Mi. Bernal-uruchurtu et al., Improving description of hydrogen bonds at the semiempirical level: Water-water interactions as test case, J COMPUT CH, 21(7), 2000, pp. 572-581
Hydrogen bonding is not well described by available semiempirical theories.
This is an important restriction because hydrogen bonds represent a key fe
ature in many chemical and biochemical processes, besides being responsible
for the singular properties of water. In this study, we describe a possibl
e solution to this problem. The basic idea is to replace the nonphysical ga
ussian correction functions (GCF) appearing in the core-core repulsion term
s of most MNDO-based semiempirical methods by a simple function exhibiting
the correct physical behavior in the whole range of intermolecular separati
on distances. The parameterized interaction function (PIF) is the sum of at
om-pair contributions, each one having five adjustable parameters. In this
work, the approach is used to study water-water interactions. The parameter
s are optimized to reproduce a reference ab initio intermolecular energy su
rface for the water-water dimer obtained at the MP2/aug-cc-pVQZ level. OO,
OH, and HH parameters are reported for the PM3 method. The results of PMS-P
IF calculations remarkably improve qualitatively and quantitatively those o
btained at the standard PM3 level, both for water-dimer properties and for
water clusters up to the hexamer. For example, the root-mean-square deviati
on of the PM3-PIF interaction energies, with respect to ab initio values ob
tained using 700 paints of the water dimer surface, is only 0.47 kcal/mol.
This value is much smaller than that obtained using the standard PM3 method
(4.2 kcal/mol). The PM3-PLF water dimer energy minimum ( 5.0 kcal/mol) is
also much closer to ab initio data ( 5.0 +/- 0.01 kcal/mol) than PM3 ( 3.50
kcal/mol). The method is therefore promising for the development of new se
miempirical approaches as well as for application of combined quantum mecha
nics and molecular mechanicstechniques to investigate chemical processes in
water. (C) 2000 John Wiley & Sons, Inc.