Using electronic polarization from the internal continuum (EPIC) for intermolecular interactions.
Recently, the vacuum-phase molecular polarizability tensor of various molecules has been accurately modeled (Truchon et al., J Chem Theory Comput 2008, 4, 1480) with an intramolecular continuum dielectric model. This preliminary study showed that electronic polarization can be accurately modeled when combined with appropriate dielectric constants and atomic radii. In this article, using the parameters developed to reproduce ab initio quantum mechanical (QM) molecular polarizability tensors, we extend the application of the "electronic polarization from internal continuu" (EPIC) approach to intermolecular interactions. We first derive a dielectric-adapted least-square-fit procedure similar to RESP, called DRESP, to generate atomic partial charges based on a fit to a QM abinitio electrostatic potential (ESP). We also outline a procedure to adapt any existing charge model to EPIC. The ability of this to reproduce local polarization, as opposed to uniform polarization, is also examined leading to an induced ESP relative root mean square deviation of 1%, relative to ab initio, when averaged over 37 molecules including aromatics and alkanes. The advantage of using a continuum model as opposed to an atom-centered polarizable potential is illustrated with a symmetrically perturbed atom and benzene. We apply EPIC to a cation-pi binding system formed by an atomic cation and benzene and show that the EPIC approach can accurately account for the induction energy. Finally, this article shows that the ab initio electrostatic component in the difficult case of the H-bonded 4-pyridone dimer, a highly polar and polarized interaction, is well reproduced without adjusting the vacuum-phase parameters.
Truchon
Jean-François
JF
Département de chimie, Université de Montréal, C.P. 6128 Succursale centre-ville, Montréal, Québec, Canada H3C 3J7.
Nicholl's
Anthony
A
Grant
J Andrew
JA
Iftimie
Radu I
RI
Roux
Benoît
B
Bayly
Christopher I
CI
D000473:Alkanes / Q000737:chemistry; D004583:Electrons; D006841:Hydrocarbons, Aromatic / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D011728:Pyridones / Q000737:chemistry; D011789:Quantum Theory; D055672:Static Electricity
D000473:Alkanes; D006841:Hydrocarbons, Aromatic; D011728:Pyridones; C534143:4-pyridone