FDE-vdW: A van der Waals inclusive subsystem density-functional theory

Journal Article · Mon Jul 28 04:00:00 EDT 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4890839· OSTI ID:22419928

Kevorkyants, Ruslan; Pavanello, Michele ^[1]; Eshuis, Henk ^[2]

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1. Department of Chemistry, Rutgers University, Newark, New Jersey 07102 (United States)
2. Department of Chemistry and Biochemistry, Montclair State University, Montclair, New Jersey 07043 (United States)

We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation–dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method. We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.

• OSTI ID: 22419928
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 4 Vol. 141; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ADDITIVES
BINDING ENERGY
DECOMPOSITION
DENSITY
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
VAN DER WAALS FORCES