Efficient calculation of van der Waals dispersion coefficients with time-dependent density functional theory in real time: Application to polycyclic aromatic hydrocarbons

TitleEfficient calculation of van der Waals dispersion coefficients with time-dependent density functional theory in real time: Application to polycyclic aromatic hydrocarbons
Publication TypePalaiseau Article
Author Address

Marques, MAL (Reprint Author), Univ Coimbra, Ctr Fis Computac, Dept Fis, Coimbra, Portugal. Univ Coimbra, Ctr Fis Computac, Dept Fis, Coimbra, Portugal. Free Univ Berlin, Inst Theoret Phys, Fachbereich Phys, D-14195 Berlin, Germany. INAF Osservatorio Astron Cagliari, Astrochem Grp, I-109012 Capoterra, CA, Italy. Ecole Polytech, Lab Solides Irradies, CNRS, CEA, Palaiseau, France. Univ Coimbra, Ctr Fis Computac, Dept Fis, Coimbra, Portugal.

DOI10.1063/1.2746031
Marques, M, Castro, A, Malloci, G, Mulas, G, Botti, S
Year of Publication2007
JournalJOURNAL OF CHEMICAL PHYSICS
Volume127
URLhttp://dx.doi.org/10.1063/1.2746031
Keywordspaper
Abstract

The van der Waals dispersion coefficients of a set of polycyclic aromatic hydrocarbons, ranging in size from the single-cycle benzene to circumovalene (C66H20), are calculated with a real-time propagation approach to time-dependent density functional theory (TDDFT). In the nonretarded regime, the Casimir-Polder integral is employed to obtain C-6, once the dynamic polarizabilities have been computed at imaginary frequencies with TDDFT. On the other hand, the numerical coefficient that characterizes the fully retarded regime is obtained from the static polarizabilities. This ab initio strategy has favorable scaling with the size of the system-as demonstrated by the size of the reported molecules-and can be easily extended to obtain higher order van der Waals coefficients. (c) 2007 American Institute of Physics.

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