Assessment of theoretical procedures for calculating barrier heights for a diverse set of water-catalyzed proton-transfer reactions

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

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

Accurate electronic barrier heights are obtained for a set of nine proton-transfer tautomerization reactions, which are either (i) uncatalyzed, (ii) catalyzed by one water molecule, or (iii) catalyzed by two water molecules. The barrier heights for reactions (i) and (ii) are obtained by means of the high-level ab initio W2.2 thermochemical protocol, while those for reaction (iii) are obtained using the W1 protocol. These three sets of benchmark barrier heights allow an assessment of the performance of more approximate theoretical procedures for the calculation of barrier heights of uncatalyzed and water-catalyzed reactions. We evaluate initially the performance of the composite G4 procedure and variants thereof (e.g., G4(MP2) and G4(MP2)-6X), as well as that of standard ab initio procedures (e.g., MP2, SCS-MP2, and MP4). We find that the performance of the G4(MP2)-type thermochemical procedures deteriorates with the number of water molecules involved in the catalysis. This behavior is linked to deficiencies in the MP2-based basis-set-correction term in the G4(MP2)-type procedures. This is remedied in the MP4-based G4 procedure, which shows good performance for both the uncatalyzed and the water-catalyzed reactions, with mean absolute deviations (MADs) from the benchmark values lying below the threshold of "chemical accuracy" (arbitrarily defined as 1 kcal mol -1 ≈ 4.2 kJ mol -1). We also examine the performance of a large number of density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. We find that, with few exceptions (most notably PW6-B95 and B97-2), the performance of the DFT procedures that give good results for the uncatalyzed reactions deteriorates with the number of water molecules involved in the catalysis. The DHDFT procedures, on the other hand, show excellent performance for both the uncatalyzed and catalyzed reactions. Specifically, almost all of them afford MADs below the "chemical accuracy" threshold, with ROB2-PLYP and B2K-PLYP showing the best overall performance.

Original languageEnglish
Pages (from-to)4211-4221
Number of pages11
JournalJournal of Physical Chemistry A
Volume116
Issue number16
DOIs
Publication statusPublished - Apr 26 2012
Externally publishedYes

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Proton transfer
protons
Water
water
Molecules
Discrete Fourier transforms
Catalysis
Density functional theory
catalysis
molecules
density functional theory
deviation
thresholds
Composite materials
composite materials
electronics

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Assessment of theoretical procedures for calculating barrier heights for a diverse set of water-catalyzed proton-transfer reactions. / Karton, Amir; O'Reilly, Robert J.; Radom, Leo.

In: Journal of Physical Chemistry A, Vol. 116, No. 16, 26.04.2012, p. 4211-4221.

Research output: Contribution to journalArticle

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abstract = "Accurate electronic barrier heights are obtained for a set of nine proton-transfer tautomerization reactions, which are either (i) uncatalyzed, (ii) catalyzed by one water molecule, or (iii) catalyzed by two water molecules. The barrier heights for reactions (i) and (ii) are obtained by means of the high-level ab initio W2.2 thermochemical protocol, while those for reaction (iii) are obtained using the W1 protocol. These three sets of benchmark barrier heights allow an assessment of the performance of more approximate theoretical procedures for the calculation of barrier heights of uncatalyzed and water-catalyzed reactions. We evaluate initially the performance of the composite G4 procedure and variants thereof (e.g., G4(MP2) and G4(MP2)-6X), as well as that of standard ab initio procedures (e.g., MP2, SCS-MP2, and MP4). We find that the performance of the G4(MP2)-type thermochemical procedures deteriorates with the number of water molecules involved in the catalysis. This behavior is linked to deficiencies in the MP2-based basis-set-correction term in the G4(MP2)-type procedures. This is remedied in the MP4-based G4 procedure, which shows good performance for both the uncatalyzed and the water-catalyzed reactions, with mean absolute deviations (MADs) from the benchmark values lying below the threshold of {"}chemical accuracy{"} (arbitrarily defined as 1 kcal mol -1 ≈ 4.2 kJ mol -1). We also examine the performance of a large number of density functional theory (DFT) and double-hybrid DFT (DHDFT) procedures. We find that, with few exceptions (most notably PW6-B95 and B97-2), the performance of the DFT procedures that give good results for the uncatalyzed reactions deteriorates with the number of water molecules involved in the catalysis. The DHDFT procedures, on the other hand, show excellent performance for both the uncatalyzed and catalyzed reactions. Specifically, almost all of them afford MADs below the {"}chemical accuracy{"} threshold, with ROB2-PLYP and B2K-PLYP showing the best overall performance.",
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