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  Specific Reaction Path Hamiltonian for Proton Transfer in Water: Reparameterized Semiempirical Models

Wu, X., Thiel, W., Pezeshki, S., & Lin, H. (2013). Specific Reaction Path Hamiltonian for Proton Transfer in Water: Reparameterized Semiempirical Models. Journal of Chemical Theory and Computation, 9(6), 2672-2686. doi:10.1021/ct400224n.

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Item Permalink: http://hdl.handle.net/11858/00-001M-0000-0014-A357-D Version Permalink: http://hdl.handle.net/11858/00-001M-0000-0014-A358-B
Genre: Journal Article

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ct400224n_si_001.pdf (Supplementary material), 2MB
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 Creators:
Wu, Xin1, Author              
Thiel, Walter1, Author              
Pezeshki, Soroosh2, Author
Lin, Hai2, Author
Affiliations:
1Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              
2Chemistry Department, University of Colorado, Denver, Colorado 80217, United State, ou_persistent22              

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Free keywords: Catalysis, Reaction Kinetics, Inorganic Reaction Mechanisms
 Abstract: The semiempirical MNDO-based AM1 and PM3 methods and the orthogonalization-corrected OM1, OM2, and OM3 models were reparameterized to improve their description of bulk water and of proton transfer in water. Reference data included the gas-phase geometries and energies of the water molecule, small water clusters, the hydronium ion, and small hydronium ion–water clusters, as well as the gas-phase potential energy surface for proton transfer between the two water molecules in a Zundel ion, all calculated at the MP2/aug-cc-pVTZ level of theory. Combined QM/MM molecular dynamics simulations were carried out for bulk water and for a proton solvated in water using large cluster models. Both the authentic and reparameterized semiempirical models were employed in the simulations. The reparameterization led to significantly better results in all cases. The new set of OM3 parameters gave the best overall results for the structural and dynamic properties of water and the hydrated proton, with a small but finite barrier of 0.1–0.2 kcal/mol in the potential of mean force for proton transfer, in agreement with ab initio path-integral molecular dynamics simulations. The reparameterized OM3 model is expected to be useful for efficient modeling of proton transfer in aqueous solution.

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Language(s): eng - English
 Dates: 2013-03-202013-05-032013-06-11
 Publication Status: Published in print
 Pages: 15
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ct400224n
 Degree: -

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Title: Journal of Chemical Theory and Computation
  Other : J. Chem. Theory Comput.
Source Genre: Journal
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Publ. Info: Washington, D.C. : American Chemical Society
Pages: 15 Volume / Issue: 9 (6) Sequence Number: - Start / End Page: 2672 - 2686 Identifier: Other: 1549-9618
CoNE: https://pure.mpg.de/cone/journals/resource/111088195283832