화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.105, No.51, 11505-11514, 2001
Alternative approaches for the calculation of induction energies: Characterization, effectiveness, and pitfalls
One of the practical difficulties precluding the generalized development of nonadditive, polarizable models for statistical simulations is rooted in the costly estimation of accurate induction energies, from which distributed polarizabilities can be derived. From a finite perturbation (FP) perspective, mapping the induction energy over a grid of points implies as many distinct quantum chemical calculations of the molecule interacting with a polarizing charge as the total number of points. Here, two alternative routes for computing accurate induction energies in a time-bound fashion are explored. The first one is based upon second-order perturbation theory and only involves a single quantum chemical calculation at the Hartree-Fock level of approximation to map the induction energy. The second one, less straightforward in its implementation, relies on a topological partitioning of the response charge density, also evaluated from a single quantum chemical calculation, yet at virtually any level of sophistication. Critical comparison with reference FP computations reveals that only appropriate scaling of the perturbative (PT) induction energies can warrant a faithful description of polarization phenomena. In the case of neutral molecules, a reasonable reproduction of molecular dipole polarizabilities is achieved when use is made of a simple scaling function that solely depends on the distance separating the points of the grid from the center of mass of the molecule. For anions, the marked anisotropy in the deviation of the PT induction energies from the target FP ones makes the definition of such a general scaling function virtually impossible. In sharp contrast, the approach based upon the topological partitioning of the response charge density does not require any adjustment or scaling, and, thus, constitutes a more robust and rigorous strategy for the computation of induction energies. Examination of distinct protocols for mapping the induction energy emphasizes the necessity to sample the space around the molecule far enough from the nuclei to reproduce molecular dipole polarizabilities accurately. Compared to the spatial extent of the grid, the density of points appears to be of lesser importance.