This review describes the vibrational self-consistent field (VSCF) method and its other variants for computing anharmonic vibrational spectroscopy of biological molecules. The superiority and limitations of this algorithm are discussed with examples. The spectroscopic accuracy of the VSCF method is compared with experimental results and other available state-of-the-art algorithms for various biologically important systems. For large biological molecules with many vibrational modes, the scaling of computational effort is investigated. The accuracy of the vibrational spectra of biological molecules using the VSCF approach for different electronic structure methods is also assessed. Finally, a few open problems and challenges in this field are discussed.

New particle formation (NPF) from gaseous precursors as a significant source of aerosol needs to be better understood to accurately predict the impacts on visibility, climate change, and human health. While ternary nucleation of sulfuric acid, amines/NH₃, and water is recognized as a significant driver for NPF, increasing evidence suggests a contribution from methanesulfonic acid (MSA) and amines under certain conditions. Here we report the formation of particles 2.5–10 nm in diameter from the reactions of MSA with methylamine (MA), dimethylamine (DMA), and NH₃ at reaction times of 2.3–7.8 s in a flow reactor and compare these particles with those previously reported to be formed from reaction with trimethylamine (TMA). The effects of water vapor and concentrations of gaseous precursors on the particle number concentration and particle size were studied. The presence of water significantly enhances particle formation and growth. Under similar experimental conditions, particle number concentrations decrease in the order MA ≫ TMA ≈ DMA ≫ NH₃, where NH₃ is 2–3 orders of magnitude less efficient than DMA. Quantum chemical calculations of likely intermediate clusters were carried out to provide insights into the role of water and the different capacities of amines/NH₃ in particle formation. Both gas-phase basicity and hydrogen-bonding capacity of amines/NH₃ contribute to the potential for particles to form and grow. Our results indicate that, although amines typically have concentrations 1–3 orders of magnitude lower than that of NH₃ in the atmosphere, they still play an important role in driving NPF.

▪ Abstract Progress in the study of a new class of chemically bound compounds of noble-gas atoms is reviewed. The focus is on rare-gas molecules of the form HNgY, where Ng is a noble-gas atom and Y is an electronegative group, prepared by photolysis of HY in the rare-gas matrix. Other related types of new molecules of noble-gas atoms are discussed as well. Topics discussed in this review include: (a) The nature of bonding and the energetic stability of the compounds. (b) The vibrational spectroscopy of the molecules, and its role in identification of the species. (c) The mechanism and dynamics of photochemical formation of HNgY in the matrix, and the pathways for thermal and infrared (IR)-induced decomposition. Specifically, attention is given to the issue of “direct” formation following photolysis of HY versus “delayed” formation involving H atom diffusion. (d) Molecules of the lighter rare gases Ar, Ne, and He, focusing on the experimentally prepared HArF and on theoretical predictions suggesting the existence of other molecules. (e) The most-recently discovered photochemically induced insertion compounds of Ng into hydrocarbons, such as HXeCCH. (f) Clusters of HNgY with other molecules. The possible existence of neat aggregates and crystals of HNgY. The reviewed state-of-the-art suggests this field is at an early stage of development with major open questions bearing on the surprising properties of the molecules and on the formation mechanisms. These are part of the challenge for the future.

Atmospheric particles influence visibility, health and climate but the mechanisms of their formation from initial clusters and their growth to detectable particles remain largely unknown. Previous studies show that reactions of methanesulfonic acid (MSA) with ammonia and amines form particles, a process which is enhanced by water. We report here results from a combined experimental-theoretical investigation of the effect of oxalic acid (OxA) on particle formation and growth from the reaction of MSA with trimethylamine (TMA) in the absence and presence of water. The gas phase reactants were mixed in an aerosol flow reactor (1 atm, 294 K). Particle number concentrations and size distributions were measured as a function of reaction time from 0.8–12 s. The interaction of OxA with TMA with and without water does not lead to significant particle formation. When OxA is present during the reaction of MSA with TMA, there is little change (≤2 times more) in the particle number concentration but particles are larger compared to the base case of MSA with TMA alone. However, the presence of water with MSA and TMA overwhelms the effect of OxA so that OxA has no significant impact on particle number concentration or size. Results of these experiments suggest the MSA hydrate is important for particle formation and growth of the four component OxA–MSA–TMA–H₂O system. These results are compared to earlier studies of the effect of OxA on the MSA–methylamine reaction and interpreted based on theoretically calculated properties of small clusters of the components.