From plasmon spectra of metallic to vibron spectra of dielectric nanoparticles.
Light interacts surprisingly differently with small particles than with bulk or gas phase materials. This can cause rare phenomena such as the occurence of a "blue moon". Spectroscopic particle phenomena of similar physical origin have also spawned countless applications ranging from remote sensing to medicine. Despite the broad interest in particle spectra, their interpretation still poses many challenges. In this Account, we discuss the challenges associated with the analysis of infrared, or vibron, extinction spectra of small dielectric particles.  The comparison with the more widely studied plasmon spectra of metallic nano-particles reveals many common features. The shape, size, and architecture of particles influence the band profiles in vibron and plasmon spectra in similar ways. However, the molecular structure of dielectric particles produces infrared spectral features that are more diverse and detailed or even unique to vibron spectra. More complexity means higher information content, but that also makes the spectra more difficult to interpret. Conventional models such as classical electromagnetic theory with a continuum description of the wavelength-dependent optical constants are often no longer applicable to these spectra. In cases where accurate optical constants are not available and for ultrafine particles, where the molecular structure and quantum effects become essential, researchers must resort to molecular models for light-particle interaction that do not require the prior knowledge of optical constants. In this Account, we illustrate how vibrational exciton approaches combined with molecular dynamics simulations and solid-state density functional calculations provide a viable solution to these challenges.  Molecular models reveal two important characteristics of vibron spectra of small molecularly structured particles. The band profiles in vibron spectra are largely determined by transition dipole coupling between the molecules in a particle. Below a specific particle size limit, conventional models fail. Molecular models explain many other phenomena in particle spectra, such as size, shape, and mixing effects, providing the foundation for a better understanding of the interaction of solar radiation with aerosols and clouds and for the design of dielectric nanomaterials.
Department of Chemistry, University of British Columbia, Vancouver, BC, Canada.
Thomas C
TC
Preston
Ruth
R
Signorell