The IMOMO method: Integration of different levels of molecular orbital approximations for geometry optimization of large systems: Test for n-butane conformation and SN2 reaction: RCl+Cl-

Journal of Chemical Physics

Volumn 105, Issue 5, 1996, Pages 1959-1967

  Humbel, Stéphane ^a   Sieber, Stefan ^a   Morokuma, Keiji ^a  

^a EMORY UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001519072     PISSN: 00219606     EISSN: None     Source Type: Journal    
DOI: 10.1063/1.472065     Document Type: Article

References (18)

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14. G. J. Szasz, N. Sheppard, and D. H. Rank, J. Chem. Phys. 16, 704 (1948); K. S. Pitzer, J. Chem. Phys. 8, 711 (1940); K. Ito, J. Am. Chem. Soc. 75, 2430 (1953); J. E. Piercy and M. G. S. Rao, J. Chem. Phys. 46, 3951 (1967).
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18. Jensen (Ref. 11) reported the MP2(non-FC)/6-31G* relative energy of the TS for Cl̄+ neopentyl chloride, relative to the reactants, to be 10.5 kcal/ mol. However, our MP2(FC)/6-31G* calculation, which reproduces all his other results, gives 15.0 kcal/mol (14.9 kcal/mol at the MP2(non-FC)/6-31G* level according to F. Maseras, private communication), as shown in Table VII. Thus, we conclude that there was an error in Jensen's results. His results were referenced in our IMOMM paper [Ref. 6(a)], where the IMOMM(MP2(non-FC)/6-31G*) gave 8.4, 8.1, 10.2. and 14.3 kcal/mol as the TS relative energy, which were compared with his MP2(non-FC)/6-31G* results of 8.4, 7.1, 9.1, and 10.4 kcal/mol, respectively, for ethyl, propyl, isobutyl, and neopentyl chloride. The origin of a large error of 3.9 kcal/mol for neopentyl was not clear at that time. If one replaces the incorrect 10.4 kcal/mol by the correct 14.9 kcal/mol, the agreement of the IMOMM method with the pure ab initio method becomes much better.