The original formula of Gibbs for the reversible work of critical nucleus formation is evaluated in three approximate ways for ordinary and heavy water. The least approximate way employs an equation of state to evaluate the pressure difference between the new and old phases. This form of the theory yields a temperature dependence for the nucleation rate close to that observed experimentally. This is a substantial improvement over the most commonly used (and most approximate) form of classical theory.

Two intermolecular potential models of methanol (TraPPE-UA and OPLS-AA) have been used in order to examine their validity in reproducing the selected structural, dynamical, and thermodynamic properties in the unary and binary systems. These two models are combined with two water models (SPC/E and TIP4P). The temperature dependence of density, surface tension, diffusion and structural properties for the unary system has been computed over specific range of temperatures (200-300K). The very good performance of the TraPPE-UA potential model in predicting surface tension, diffusion, structure, and density of the unary system led us to examine its accuracy and performance in its aqueous solution. In the binary system the same properties were examined, using different mole fractions of methanol. The TraPPE-UA model combined with TIP4P-water shows a very good agreement with the experimental results for density and surface tension properties; whereas the OPLS-AA combined with SPCE-water shows a very agreement with experimental results regarding the diffusion coefficients. Two different approaches have been used in calculating the diffusion coefficient in the mixture, namely the Einstein equation (EE) and Green-Kubo (GK) method. Our results show the advantageous of applying GK over EE in reproducing the experimental results and in saving computer time.

We study the internal structure of nanometer-sized D2O-nonane aerosol droplets formed in supersonic nozzle expansions using a variety of experimental techniques including small angle X-ray scattering (SAXS). By fitting the SAXS spectra to a wide range of droplet structure models, we find that the experimental results are inconsistent with mixed droplets that form aqueous core-organic shell structures, but are quite consistent with spherically asymmetric lens-on-sphere structures. The structure that agrees best with the SAXS data and Fourier transform infra-red spectroscopy measurements is that of a nonane lens on a sphere of D2O with a contact angle in the range of 40°-120°.

Our molecular dynamics (MD) simulations have shown that nanodroplets containing water and nonane are nonspherical and strongly phase-separated. This "Russian doll" structure may be simply but realistically modeled as a spherical nonane lens that partially wets a spherical water droplet. We call this the lens-on-sphere model. Here, we present an analytical calculation of the particle form factor, P(q), needed to analyze the intensity curves for small-angle neutron and X-ray scattering by aerosol particles with this type of structure. For this model, the particle form factor must be evaluated by numerical integration. In addition, an exact formulation of the particle form factor is presented for cylindrically symmetric droplets with otherwise arbitrary position-dependent scattering length density. This result enables direct calculation of P(q) from numerical MD simulation data. Results using both formulations are compared, and excellent agreement is found between them. Analytical results are also presented for two limiting cases of the general result: the sphere-on-sphere model and the sphere-in-sphere (SIS) model, corresponding to contact angles of 180° and 0°, respectively. Finally, a generalization of the SIS model to ellipsoidal droplets is given.