title: Hybrid Complex Polarization Propagator/Molecular Mechanics Method for Heterogeneous Environments.
abstract: We introduce a hybrid complex polarization propagator/molecular mechanics method for the calculation of near-resonant and resonant response properties of molecules in heterogeneous environments, which consist of a metallic surface, or nanoparticle, and a solvent. The applicability and performance of the method is demonstrated by computations of linear absorption spectra of p-nitroaniline physisorbed at a gold/dimethyl sulfoxide interface in the UV/vis and near-carbon-K-edge regions of the spectrum. It is shown that the shift of absorption cross-section induced by the heterogeneous environment varies significantly depending on the nature of the excited states encountered in the targeted frequency region as well as on the actual size of the resonant frequencies, and that the solvent component of the heterogeneous environment is responsible for the major part of the environmental shift, especially in the higher frequency range of the carbon K-edge region.
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology , SE-106 91 Stockholm, Sweden.|Swedish e-Science Research Centre, KTH Royal Institute of Technology , SE-104 50 Stockholm, Sweden.
authors.forename: Zilvinas
authors.initials: Z
authors.lastname: Rinkevicius
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology , SE-106 91 Stockholm, Sweden.
authors.forename: Jaime A R
authors.initials: JA
authors.lastname: Sandberg
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology , SE-106 91 Stockholm, Sweden.
authors.forename: Xin
authors.initials: X
authors.lastname: Li
authors.affiliation: Department of Physics, Chemistry and Biology, Linköping University , SE-581 83 Linköping, Sweden.|Swedish e-Science Research Centre, Linköping University , SE-581 83 Linköping, Sweden.
authors.forename: Mathieu
authors.initials: M
authors.lastname: Linares
authors.affiliation: Department of Physics, Chemistry and Biology, Linköping University , SE-581 83 Linköping, Sweden.
authors.forename: Patrick
authors.initials: P
authors.lastname: Norman
authors.affiliation: Division of Theoretical Chemistry and Biology, School of Biotechnology, KTH Royal Institute of Technology , SE-106 91 Stockholm, Sweden.
authors.forename: Hans
authors.initials: H
authors.lastname: Ågren