Experimentation with different thermodynamic cycles used for pKa calculations on carboxylic acids using Complete Basis Set and Gaussian-n Models combined with CPCM Continuum Solvation Methods

Complete basis set and Gaussian-n methods were combined with Barone and Cossi's implementation of the polarizable conductor model (CPCM) continuum solvation methods to calculate pKa values for six carboxylic acids. Four different thermodynamic cycles were considered in this work. An experimental value of −264.61 kcal/mol for the free energy of solvation of H+, ΔGs(H+), was combined with a value for Ggas(H+) of −6.28 kcal/mol, to calculate pKa values with cycle 1. The complete basis set gas-phase methods used to calculate gas-phase free energies are very accurate, with mean unsigned errors of 0.3 kcal/mol and standard deviations of 0.4 kcal/mol. The CPCM solvation calculations used to calculate condensed-phase free energies are slightly less accurate than the gas-phase models, and the best method has a mean unsigned error and standard deviation of 0.4 and 0.5 kcal/mol, respectively. Thermodynamic cycles that include an explicit water in the cycle are not accurate when the free energy of solvation of a water molecule is used, but appear to become accurate when the experimental free energy of vaporization of water is used. This apparent improvement is an artifact of the standard state used in the calculation. Geometry relaxation in solution does not improve the results when using these later cycles. The use of cycle 1 and the complete basis set models combined with the CPCM solvation methods yielded pKa values accurate to less than half a pKa unit. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001

IORs in development assistance: USAID's agricultural project in Bosnia

We employ the case of USAID's Linking Agricultural Markets with Producers (LAMP) project to address opportunities and obstacles to development assistance. Framed within LAMP's identification of constraints to growth within Bosnia's agricultural market, we explore the complex interorganizational linkages required for success. We identify three distinct linkage types inherent to development situations. Relationships exist (1) within the international community, (2) within the local Bosnian community and (3) between international and local organizations.

The interorganizational challenge of agricultural reform in Bosnia and Herzegovina

The case study reported below examines USAID's "Linking Agricultural Markets with Producers" program. This program complemented Bosnia and Herzegovina's overall sustainable agriculture policies. Implementing organizations quickly recognized that sustainability must be achieved not only from an environmental perspective, but in the interorganizational domain as well. Public, private and nonprofit players had to develop the social, economic and political infrastructure required for sustainable agricultural projects to succeed. These institutional changes were at times more difficult than the sustainable agriculture policies and practices they supported. Framed within LAMP's identification of constraints and proposed solutions for agricultural reform, we explored the interorganizational linkages required for success. We identified three distinct types: 1) those within the international community, 2) those within the local community and 3) those between international and local organizations. The case illustrates the institutional and managerial obstacles to and opportunities for implementing sustainable development reforms in transition settings.

Agricultural Policymaking: Interest Groups and Access to Governmental Officials

Conservation agriculture that focuses on soil recovery is both economically and environmentally sustainable. This lies in contrast with many of the current agricultural practices, which push for high production, which, in turn lead to over-depletion of the soil. Agricultural interest groups play a role in crafting farming policies with governmental officials. Therefore, my study examined three interest group types agribusinesses, farmer organizations, and environmental NGOs that seek to influence agricultural policy, specifically focusing on the federal farm bill, due to its large impact throughout the nation. The research in which data wasgathered through subject interviews, a literature review, and databases found that access to governmental officials affects the amount of influence a group can have. Access is contingent upon: 1) the number of networks (social, professional, and political), 2) amount of money spent through campaign contributions and lobbying expenditures, and 3) extent of business enterprises and subsidiaries. The evidence shows that there is a correlation between these variables and the extent of access. My research concludes that agribusiness interest groups have the most access to government officials, and thus have the greatest influence on agricultural policies. Because agribusinesses support subsidies of commodity-crops this indirectly impacts conservation agriculture, as the two programs compete in a zero-sum game for funding in the farm bills.