On the relative acidities of organic compounds: Electronic and geometric relaxation energies

Journal of the American Chemical Society

Volumn 121, Issue 48, 1999, Pages 11217-11222

  Bökman, Fredrik ^a  

^a UPPSALA UNIVERSITY   (Sweden)

Author keywords

[No Author keywords available]

Indexed keywords

ORGANIC COMPOUND;

ACIDITY; ARTICLE; ENERGY TRANSFER; MOLECULAR DYNAMICS; MOLECULAR STABILITY; PROTON TRANSPORT;

EID: 0033537056     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992759k     Document Type: Article

References (44)

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35. 17 was used, the calculated ΔH(298)-values increased by 0.9-1.2 kcal/mol (see Supporting Information). This gave a slightly worse agreement with the experimental ΔH(298)-values (mean deviation +1.0 kcal/mol and rms deviation 1.5 kcal/mol). Since the thermochemical corrections do not enter into the following discussion of relaxation energies, the choice of scale factor is not crucial.
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40. 3) for molecules of similar size: propane 6.37 - ethanol 5.11 - formic acid 3.4 and iso-butane 8.14 - 2-propanol 6.97 - acetic acid 5.1 (Miller, T. M. Atomic and Molecular Polarizabilities. In CRC Handbook of Chemistry and Physics, 76th ed.; Lide, D. R., Ed.; CRC Press: Boca Raton, FL,1995; pp 10/198-10/206).
41. 2=0.9973).)
42. The relative errors (|calculated - experimental|/|experimental|) in ΔΔH(298) for entries a, c, and e of Table 3 are 0.08, 0.02, and 0.23, respectively.
43. 10 (also RHF/6-31++G**) lie well above the correlation line while the three heaviest of the first period hydrides lie well below the line. Common to all three of these series is, however, that R1 increases when -V(H) increases.
44. Taft, R. W.; Taagepera, M.; Abboud, J. L. M.; Wolf, J. F.; DeFrees, D. J.; Hehre, W. J.; Bartmess, J. E.; McIver, R. T., Jr. J. Am. Chem. Soc. 1978, 100, 7765-7767.