A Theoretical Investigation of Small Organic Molecules on Transition Metal Surfaces

With the ever growing number of proposed desnity functional theory (DFT) functionals it becomes necessary to thoroughly screen any new method to determine its merit. Especially relevant methods include a proper description of the van der Waals (vdW) interaction, which can prove vital to a correct description of a myriad of systems of technological importance. The first part of this dissertation explores the utility of several vdW-inclusive DFT functionals including optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, rPW86-vdW2, and SCAN+rVV10 by applying them to model systems of small organic molecules, pyridine and thiophene, on transition metal surfaces. Overall, we find the optB88-vdW functional gives the best, most balanced description of both thiophene and pyridine on transition metal surfaces while revPBE-vdW, rPW86-vdW2, and SCAN+rVV10 functionals perform especially poorly for these systems. In the second part of this dissertation we change our focus to potential applications of DFT. Specifically, we study the hydrodesulfurization (HDS) process and molecules that could be used in molecular electronics. The removal of sulfur containing molecules from petrochemicals through HDS is an exceptionally important process economically, and the field of molecular electronics is rapidly developing with hopes of competing with and replacing their silicon analogues. First we investigate the hydrodesulfurization of thiophene. In this dissertation we manage to map the HDS rate of thiophene in realistic reaction conditions to the charge transfer and adsorption energy of thiophene on bare transition metal surfaces in hopes of predicting ever more active HDS catalysis. Finally we look at the adsorption of polythiophenes and 5,14-dihydro-5,7,12,14-tetraazapentacene (DHTAP) on Au(111) and Cu(110). We find that polythiophenes may dissociate of Au(111), presenting an issue for their use in molecular electronics. DHTAP, in contrast, proves to a suitable candidate for use practical devices

Comparing three approaches of spatial disaggregation of legacy soil maps based on 1 DSMART algorithm

Enhancing the spatial resolution of pedological information is a great challenge in the field of Digital Soil 34 Mapping (DSM). Several techniques have emerged to disaggregate conventional soil maps initially 35 available at coarser spatial resolution than required for solving environmental and agricultural issues. At the 36 regional level, polygon maps represent soil cover as a tessellation of polygons defining Soil Map Units 37 (SMU), where each SMU can include one or several Soil Type Units (STU) with given proportions derived 38 from expert knowledge. Such polygon maps can be disaggregated at finer spatial resolution by machine 39 learning algorithms using the Disaggregation and Harmonisation of Soil Map Units Through Resampled 40 Classification Trees (DSMART) algorithm. This study aimed to compare three approaches of spatial 41 disaggregation of legacy soil maps based on DSMART decision trees to test the hypothesis that the 42 disaggregation of soil landscape distribution rules may improve the accuracy of the resulting soil maps. 43 Overall, two modified DSMART algorithm (DSMART with extra soil profiles, DSMART with soil 44 landscape relationships) and the original DSMART algorithm were tested. The quality of disaggregated soil 45 maps at 50 m resolution was assessed over a large study area (6,775 km2) using an external validation based 46 on independent 135 soil profiles selected by probability sampling, 755 legacy soil profiles and existing 47 detailed 1:25,000 soil maps. Pairwise comparisons were also performed, using Shannon entropy measure, 48 to spatially locate differences between disaggregated maps. The main results show that adding soil landscape 49 relationships in the disaggregation process enhances the performance of prediction of soil type distribution. 50 Considering the three most probable STU and using 135 independent soil profiles, the overall accuracy 51 measures are: 19.8 % for DSMART with expert rules against 18.1 % for the original DSMART and 16.9 % 52 for DSMART with extra soil profiles. These measures were almost twofold higher when validated using 53 3x3 windows. They achieved 28.5% for DSMART with soil landscape relationships, 25.3% and 21% for 54 original DSMART and DSMART with extra soil observations, respectively. In general, adding soil 55 landscape relationships as well as extra soil observations constraints the model to predict a specific STU 56 that can occur in specific environmental conditions. Thus, including global soil landscape expert rules in 57 the DSMART algorithm is crucial to obtain consistent soil maps with clear internal disaggregation of SMU 58 across the landscape

Photoexcitation dynamics in perylene diimide dimers

We utilize first-principles theory to investigate photo-induced excited-state dynamics of functionalized perylene diimide. This class of materials is highly suitable for solar energy conversion because of the strong optical absorbance, efficient energy transfer, and chemical tunability. We couple time-dependent density functional theory to a recently developed time-resolved non-adiabatic dynamics approach based on a semi-empirical description. By studying the monomer and dimer, we focus on the role stacking plays on the time-scales associated with excited-state non-radiative relaxation from a high excitonic state to the lowest energy exciton. We predict that the time-scale for energy conversion in the dimer is significantly faster than that in the monomer when equivalent excited states are accounted for. Additionally, for the dimer, the decay from the second to the nearly degenerate lowest energy excited-state involves two time-scales: a rapid decay on the order of ∼10 fs followed by a slower decay of ∼100 fs. Analysis of the spatial localization of the electronic transition density during the internal conversion process points out the existence of localized states on individual monomers, indicating that the strength of thermal fluctuations exceeds electronic couplings between the states such that the exciton hops between localized states throughout the simulation.Fil: Mukazhanova, Aliya. Boston University; Estados UnidosFil: Malone, Walter. Los Alamos National High Magnetic Field Laboratory; Estados UnidosFil: Negrín Yuvero, Lázaro Hassiel. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Fernández Alberti, Sebastián. Universidad Nacional de Quilmes. Departamento de Ciencia y Tecnología; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Tretiak, Sergei. Los Alamos National High Magnetic Field Laboratory; Estados UnidosFil: Sharifzadeh, Sahar. Boston University; Estados Unido

How Should Research And Monitoring Be Integrated?

