Calculated gas-phase acidities using density functional theory: Is it reliable?

Journal of Physical Chemistry

Volumn 100, Issue 44, 1996, Pages 17465-17471

  Merrill, Grant N ^a   Kass, Steven R ^a  

^a University of Minnesota ^*  (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 22244435668     PISSN: 00223654     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp961557x     Document Type: Article

References (68)

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45. It is also worth noting that density functional theory often gives positive eigenvalues for the highest occupied molecular orbitals of anions. Although this is troubling, it does not necessarily diminish the utility of DFT for calculating proton affinities of anionic systems. Similar studies involving anions, specifically the calculation of electron affinities, give good results. See: (a) Galbraith, J. M.; Schaefer, H. F., III J. Chem. Phys. 1996, 105, 862.
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48. 2 stationary point at the HF level.
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54. - is poorly described by most common basis sets.
55. The average experimental uncertainty for the acids in Tables 1 and 2 is 1.7 kcal/mol.
56. 2SO, and 3.5 (HCN)).
57. 3Cl), and 4.3 (HCN) kcal/mol).
58. B-null, B-VWN, and B-LYP have 24, 6, and 14 proton affinities, respectively, which differ from experimental values by ≥5 kcal/mol, and these numbers increase to 28, 11, and 20 if one sets the limit to ≥4 kcal/ mol.
59. 2SO, which is 0.9 kcal/mol too big.
60. 2 = 0.983, for B-null and B-LYP proton affinities, respectively. In the former case 3 acidities deviate by ≥5 kcal/ mol, 5 by ≥4 kcal/mol, and 12 by ≥3 kcal/mol. The corresponding numbers for the latter functional are 2, 3, and 5, respectively.
61. 2 = 0.975, but the results are only slightly improved and there still are an unacceptable number of outlying points (i.e., 3 at ≥5 kcal/mol, 7 at ≥4 kcal/mol, and 10 at ≥3 kcal/mol).
62. 2CN) kcal/mol.
63. The aug-cc-pVDZ basis set is only slightly larger for heavy (non-hydrogenic) atoms than the 6-31+G(d) basis set, whereas the aug-cc-pVTZ basis set is approximately 50% bigger than the 6-311++G(2df,2pd) basis set for non-hydrogenic atoms.
64. It is likely that other parametrized functionals (e.g., B3-LYP and B3-P86) will also perform well.
65. 2 = 0.993 (B3-PW91/IV). When the calculated acidities are scaled, the average unsigned errors are reduced to 2.0 (S-null/III), 2.2 (S-null/IV), 1.8 (S-VWN/III), 2.0 (S-VWN/IV), 2.1 (S-LYP/III), 2.4 (S-LYP/IV), 1.8 (B-null/III), 2.2 (B-null/IV), 1.8 (B-VWN/ III), 2.2 (B-VWN/IV), 1.3 (B-LYP/III), 1.8 (B-LYP/IV), 1.1 (B3-PW91/ III), and 1.2 (B3-PW91/IV) kcal/mol.
66. Del Bene, J. E. J. Phys. Chem. 1993, 97, 107.
67. 2 = 0.978, owing to small differences in the experimental data that was used.
68. B-VWN calculations are also faster than those carried out using B-LYP.