Symmetry-adapted perturbation theory intermolecular forces

Moszynski R, Wormer PES, Van derAvoird A (2000) Symmetry adapted perturbation theory applied to the computation of intermolecular forces. In Bunker PR, Jensen P (eds) Computational molecular spectroscopy, Wiley, New York, pp69-109... 

Recently, a new theoretical method of calculating potential energy and dipole/polarizability surfaces for van der Waals molecules based on symmetry-adapted perturbation theory (sapt) of intermolecular forces (12)— (15) has been developed (16)-(24). In this method, referred to as many-body symmetry-adapted perturbation theory, all physically important contributions to the potential and the interaction-induced properties, such as electrostatics, exchange, induction, and dispersion are identified and computed separately. By making a perturbation expansion in the intermolecular interaction as well as in the intramolecular electronic correlation, it is possible to sum the correlation contributions to the different physical... 

The interaction energies of clusters of molecules can be decomposed into pair contributions and pairwise-nonadditive contributions. The emphasis of this chapter is on the latter components. Both the historical and current investigations are reviewed. The physical mechanisms responsible for the existence of the many-body forces are described using symmetry-adapted perturbation theory of intermolecular interactions. The role of nonadditive effects in several specific trimers, including some open-shell trimers, is discussed. These effects are also discussed for the condensed phases of argon and water. 

Symmetry-adapted perturbation theory (SAPT) The method describing the intermolecular forces including the hydrogen bonds. 

Some of the contributions address the calculation of intermolecular forces at a fimdamental level, while the majority are concerned with appHcations, ranging from water clusters, through smfaces, to crystal structures. Sza-lewicz, Patkowski and Jeziorski provide a timely review of how perturbation theory can be used to address intermolecular forces in a systematic way. In particular, they describe a new version of symmetry-adapted perturbation theory, which is based on a density functional theory description of the monomers. The interpretation of bonding patterns for both intra- and intermolecular interactions is addressed in Popelier s review, which focuses on quantum chemical topology. He suggests a novel perspective for treating several of the most important contributions to intermolecular forces, and explains how these ideas are related to quantum delocalization. 

SAPT The review articles by Jeziorski, Szalewicz, and others (Jeziorski and Szalewicz 1998, 2002 Jeziorski et al. 1994 Szalewicz 2002 Szalewicz et al. 2005) are probably the most comprehensive articles on symmetry-adapted perturbation theory. See also the discussion of these theories in Stone (1996). For a detailed examination of symmetry-forcing techniques and the convergence of intermolecular perturbation theories see Szalewicz et al. (2005). SAPT(DFT) The theory of the SAPT(DFT) method is described in Misquitta et al. (2005b) and DF-SAPT(DFT) in Podeszwa et al. (2006b). The DF-DFT-SAPT method is described in Hesselmann et al. (2005). 

Misquitta, A. J., 8c Szalewicz, K. (2005). Symmetry-adapted perturbation-theory calculations of intermolecular forces employing density-functional description of monomers. Journal of Chemical Physics, 122, 214109. 

The concept of calculating the interaction energy of two chemical systems A and B perturbatively is not at all a new idea. The first intermolecular perturbation expansion was proposed [22] just a few years after the foundations of quantum mechanics had been laid. Since then, numerous other expansions, now known under a common name of symmetry-adapted perturbation theory, have been introduced and the perturbation theory of intermolecular forces is now a fully mature approach. Thanks to the development of the many-body SAPT [23] and of a general-utility closed-shell SAPT computer code [24], the perturbative approach to intermolecular interactions has been successfully applied to construct PESs for numerous interacting dimers of theoretical and experimental interest [19-21,25-27]. One of the notable achievements of SAPT is an accurate description of the interactions between water molecules [21,28-32]. A recent paper by Keutsch et al. [33] compares the complete spectra of the water dimer with theoretical predictions obtained using an empirical potential fitted to extensive spectroscopic data, and with the predictions from a SAPT potential. These comparisons show that the latter potential probably provides the best current characterization of the water dimer force field. In another recent application, an SAPT PES for heUum in-... 

---