Abstract
The electrostatic continuum solvent model developed by [Fattebert and Gygi J. Comput. Chem. 23, 662 (2002); Int. J. Quantum Chem. 93, 139 (2003)] is combined with a first-principles formulation of the cavitation energy based on a natural quantum-mechanical definition for the surface of a solute. Despite its simplicity, the cavitation contribution calculated by this approach is found to be in remarkable agreement with that obtained by more complex algorithms relying on a large set of parameters. Our model allows for very efficient Car-Parrinello simulations of finite or extended systems in solution and demonstrates a level of accuracy as good as that of established quantum-chemistry continuum solvent methods. We apply this approach to the study of tetracyanoethylene dimers in dichloromethane, providing valuable structural and dynamical insights on the dimerization phenomenon.
| Original language | English |
|---|---|
| Article number | 074103 |
| Journal | Journal of Chemical Physics |
| Volume | 124 |
| Issue number | 7 |
| DOIs | |
| State | Published - 2006 |
| Externally published | Yes |
Funding
The authors thank Patrick Sit for his help in postprocessing the velocity autocorrelation functions and for useful discussions. The authors also thank the reviewer for helpful remarks. This research was supported by the MURI Grant No. DAAD 19-03-1-0169 and by the Institute of Soldier Nanotechnologies, Contract No. DAAD-19-02-D0002, with the U.S. Army Research Office. A portion of this work was performed under the auspices of the U.S. Department of Energy by University of California Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48