The Role of Anharmonicity in Hydrogen-Bonded Systems: The Case of Water Clusters

ACS Citation

Temelso, B.; Shields, G. C. The Role of Anharmonicity in Hydrogen-Bonded Systems: The Case of Water Clusters. J. Chem. Theory Comput. 2011, 7 (9), 2804-2817.


The nature of vibrational anharmonicity has been examined for the case of small water clusters using second-order vibrational perturbation theory (VPT2) applied on second-order Møller-Plesset perturbation theory (MP2) potential energy surfaces. Using a training set of 16 water clusters (H2O)n=2-6,8,9 with a total of 723 vibrational modes, we determined scaling factors that map the harmonic frequencies onto anharmonic ones. The intermolecular modes were found to be substantially more anharmonic than intramolecular bending and stretching modes. Due to the varying levels of anharmonicity of the intermolecular and intramolecular modes, different frequency scaling factors for each region were necessary to achieve the highest accuracy. Furthermore, new scaling factors for zero-point vibrational energies (ZPVE) and vibrational corrections to the enthalpy (ΔHvib) and the entropy (Svib) have been determined. All the scaling factors reported in this study are different from previous works in that they are intended for hydrogen-bonded systems, while others were built using experimental frequencies of covalently bonded systems. An application of our scaling factors to the vibrational frequencies of water dimer and thermodynamic functions of 11 larger water clusters highlights the importance of anharmonic effects in hydrogen-bonded systems.

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Journal of Chemical Theory and Computation

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