Moreover, the performance significantly deteriorates with increasing size of the clusters. Similar observations apply to complexation energies in water clusters, and to barrier heights for proton exchange in ammonia and hydrogen fluoride clusters. We propose a modified version of G4(MP2)-6X (denoted G4(MP2)-6X+) that includes sp- and d-diffuse functions in the CCSD(T) term, which gives excellent proton-exchange barrier heights at a computational cost only slightly greater than that of standard G4(MP2). G4(MP2)-6X+ also leads to a substantial improvement over G4(MP2) and G4(MP2)-6X for the calculation of electron affinities.

Original languageEnglish
Pages (from-to)3128-3136
Number of pages9
JournalJournal of Chemical Theory and Computation
Volume8
Issue number9
DOIs
Publication statusPublished - Sep 11 2012
Externally publishedYes

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Hydrofluoric Acid
hydrofluoric acid
Ammonia
fluorides
Protons
ammonia
Ion exchange
Hydrogen
protons
Water
Complexation
water
Electron affinity
electron affinity
energy
Costs
costs
composite materials
Composite materials
interactions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications

Cite this

Determination of barrier heights for proton exchange in small water, ammonia, and hydrogen fluoride clusters with G4(MP2)-type, MPn, and SCS-MPn procedures-a caveat. / Karton, Amir; O'Reilly, Robert J.; Chan, Bun; Radom, Leo.

In: Journal of Chemical Theory and Computation, Vol. 8, No. 9, 11.09.2012, p. 3128-3136.

Research output: Contribution to journalArticle

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