Modern Computational Chemistry Methods for Prediction of Ground- and Excited-State Properties in Open-Shell Systems

The main goal of the research presented in this work is to provide some important insights about computational modeling of open-shell species. Such projects are: the investigation of the size-extensivity error in Equation-of-Motion Coupled Cluster methods, the analysis of the Long-Range corrected scheme in predicting UV-Vis spectra of Cu(II) complexes with the 4-imidazole acetate and its ethylated derivative, and the exploration of the importance of choosing a proper basis set for the description of systems such as the lithium monoxide anion. The most significant findings of this research are: (i) The contribution of the left operator to the size-extensivity error of the CR-EOMCC(2,3) approach, (ii) The cause of d-d shifts when varying the range-separation parameter and the amount of the exact exchange arising from the imbalanced treatment of localized vs. delocalized orbitals via the "tuned" CAM-B3LYP* functional, (iii) The proper acidity trend of the first-row hydrides and their lithiated analogs that may be reversed if the basis sets are not correctly selected.

IMPROVEMENTS IN SUSTAINABILITY OF GRAVITY-FED WATER SYSTEMS IN THE COMARCA NGÄBE-BUGLÉ, PANAMA: SPRING CAPTURES AND CIRCUIT RIDER MODEL

Gravity-flow aqueducts are used to bring clean water from mountain springs in the Comarca Ngäbe-Buglé, Panama, to the homes of the indigenous people who reside there. Spring captures enclose a spring to direct the flow of water into the transmission line. Seepage contact springs are most common, with water appearing above either hard basalt bedrock or a dense clay layer. Spring flows vary dramatically during wet and dry seasons, and discharge points of springs can shift, sometimes enough to impact the capture structure and its ability to properly collect all of the available water. Traditionally, spring captures are concrete boxes. The spring boxes observed by the author were dilapidated or out of alignment with the spring itself, only capturing part of the discharge. An improved design approach was developed that mimics the terrain surrounding the spring source to address these issues. Over the course of a year, three different spring sites were evaluated, and spring captures were designed and constructed based on the new approach. Spring flow data from each case study demonstrate increased flow capture in the improved structures. Rural water systems, including spring captures, can be sustainably maintained by the Circuit Rider model, a technical support system in which technical assistance is provided for the operation of the water systems. During 2012-2013, the author worked as a Circuit Rider and facilitated a water system improvement project while exploring methods of community empowerment to increase the capacity for system maintenance. Based on these experiences, recommendations are provided to expand the Circuit Rider model in the Comarca Ngäbe-Buglé under the Panamanian Ministry of Health’s Water and Sanitation Project (PASAP)