Dispersion corrections to density functionals for water aromatic interactions

Abstract

We investigate recently published methods for extending density functional theory to the description of long-range dispersive interactions. In all schemes an empirical correction consisting of a C6r(-6) term is introduced that is damped at short range. The coefficient C6 is calculated either from average molecular or atomic polarizabilities. We calculate geometry-dependent interaction energy profiles for the water benzene cluster and compare the results with second-order Møller-Plesset calculations. Our results indicate that the use of the B3LYP functional in combination with an appropriate mixing rule and damping function is recommended for the interaction of water with aromatics.

Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections

“…Following the general form of the DFT-D scheme [30][31][32][33][34][35][36][37][38][39][40][41][42][43], our total energy…”

“…Such an approach was used long ago to correct HF calculations [29], and over the past 8 years has been incorporated into density functional theory [30][31][32][33][34][35][36][37][38][39][40][41][42][43]. These DFT-D (density functional theory with empirical dispersion corrections) schemes have shown generally satisfactory performance on a large set of non-covalent systems [35,40].…”

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications

“…183−185 This potential served as a basis for vdW corrections to theories ranging from the HF mean-field approximation, 186 to the Lennard−Jones potential, to semiempirical quantum-chemical methods, long before having been used in DFT. 79,187,188 . In 2004, Grimme popularized this approach in DFT by illustrating that even a simple empirical scheme of this kind improves the performance of standard semilocal exchange-correlation functionals for vdW-bound systems.…”

Adenine versus guanine quartets in aqueous solution: dispersion-corrected DFT study on the differences in π-stacking and hydrogen-bonding behavior

“…Calculations were done using dispersion-corrected DFT-D as developed by Grimme [41][42][43][44][45][46][47] for a correct treatment of the stacking interactions between the DNA bases. The density functionals are augmented with an empirical correction for long-range dispersion effects, described by a sum of damped interatomic potentials of the form C 6 R -6 added to the usual DFT energy [41][42][43][44][45][46][47].…”

“…The density functionals are augmented with an empirical correction for long-range dispersion effects, described by a sum of damped interatomic potentials of the form C 6 R -6 added to the usual DFT energy [41][42][43][44][45][46][47]. Equilibrium structures were optimized using analytical gradient techniques [38].…”