Gas-phase energetics

C. F. Correia, P. M. Nunes, R. M. Borges dos Santos, J. A. Martinho Simoes. Gas-Phase Energetics of Organic Free Radicals Using Time-Resolved Photoacoustic Calorimetry. Thermochim. Acta 2004, 420, 3-11. 

With respect to accuracy, it is again important to employ basis sets including diffuse functions when anions are present as either reactants or products. With large well balanced basis sets, B3LYP for gas-phase energetics, and a PB SCRF solvation model, Baik and... 

Molecular dynamics simulations are attractive because they can provide not only quantitative information about rates and pathways of reactions, but also valuable insight into the details of ho y the chemistry occurs. Furthermore, a dynamical treatment is required if the statistical assumption is not valid. Yet another reason for interest in explicit atomic-level simulations of the gas-phase reactions is that they contribute to the formulation of condensed-phase models and, of course, are needed if one is to include the initial stages of the vapor-phase chemistry in the simulations of the decomposition of energetic materials. These and other motivations have lead to a lot of efforts to develop realistic atomic-level models that can be used in MD simulations of the decomposition of gas-phase energetic molecules. 

For most purposes, it suffices to have relative electrode potentials in order to gain the thermodynamic information being sought. This is a fortunate situation since the electrode potential for a half reaction cannot be measured. There are instances where it would be very desirable to be able to estimate the energy of such a reaction. Since the gas phase ionization reactions (39) and (40) can be studied, it is possible to relate the gas phase energetics, the ioniza-... 

UV absorption spectra have been calculated for l,3,5,2,4,6-trithiatriarsinane-2,4,6-trithiol 158 and arsenic(m) sulfide (orpiment, AS4S6) 157 in aqueous solution at CIS and TD B3LYP levels of theory using the 6-311+G(2d,p) basis set <2001MI239>. The bond distances, vibrational frequencies, gas-phase energetics, and proton affinity of 158 have been estimated by means of MO theory <1995M14591>. 

Hoerner, J.K., Xiao, H., Dobo, A., Kaltashov, I.A. (2004) Is there hydrogen scrambling in the gas phase Energetic and structural determinants of proton mobility within protein ions. J Am Chem Soc, 126 (24), 7709-7717. 

Maijolin A, Gourlaouen C, Clavaguera C, Ren P, Wu J, Gresh N, et al. Toward accurate solvation dynamics of lanthanides and actinides in water using polarizable force fields from gas-phase energetics to hydration free energies. Theor Chem Acc. 2012 131 1198. 

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