Condensed Phase Interactions

Unlike the chemistry of simple mixtures of small numbers of reactants, the chemistry of the atmosphere involves complex interactions of large numbers of species. However, several key aspects of these interactions have been identified that account for major observable properties of the atmospheric chemical system. It is convenient to separate the description into gas phase and condensed phase interactions, not least because different chemical and physical processes are involved in these two cases. 

3 Downward flux to troposphere, small difference between 1 and 2 

7 Release of CH4 at ground by variety of sources with range 1.3-3.3 E13 moles/year (E13 = 10 ). 2.5 E13 with average OH concentration of 6E 5 molecules cm  

CH3 -F O2 + H CH3O2 + M CH3O2 + NO- CH3O -F NO2 CH3O -F 02 CH2O -F HO2 CH2O-F hv CO + H2 and other oxidation routes. 

11a Release of CO from variety of sources, mostly man-made. 

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Condensed phase interactions can be divided roughly into two further categories chemical and physical. The latter involves all purely physical processes such as condensation of species of low volatility onto the surfaces of aerosol particles, adsorption, and absorption into liquid cloud and rainwater. Here, the interactions may be quite complex. For example, cloud droplets require a CCN, which in many instances is a particle of sulfate produced from SO2 and gas-particle conversion. If this particle is strongly acidic (as is often the case) HNO3 will not deposit on the aerosol particle rather, it will be dissolved in liquid water in clouds and rain. Thus, even though HNO3 is not very soluble in... 

Since chemical species in condensed phases interact strongly, solids and liquids are more complicated than gases, where intermolecular forces are usually negligible. The interactions of atoms, molecules, and ions are electrostatic in origin, but there are several types of interaction with quite different energies ... 

From a fundamental point of view, the study of gas-phase and condensed-phase interactions between alkali-metal ions and biologically active molecules is of great interest, as these interactions relate to chemical and biological processes oeemring in the heterogeneous regions. This can help to study processes such as ion solvation. 

As in the other systems already considered, condensed phase interactions determine the effectiveness of the fire retardant. 

The total interaction between two slabs of infinite extent and depth can be obtained by a summation over all atom-atom interactions if pairwise additivity of forces can be assumed. While definitely not exact for a condensed phase, this conventional approach is quite useful for many purposes [1,3]. This summation, expressed as an integral, has been done by de Boer [8] using the simple dispersion formula, Eq. VI-15, and following the nomenclature in Eq. VI-19 ... 

Of course, condensed phases also exliibit interesting physical properties such as electronic, magnetic, and mechanical phenomena that are not observed in the gas or liquid phase. Conductivity issues are generally not studied in isolated molecular species, but are actively examined in solids. Recent work in solids has focused on dramatic conductivity changes in superconducting solids. Superconducting solids have resistivities that are identically zero below some transition temperature [1, 9, 10]. These systems caimot be characterized by interactions over a few atomic species. Rather, the phenomenon involves a collective mode characterized by a phase representative of the entire solid. 

The existence of intennolecular interactions is apparent from elementary experimental observations. There must be attractive forces because otherwise condensed phases would not fomi, gases would not liquefy, and liquids would not solidify. There must be short-range repulsive interactions because otherwise solids and liquids could be compressed to much smaller volumes with ease. The kernel of these notions was fomuilated in the late eighteenth century, and Clausius made a clear statement along the lines of this paragraph as early as 1857 [1]. 

Kramers solution of the barrier crossing problem [45] is discussed at length in chapter A3.8 dealing with condensed-phase reaction dynamics. As the starting point to derive its simplest version one may use the Langevin equation, a stochastic differential equation for the time evolution of a slow variable, the reaction coordinate r, subject to a rapidly statistically fluctuating force F caused by microscopic solute-solvent interactions under the influence of an external force field generated by the PES F for the reaction... 

Of great interest to physical chemists and chemical physicists are the broadening mechanisms of Raman lines in the condensed phase. Characterization of tliese mechanisms provides infomiation about the microscopic dynamical behaviour of material. The line broadening is due to the interaction between the Raman active chromophore and its environment. 

The scope of this section restricts the discussion. One omitted topic is the collision and interaction of molecules with surfaces (see [20, 21] and section A3.9). This topic coimects quantum molecular dynamics in gas and condensed phases. Depending on the time scales of the interaction of a molecule witli a surface, the... 

The most important molecular interactions of all are those that take place in liquid water. For many years, chemists have worked to model liquid water, using molecular dynamics and Monte Carlo simulations. Until relatively recently, however, all such work was done using effective potentials [4T], designed to reproduce the condensed-phase properties but with no serious claim to represent the tme interactions between a pair of water molecules. 

Interaction between Gaseous and Condensed Phases. In a closed vessel of volume Ucontaining a nonionized, unexcited molecular gas having total number of molecules A/, the change in the pressure P in the gas can often be predicted if the steady-state absolute temperature Tis changed to another steady, constant level ... 

Proper condensed phase simulations require that the non-bond interactions between different portions of the system under study be properly balanced. In biomolecular simulations this balance must occur between the solvent-solvent (e.g., water-water), solvent-solute (e.g., water-protein), and solute-solute (e.g., protein intramolecular) interactions [18,21]. Having such a balance is essential for proper partitioning of molecules or parts of molecules in different environments. For example, if the solvent-solute interaction of a glutamine side chain were overestimated, there would be a tendency for the side chain to move into and interact with the solvent. The first step in obtaining this balance is the treatment of the solvent-solvent interactions. The majority of biomolecular simulations are performed using the TIP3P [81] and SPC/E [82] water models. 

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