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

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 non-retarded regime, the Casimir-Polder integral is employed to obtain C6, 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.

submitted to J. Chem. Phys

References in corpus (8)

• On-line database of the spectral properties of polycyclic aromatic hydrocarbons
• Stacked clusters of polycyclic aromatic hydrocarbon molecules
• Assessment of exchange-correlation functionals for the calculation of dynamical properties of small clusters in TDDFT
• Formation and destruction of polycyclic aromatic hydrocarbon clusters in the interstellar medium
• Theoretical evaluation of PAH dications properties
• Optical response of small carbon clusters
• Retarded and nonretarded van der Waals interactions between a cluster and a second cluster or a conducting surface
• Fully retarded van der Waals interaction between dielectric nanoclusters

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• Origin of the size-dependence of the equilibrium van der Waals binding between nanostructures
• Accurate ground state- and quasiparticle energies: beyond the RPA and GW methods with adiabatic exchange-correlation kernels
• Linear/circular spectropolarimetry of diffuse interstellar bands
• Cluster-surface and cluster-cluster interactions: Ab initio calculations and modeling of van der Waals forces
• A computational scheme to evaluate Hamaker constants of molecules with practical size and anisotropy
• Assessment of range-separated time-dependent density-functional theory for calculating C6 dispersion coefficients
• Energy scaling law for nanostructured materials
• Van der Waals Coefficients of Atoms and Molecules from a Simple Approximation for the Polarizability