Scientific knowledge of Chesapeake Bay and tidal tributaries has accumulated over many years beginning mostly with descriptive surveys prior to the 1960\u27s and 1970\u27s and evolving towards a coupling of monitoring and research in recent years. This essay discusses the need to more fully couple monitoring and research efforts in the Bay system because such a union of efforts is argued to be the most effective way to assess gross trends in the health of the system (monitoring) and to understand the basic forces causing these trends (research). We argue that together they provide part of the framework necessary for effective management of the living resources of the bay region.https://scholarworks.wm.edu/vimsbooks/1176/thumbnail.jp

Data-driven methods for diffusivity prediction in nuclear fuels

The growth rate of structural defects in nuclear fuels under irradiation is intrinsically related to the diffusion rates of the defects in the fuel lattice. The generation and growth of atomistic structural defects can significantly alter the performance characteristics of the fuel. This alteration of functionality must be accurately captured to qualify a nuclear fuel for use in reactors. Predicting the diffusion coefficients of defects and how they impact macroscale properties such as swelling, gas release, and creep is therefore of significant importance in both the design of new nuclear fuels and the assessment of current fuel types. In this article, we apply data-driven methods focusing on machine learning (ML) to determine various diffusion properties of two nuclear fuels, uranium oxide and uranium nitride. We show that using ML can increase, often significantly, the accuracy of predicting diffusivity in nuclear fuels in comparison to current analytical models. We also illustrate how ML can be used to quickly develop fuel models with parameter dependencies that are more complex and robust than what is currently available in the literature. These results suggest there is potential for ML to accelerate the design, qualification, and implementation of nuclear fuels

Triphenylene-Derived Electron Acceptors and Donors on Ag(111):Formation of Intermolecular Charge-Transfer Complexes with Common Unoccupied Molecular States

Over the past years, ultrathin films consisting of electron donating and accepting molecules have attracted increasing attention due to their potential usage in optoelectronic devices. Key parameters for understanding and tuning their performance are intermolecular and molecule–substrate interactions. Here, the formation of a monolayer thick blend of triphenylene‐based organic donor and acceptor molecules from 2,3,6,7,10,11‐hexamethoxytriphenylene (HAT) and 1,4,5,8,9,12‐hexaazatriphenylenehexacarbonitrile (HATCN), respectively, on a silver (111) surface is reported. Scanning tunneling microscopy and spectroscopy, valence and core level photoelectron spectroscopy, as well as low‐energy electron diffraction measurements are used, complemented by density functional theory calculations, to investigate both the electronic and structural properties of the homomolecular as well as the intermixed layers. The donor molecules are weakly interacting with the Ag(111) surface, while the acceptor molecules show a strong interaction with the substrate leading to charge transfer and substantial buckling of the top silver layer and of the adsorbates. Upon mixing acceptor and donor molecules, strong hybridization occurs between the two different molecules leading to the emergence of a common unoccupied molecular orbital located at both the donor and acceptor molecules. The donor acceptor blend studied here is, therefore, a compelling candidate for organic electronics based on self‐assembled charge‐transfer complexes

MP758: East Regional Potato Trials 2006: Summary of NE1014 Regional Project Field Testing of New Potato Clones

The objectives of this regional potato trial are (1) to develop pest-resistant, early-maturing, long-dormant potato varieties that will process from cold storage; (2) to evaluate new and specialty variet­ies developed in the Northeast; (3) to determine climatic effects on performance to develop pre­dictive models for potato improvement; and (4) determine heritability/linkage relationships and improve the genetic base of tetraploid cultivated varieties. The results presented in this report reflect a portion of the activity directed toward objectives 1, 2 and 3.https://digitalcommons.library.umaine.edu/aes_miscpubs/1017/thumbnail.jp

MP760: East Regional Potato Trials 2007: Summary of NE1014 Regional Project Field Testing of New Potato Clones

The objectives of this regional potato trial are (1) to develop pest-resistant, early-maturing, long-dormant potato varieties that will process from cold storage; (2) to evaluate new and specialty variet­ies developed in the Northeast; (3) to determine climatic effects on performance to develop pre­dictive models for potato improvement; and (4) determine heritability/linkage relationships and improve the genetic base of tetraploid cultivated varieties. The results presented in this report reflect a portion of the activity directed toward objectives 1, 2 and 3.https://digitalcommons.library.umaine.edu/aes_miscpubs/1016/thumbnail.jp

MP757: Eastern Regional Potato Trials 2005: Summary of NE1014 Regional Project Field Testing of New Potato Clones

The objectives of this regional potato trial are (1) to develop pest-resistant, early-maturing, long-dormant potato varieties that will process from cold storage; (2) to evaluate new and specialty variet­ies developed in the Northeast; (3) to determine climatic effects on performance to develop pre­dictive models for potato improvement; and (4) determine heritability/linkage relationships and improve the genetic base of tetraploid cultivated varieties. The results presented in this report reflect a portion of the activity directed toward objectives 1, 2 and 3.https://digitalcommons.library.umaine.edu/aes_miscpubs/1018/thumbnail.jp