Theoretical method for near-field Raman spectroscopy with multipolar Hamiltonian and real-time-TDDFT: Application to on- and off-resonance tip-enhanced Raman spectroscopy.

Tip-enhanced Raman spectroscopy in combination with scanning tunneling microscopy could produce ultrahigh-resolution Raman spectra and images for single-molecule vibrations. Furthermore, a recent experimental study successfully decoupled the interaction between the molecule and the substrate/tip to investigate the intrinsic properties of molecules and their near-field interactions by Raman spectroscopy. In such a circumstance, more explicit treatments of the near field and molecular interactions beyond the dipole approximation would be desirable.

Combined computational quantum chemistry and classical electrodynamics approach for surface enhanced infrared absorption spectroscopy.

Surface enhanced spectroscopy, which enhances the signal intensity of molecules on a surface, facilitates the study of molecular properties, even down to a single-molecule level if a scanning probe is used. To realize the full potential of surface enhanced spectroscopy, a clear theoretical understanding is indispensable. However, quantum chemical calculations for surface enhanced spectroscopy are not simple because of the violation of the widely used dipole approximation.

Single-molecule resonance Raman effect in a plasmonic nanocavity.

Tip-enhanced Raman spectroscopy (TERS) is a versatile tool for chemical analysis at the nanoscale. In earlier TERS experiments, Raman modes with components parallel to the tip were studied based on the strong electric field enhancement along the tip. Perpendicular modes were usually neglected.

First Principles Calculations Toward Understanding SERS of 2,2'-Bipyridyl Adsorbed on Au, Ag, and Au-Ag Nanoalloy.

First principles electrodyanmics and quantum chemical simulations are performed to gain insights into the underlying mechanisms of the surface enhanced Raman spectra of 22BPY adsorbed on pure Au and Ag as well as on Au-Ag alloy nanodiscs. Experimental SERS spectra from Au and Ag nanodiscs show similar peaks, whereas those from Au-Ag alloy reveal new spectral features. The physical enhancement factors due to surface nano-texture were considered by numerical FDTD simulations of light intensity distribution for the nano-textured Au, Ag, and Au-Ag alloy and compared with experimental results.

Generalized theoretical method for the interaction between arbitrary nonuniform electric field and molecular vibrations: Toward near-field infrared spectroscopy and microscopy.

A theoretical method to compute infrared absorption spectra when a molecule is interacting with an arbitrary nonuniform electric field such as near-fields is developed and numerically applied to simple model systems. The method is based on the multipolar Hamiltonian where the light-matter interaction is described by a spatial integral of the inner product of the molecular polarization and applied electric field. The computation scheme is developed under the harmonic approximation for the molecular vibrations and the framework of modern electronic structure calculations such as the density functional theory.