Clusters of classical water models
Authors: Kiss Péter T. , Baranyai András 
Published: November 2009

The properties of clusters can be used as tests of models constructed for molecular simulation of water. We searched for configurations with minimal energies for a small number of molecules. We identified topologically different structures close to the absolute energy minimum of the system by calculating overlap integrals and enumerating hydrogen bonds. Starting from the dimer, we found increasing number of topologically different, low-energy arrangements for the trimer(3), the tetramer(6), the pentamer(6), and the hexamer(9). We studied simple models with polarizable point dipole. These were the BSV model [J. Brodholt et al., Mol. Phys. 86, 149 (1995)], the DC model [L. X. Dang and T. M. Chang, J. Chem. Phys. 106, 8149 (1997)], and the GCP model [P. Paricaud et al., J. Chem. Phys. 122, 244511 (2005)]. As an alternative the SWM4-DP and the SWM4-NDP charge-on-spring models [G. Lamoureux et al., Chem. Phys. Lett. 418, 245 (2006)] were also investigated. To study the impact of polarizability restricted to the plane of the molecule we carried out calculations for the SPC-FQ and TIP4P-FQ models, too [S. W. Rick et al., J. Chem. Phys. 101, 6141 (1994)]. In addition to them, justified by their widespread use even for near critical or surface behavior calculations, we identified clusters for five nonpolarizable models of ambient water, SPC/E [H. J. C. Berendsen et al., J. Phys. Chem. 91, 6269 (1987)], TIP4P [W. L. Jorgensen et al., J. Chem. Phys. 79, 926 (1983)], TIP4P-EW [H. W. Horn et al., J. Chem. Phys. 120, 9665 (2004)], and TIP4P/2005 [J. L. F. Abascal and C. Vega, J. Chem. Phys. 123, 234505 (2005)]. The fifth was a five-site model named TIP5P [M. W. Mahoney and W. L. Jorgensen, J. Chem. Phys. 112, 8910 (2000)]. To see the impact of the vibrations we studied the flexible SPC model. [K. Toukan and A. Rahman, Phys. Rev. B 31, 2643 (1985)]. We evaluated the results comparing them with experimental data and quantum chemical calculations. The position of the negative charge in the models plays a crucial role. In this respect models with SPC geometry provided structures different from the TIP4P-type potentials, including polarizable ones. The TIP4P variants form configurations similar to one another. Results for TIP4P-EW and for TIP4P/2005 were especially close to each other in every respect. This is also true for the BSV and the DC pair. The charge-on-spring models (SWM4-DP and SWM4-NDP) are also very similar to each other, despite the sign exchange of charges on the spring particle and the oxygen. The spherical polarization of water is crucial. Due to the planar polarization of the SPC-FQ and the TIP4P-FQ models, they prefer planar arrangements contrary to other polarizable models and quantum chemical calculations. The tetrahedral geometry of TIP5P stabilizes additional clusters with peculiar geometries and small O–O distances. Inclusion of vibrations causes only insignificant changes in the characteristic geometries but decreases the internal energy relative to its reference rigid version. Comparing with quantum mechanical calculations the GCP model provided the best overall results.