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Extension of the PDDG/PM3 semiempirical molecular orbital method to sulfur, silicon, and phosphorus
被引:62
作者:
Tubert-Brohman, I
[1
]
Guimaraes, CRW
[1
]
Jorgensen, WL
[1
]
机构:
[1] Yale Univ, Dept Chem, New Haven, CT 06520 USA
关键词:
D O I:
10.1021/ct0500287
中图分类号:
O64 [物理化学(理论化学)、化学物理学];
学科分类号:
070304 ;
081704 ;
摘要:
The PDDG/PM3 semiempirical molecular orbital method has been parametrized for molecules, ions, and complexes containing sulfur; the mean absolute error (MAE) for heats of formation, Delta H-f, of 6.4 kcal/mol is 35-40% smaller than those for PM3, AM1, and MNDO/d. For completeness, parametrization was also carried out for silicon and phosphorus. For 144 silicon-containing molecules, the Delta H-f MAE for PDDG/PM3, PM3, and AM1 is 11 -12 kcal/mol, whereas MNDO/d yields 9.4 kcal/mol. For the limited set of 43 phosphorus-containing molecules, MNDO/d also yields the best results followed by PDDG/PM3, AM1, and PM3. The benefits of the d orbitals in MNDO/d for hypervalent compounds are apparent for silicon and phosphorus, whereas they are masked in the larger dataset for sulfur by large errors for branched compounds. Overall, for 1480 molecules, ions, and complexes containing the elements H, C, N, O, F, Si, P, S, Cl, Br, and I, the MAEs in kcal/mol for Delta Hf are 6.5 (PDDG/PM3), 8.7 (PM3), 10.3 (MNDO/d), 10.8 (AM1), and 19.8 (MNDO).
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页码:817 / 823
页数:7
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