PNNL

Abstract

Semiempirical SCF methods such as MNDO, AM1, and PM3 have the ability to treat the formation and breaking of chemical bonds but have been found to poorly describe hydrogen bonding and weak electrostatic complexes. In contrast, most empirical potentials are not able to describe bond-breaking and formation, but have the ability to add missing elements of hydrogen bonding using classical electrostatic interactions. We present a new method which combines aspects of both NDDO-based SCF techniques and classical descriptions of polarization to describe the diffuse nature of the electronic wavefunction in a self-consistent manner. We develop the “self-consistent polarization neglect of differential diatomic overlap” (SCP-NDDO) theory with the additional description of molecular dispersion developed as a second-order perturbation theory expression. The current study seeks to model water-water interactions as a test case. To this end, we have parameterized the SCP-NDDO model to the accurate MP2/CBS estimates of small water cluster binding energies of Xantheas et al.[S. S. Xantheas, C. J. Burnham, and R. J. Harrison, J. Chem. Phys. 116, 1493 (2002); S. S. Xantheas and E. Aprà, J. Chem. Phys. 120, 823 (2004)]. Overall agreement with the ab initio binding energies (n = 2 – 6, 8) is achieved with an RMS error of 0.20 kcal/mol. We achieve noticeable improvements in the structure, vibrational frequencies, and energetic predictions of water clusters (n = 21) relative to standard NDDO-based methods.