MPW1K performs much better than B3LYP in DFT calculations on reactions that proceed by proton-coupled electron transfer (PCET)

Journal of Chemical Theory and Computation

Volumn 2, Issue 3, 2006, Pages 740-745

  Lingwood, Mark ^a   Hammond, Jeff R ^a   Hrovat, David A ^a,b   Mayer, James M ^a   Borden, Weston Thatcher ^a,b  

^a UNIVERSITY OF WASHINGTON   (United States)

^b UNIVERSITY OF NORTH TEXAS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 33746875442     PISSN: 15499618     EISSN: None     Source Type: Journal    
DOI: 10.1021/ct050282z     Document Type: Article

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28. Selected geometries were also reoptimized with the 6-311+G(2df,2p) basis set. However, the relative (U)MPW1K and (U)B3LYP energies at these geometries were essentially the same as the single-point aug-cc-pVTZ energies, computed at the geometries optimized with the 6-31+G(d,p) basis set.
29. 7
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31. -4. There are obvious inaccuracies in using enthalpy and entropy, computed for the gas phase, to calculate the equilibrium constant for hydrogen-bonded complex formation in the solvent mixtures used in ref 9. Nevertheless, the very small equilibrium constant that we do obtain provides good reason to believe that the phenoxyl does not react with α-naphthol in an irreversibly formed hydrogen-bonded complex between them. Instead, our calculations predict that complex formation is reversible, so that the overall enthalpy of activation should be based on the free reactants, rather than on the hydrogen-bonded complex between them.
32. 9