Exact functional derivative of the nonadditive kinetic-energy bifunctional in the long-distance limit.
We have investigated the functional derivative of the nonadditive kinetic-energy bifunctional, which appears in the embedding potential that is used in the frozen-density embedding formalism, in the limit that the separation of the subsystems is large. We have derived an exact expression for this kinetic-energy component of the embedding potential and have applied this expression to deduce its exact form in this limit. Comparing to the approximations currently in use, we find that while these approximations are correct at the nonfrozen subsystem, they fail completely at the frozen subsystem. Using test calculations on two model systems, a H2O...Li+ complex and a cluster of aminocoumarin C151 surrounded by 30 water molecules, we show that this failure leads to a wrong description of unoccupied orbitals, which can lead to convergence problems caused by too low-lying unoccupied orbitals and which can further have serious consequences for the calculation of response properties. Based on our results, a simple correction is proposed, and we show that this correction is able to fix the observed problems for the model systems studied.
Jacob
Christoph R
CR
Department of Theoretical Chemistry, Faculty of Sciences, Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV Amsterdam, The Netherlands. jacob@few.vu.nl
Beyhan
S Maya
SM
Visscher
Lucas
L