A Hybrid Density Functional Theory/Molecular Mechanics Approach for Linear Response Properties in Heterogeneous Environments

• Published in: Journal of chemical theory and computation 2014-03, Vol.10 (3), p.989-1003
• Main Authors: Rinkevicius, Zilvinas, Li, Xin, Sandberg, Jaime A. R, Mikkelsen, Kurt V, Ågren, Hans
• Format: Article
• Language: English
• Subjects: Energies; Force-Fields; Gas-Phase; Molecular-Dynamics Simulations; Particle Mesh Ewald; Polarizabilities; Proteins; Qm/Mm Approach; Systems
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/ct400897s

We introduce a density functional theory/molecular mechanical approach for computation of linear response properties of molecules in heterogeneous environments, such as metal surfaces or nanoparticles embedded in solvents. The heterogeneous embedding environment, consisting from metallic and nonmetallic parts, is described by combined force fields, where conventional force fields are used for the nonmetallic part and capacitance–polarization-based force fields are used for the metallic part. The presented approach enables studies of properties and spectra of systems embedded in or placed at arbitrary shaped metallic surfaces, clusters, or nanoparticles. The capability and performance of the proposed approach is illustrated by sample calculations of optical absorption spectra of thymidine absorbed on gold surfaces in an aqueous environment, where we study how different organizations of the gold surface and how the combined, nonadditive effect of the two environments is reflected in the optical absorption spectrum.