We propose to study the electronic structure and electron dynamics at molecule/solid-surface interfaces in the context of clean energy generation, and green house gas capture. The theoretical calculations performed on the Cascade cluster will be motivated by or will provide theoretical guidance for experiments to be performed with atomic scale spatial and femtosecond temporal resolution at the University of Pittsburgh and the University of Science and Technology of China. Building on our successes in determining the alignment of molecular levels at solid surfaces, specifically the CH3OH/TiO2 system, we will explore the structure and interfacial charge transfer dynamics of small molecules chemisorbed on TiO2 surfaces. The studies will be expanded from the well-known rutile (110) surface to much less well-known anatase surfaces, as well as rutile surfaces with noncompensated doping. The proposed research will elucidate the primary charge transfer processes in TiO2 photocatalysis and strategies for enhancing the solar energy capture. In addition, nonadiabatic molecular dynamics methods will be used to study the structure dependent hole lifetimes in adsorbate localized orbitals on various TiO2 surfaces. Additional research will be performed on atomically resolved studies of CO2 capture by metal surface supported 1D and 2D metal organic chains (MOCs). STM studies performed at the University of Pittsburgh show remarkable ability of 1D MOCs to undergo large-scale surface translation in response to dosing with CO2 molecules. Vibrational and x-ray photoemission spectroscopy of such surfaces indicates the formation of CO2- at the primary adsorption sites. This robust finding, however, is not predicted by DFT calculations, demanding application of quantum chemical approaches. In addition to the primary chemisorption of CO2-, STM imaging shows that the primary chemisorption sites seed the CO2 molecular cluster condensation. Such collective interactions are known from gas phase cluster studies to lead to significant stabilization of the charged species. Thus, the CO2-MOC interactions hold promise as a platform for studying CO2 capture and reduction through combined effort of space and time resolved experiments working in partnership with theory. The proposed studies will advance our understanding of application of electronic materials in energy related applications. The electronic and dynamical properties of molecule-covered solid surfaces are at the forefront of the electronic structure theory and require high-performance computing facilities provided by EMSL. The results of the proposed research are likely to have an impact on the fundamental molecular science for reducing the human impact on global climate and environment.