Comparison of Model Chemistry and Density Functional Theory Thermochemical Predictions with Experiment for Formation of Ionic Clusters of the Ammonium Cation Complexed with Water and Ammonia; Atmospheric Implications

The G2, G3, CBS-QB3, and CBS-APNO model chemistry methods and the B3LYP, B3P86, mPW1PW, and PBE1PBE density functional theory (DFT) methods have been used to calculate ΔH° and ΔG° values for ionic clusters of the ammonium ion complexed with water and ammonia. Results for the clusters NH4+(NH3)n and NH4+(H2O)n, where n = 1−4, are reported in this paper and compared against experimental values. Agreement with the experimental values for ΔH° and ΔG° for formation of NH4+(NH3)n clusters is excellent. Comparison between experiment and theory for formation of the NH4+(H2O)n clusters is quite good considering the uncertainty in the experimental values. The four DFT methods yield excellent agreement with experiment and the model chemistry methods when the aug-cc-pVTZ basis set is used for energetic calculations and the 6-31G* basis set is used for geometries and frequencies. On the basis of these results, we predict that all ions in the lower troposphere will be saturated with at least one complete first hydration shell of water molecules.

Hydration of OCS with One to Four Water Molecules in Atmospheric and Laboratory Conditions

Carbonyl sulfide is the most abundant sulfur gas in the atmosphere. We have used MP2 and CCSD(T) theory to study the structures and thermochemistries of carbonyl sulfide interacting with one to four water molecules. We have completed an extensive search for clusters of OCS(H2O)n, where n = 1−4. We located three dimers, two trimers, five tetramers, and four pentamers with the MP2/aug-cc-pVDZ method. In each of the complexes with two or more waters, OCS preferentially interacts with low-energy water clusters. Our results match current theoretical and experimental literature, showing correlation with available geometries and frequencies for the OCS(H2O) species. The CCSD(T)/aug-cc-pVTZ thermochemical values combined with the average amount of OCS and the saturated concentration of H2O in the troposphere, lead to the prediction of 106 OCS(H2O) clusters·cm−3 and 102 OCS(H2O)2 clusters·cm−3 at 298 K. We predict the structures of OCS(H2O)n, n = 1−4 that should predominate in a low-temperature molecular beam and identify specific infrared vibrations that can be used to identify these different clusters.

The Tea Party and Social Movements

The recent rise of the Tea Party movement has added a new dimension to our discussion of domestic politics. The main question is: what effect will the Tea Party have on the political landscape? The best way to answer this question is to place the Tea Party in historical and theoretical context, in order to discuss what type of social movement the Tea Party is and what impact it might have. To this end, I will define and discuss the two major literatures in socialmovement theory: Issue Evolution and Political Process theory. This theoretical framework will provide the basis for a more concrete definition of the Tea Party movement itself. I will attemptto define the Tea Party movement based on its demographics, goals and political successes and will discuss it within the context of this theoretical framework. In addition, I will discuss four landmark social movements within our country’s history through the lens of the theoretical framework. I have found that successful movements rely on a combination of internal organizations and networks and external political opportunities to achieve and maintain nationalrelevance. In the end, I will come to the conclusion that the Tea Party will not likely have a major lasting impact on the political arena. It lacks key parts of the internal structure that makes some movements, such as the Civil Rights movement, so influential. But in the short term it will succeed in pushing the Republican Party towards a more fiscally conservative position.