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Study of hydrogen bonding interactions relevant to biomolecular structure and function
Author(s) -
Zheng YaJun,
Merz Kenneth M.
Publication year - 1992
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540130916
Subject(s) - hydrogen bond , chemistry , function (biology) , computational chemistry , chemical physics , biology , molecule , evolutionary biology , organic chemistry
Ab initio molecular orbital calculations were used to study hydrogen bonding interactions and interatomic distances of a number of hydrogen bonded complexes that are germane to biomolecular structure and function. The calculations were carried out at the STO‐3G, 3‐21G, 6‐31G*, and MP2/6‐31G* levels (geometries were fully optimized at each level). For anionic species, 6‐31 + G* and MP2/6‐31 + G* were also used. In some cases, more sophisticated calculations were also carried out. Whenever possible, the corresponding enthalpy, entropy, and free energy of complexation were calculated. The agreement with the limited quantity of experimental data is good. For comparison, we also carried out semiempirical molecular orbital calculations. In general, AM1 and PM3 give lower interaction enthalpies than the best ab initio results. With regard to structural results, AM1 tends to favor bifurcated structures for OH‐O and NHO types of hydrogen bonds, but not for hydrogen bonds involving O‐HS and S‐HO, where the usual hydrogen bond patterns are observed. Overall, AM1 geometries are in general in poor agreement with ab initio structural results. On the other hand, PM3 gives geometries similar to the ab initio ones. Hence, from the structural point of view PM3 does show some improvement over AM1. Finally, insights into the formation of cyclic or open formate–water hydrogen bonded complexes are presented. © 1992 by John Wiley & Sons, Inc.