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.

Comparison of CBS-QB3, CBS-APNO, G2, and G3 thermochemical predictions with experiment for formation of ionic clusters of hydronium and hydroxide ions complexed with water

The GAUSSIAN 2, GAUSSIAN 3, complete basis set-QB3, and complete basis set-APNO methods have been used to calculate ΔH∘ and ΔG∘ values for ionic clusters of hydronium and hydroxide ions complexed with water. Results for the clusters H3O+(H2O)n andOH−(H2O)n, where n=1–4 are reported in this paper, and compared against experimental values contained in the National Institutes of Standards and Technology (NIST) database. Agreement with experiment is excellent for the three ab initio methods for formation of these clusters. The high accuracy of these methods makes them reliable for calculating energetics for the formation of ionic clusters containing water. In addition this allows them to serve as a valuable check on the accuracy of experimental data reported in the NIST database, and makes them useful tools for addressing unresolved issues in atmospheric chemistry.

Response to the Discussion of "The Effect on Financial Reporting Quality of an Exemption From the SEC Reporting Requirements for Foreign Private Issuers"

We appreciate the thorough discussion provided by Professor Yuan Ding. His comments raise legitimate issues. In this response, we offer clarifications and suggest avenues for future research. Our response follows the structure of the discussant’s paper and elaborates on each point separately.

Evaluating Bucknell's Waste Stream

This thesis examines three questions regarding the content of Bucknell University‟s waste stream and the contributors to campus recycling and solid waste disposal. The first asks, “What does Bucknell‟s waste stream consist of?” To answer this question, I designed a campus-wide waste audit procedure that sampled one dumpster from each of the eleven „activity‟ types on campus in order to better understand Bucknell‟s waste composition. The audit was implemented during the Fall semester of the 2011-2012 school year. The waste from each dumpster was sorted into several recyclable and non-recyclable categories and then weighed individually. Results showed the Bison and Carpenter Shop dumpsters to contain the highest percentage of divertible materials (through recycling and/or composting). When extrapolated, results also showed the Dining Services buildings and Facilities buildings to be the most waste dense in terms of pounds of waste generated per square foot. The Bison also generated the most overall waste by weight. The average composition of all dumpsters revealed that organic waste composed 24% of all waste, 23% was non-recyclable paper, and 20% was non-recyclable plastic. It will be important to move forward using these results to help create effective waste programs that target the appropriate areas of concern. My second question asks, “What influences waste behavior to contribute to this „picture‟ of the waste stream?” To answer this question, I created a survey that was sent out to randomly selected sub-group of the university‟s three constituencies: students, faculty, and staff. The survey sought responses regarding each constituency‟s solid waste disposal and recycling behavior, attitudes toward recycling, and motivating factors for solid waste disposal behaviors across different sectors of the university. Using regression analysis, I found three statistically significant motivating factors that influence solid waste disposal behavior: knowledge and awareness, moral value, and social norms. I further examined how a person‟s characteristics associate to these motivating factors and found that one‟s position on campus proved a significant association. Consistently, faculty and staff were strongly influenced by the aforementioned motivating factors, while students‟ behavior was less influenced by them. This suggests that new waste programs should target students to help increase the influence of these motivators to improve the recycling rate and lower overall solid waste disposal on campus. After making overall conclusions regarding the waste audit and survey, I ask my third question, which inquires, “What actions can Bucknell take to increase recycling rates and decrease solid waste generation?” Bucknell currently features several recycling and waste minimization programs on campus. However, using results from the waste audit and campus survey, we can better understand what are the issues of the waste stream, how do we go about addressing these issues, and who needs to be addressed. I propose several suggestions for projects that future students may take on for summer or thesis research. Suggestions include targeting the appropriate categories of waste that occur most frequently in the waste stream, as well as the building types that have the highest waste density and potential recovery rates. Additionally, certain groups on campus should be targeted more directly than others, namely the student body, which demonstrates the lowest influence by motivators of recycling and waste behavior. Several variables were identified as significant motivators of waste and recycling behavior, and could be used as program tactics to encourage more effective behavior.