Large molecular aggregates with sizes ranging from subnanometers to microns are ubiquitous. As atmospheric aerosols they influence our climate, in interstellar space they are discussed as reactive sites, and in medicine small particles are considered as promising candidates to achieve a targeted drug delivery. The present contribution is focused on the characterization of the physical-chemical properties of these particles and on their targeted generation. One of the greatest challenges is to understand the properties of these aggregates on a molecular level. The latter point is discussed in detail focussing on the vibrational dynamics of these particles.

The spectroscopy of aerosols is developing into an active and important field. It allows us to characterize aerosols in a nonintrusive way, in real time, and on site. Understanding the spectroscopic features of these highly complex systems requires the development of novel experimental as well as theoretical methods. This review focuses on infrared extinction spectra. The main goal is to summarize how information about intrinsic particle properties (such as size, shape, and architecture) can be gathered from observed spectroscopic patterns. We discuss the limitations of standard continuum approaches, which have been used for decades to analyze infrared spectra, and we demonstrate the importance of molecular models for the analysis of spectroscopic data.

Infrared extinction spectra of ammonia ice nanoparticles with radii between 2 and 10 nm show pronounced band shape variations depending on the conditions of particle formation by collisional cooling. We present experimental and theoretical evidence showing that the variations in the region of the nu2 (umbrella) fundamental are due to changes in the particle size. The effect is analyzed in terms of an explicit atomistic model of the particles' structure and vibrational dynamics. An explicit potential function combined with a novel extension of the vibrational exciton approach allows us to simulate extinction spectra for particles containing up to 16,000 atoms. It is shown that the particles formed under the conditions of our experiments consist of a crystalline core surrounded by an amorphous shell with an approximately constant thickness of 1-2 nm. For the nu2 fundamental, this shell gives rise to a broad band [full width at half maximum (FWHM) 72 cm(-1)] blueshifted by about 19 cm(-1) relative to a narrow peak (FWHM of 19 cm(-1)) which arises from the crystalline core.

Information on the phase, shape, and architecture of pure SF(6) and mixed SF(6)/CO(2) aerosol particles is extracted from experimental infrared spectra by comparison with predictions from quantum mechanical exciton calculations. The radius of the particles lies around 50 nm. The following extensions to our previous vibrational exciton model are included: (i) To account for the many degrees of freedom of degenerate vibrational bands of aerosol particles, we take a time-dependent approach to calculate infrared absorption spectra directly from the dipole autocorrelation function. (ii) In addition to the dipole-dipole interaction, dipole-induced dipole terms are included to account for the high polarizability of SF(6) and CO(2). We find SF(6) aerosol particles with a cubiclike shape directly after their formation and a change in the shape toward elongated particles with increasing time. Our microscopic model reveals that the cubic-to-monoclinic phase transition at 96 K found in the bulk cannot be observed with infrared spectroscopy because the two phases show almost identical spectra. Infrared spectra of two-component SF(6)/CO(2) particles with core-shell structure show characteristic split absorption bands for the shell. By contrast, homogeneously mixed SF(6)/CO(2) particles lead to broad infrared bands for both the core and the shell. The molecular origin of these various spectral features is uncovered by the analysis of the vibrational eigenfunctions.

Mid-infrared spectra of acetylene aerosol particles generated under conditions relevant to Titan's atmosphere are analyzed in terms of the vibrational exciton model. The analysis reveals that acetylene aerosol particles do not form single crystals below 110 K as previously assumed. Instead, less ordered structures such as polycrystalline particles with orthorhombic crystalline domains or possibly partially amorphous particles derived from an orthorhombic crystal structure are found to be very stable. Annealing of these particles leads to the formation of crystalline particles with an orthorhombic crystal structure. Particles with a cubic crystal structure were never observed at these temperatures in agreement with the phase behavior of bulk acetylene.