A molecular dynamics study of the hydroxyl radical in solution applying self-interaction-corrected density functional methods.
We have performed density functional theory based molecular dynamics (MD) simulations of the *OH radical in solution using self-interaction corrected (SIC) methods. We use a scheme recently proposed by M. d'Avezac, M. Calandra and F. Mauri [arXiv:cond-mat/0407750] in which a correction is only applied to the spin density within a restricted open shell formulation. In addition to two correction formulas employed within this scheme by M. d'Avezac, M. Calandra and F. Mauri, we propose and test an new empirical form which only introduces a scaled Coulomb term. This new functional leads to good agreement with reference calculations on radical cation dimers and on the hydroxyl water dimer in the gas phase. Applied in ab initio MD simulations, these three SIC methods provide a picture of the *OH solvation that differs qualitatively from the one obtained using the standard generalised gradient approximation (GGA). Hemibonded water, observed in GGA simulations and believed to be an artefact due to self-interaction error, is not present. We find that the *OH acts as a good hydrogen bond donor, but accepts less than two hydrogen bonds on average. These hydrogen bonds are part of a mobile, otherwise quasi-hydrophobic solvation cage. Our results show the potential of this computationally expedient scheme, which might extend the range of problems that can be modelled adequately with density functional theory.
Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, UK CB2 1EW. jv244@cam.ac.uk
Joost
J
VandeVondele
Michiel
M
Sprik
D003198:Computer Simulation; D017665:Hydroxyl Radical / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D012996:Solutions
D012996:Solutions; D017665:Hydroxyl Radical