Joseph Gabriel Cordaro

Coumarin dyes for dye-sensitized solar cells: A long-range-corrected density functional study

The excited-state properties in a series of coumarin solar cell dyes are investigated with a long-range-corrected (LC) functional which asymptotically incorporates Hartree-Fock exchange. Using time-dependent density functional theory (TDDFT), we calculate excitation energies, oscillator strengths, and excited-state dipole moments in each of the dyes as a function of the range-separation parameter mu. To investigate the acceptable range of mu and to assess the quality of the LC-TDDFT formalism, an extensive comparison is made between LC-BLYP excitation energies and approximate coupled-cluster singles and doubles calculations. When using a properly optimized value of mu, we find that the LC technique provides a consistent picture of charge-transfer excitations as a function of molecular size. In contrast, we find that the widely used B3LYP hybrid functional severely overestimates excited-state dipole moments and underestimates vertical excitation energies, especially for larger dye molecules. The results of the present study emphasize the importance of long-range exchange corrections in TDDFT for investigating the excited-state properties in solar cell dyes.

Multicomponent Molten Salt Mixtures Based on Nitrate/Nitrite Anions

Molten salts are a promising medium for thermal energy transfer and storage. They have a very low vapor pressure and most are unreactive in air. Over the past 3 decades, Sandia National Laboratories has investigated a variety of molten salt mixtures of alkali nitrates and, most recently, quaternary mixtures of sodium, calcium, lithium, and potassium nitrate salts. This effort led to the discovery of mixtures with liquidus temperatures below 100°C. We have now extended this work to the mixed nitrate/nitrite anion system and found compositions with liquidus temperatures below 80°C. In this paper, we present experimental results exploring the lithium, sodium, and potassium compositional space with a 1:1 molar mixture of nitrate/nitrite. From our work, we have identified a five-component system with a liquidus temperature near 70°C. Physical properties of these salts, such as viscosity and density, are reported as well as thermal stability in air. Such a molten salt mixture, with a low liquidus temperature, has the potential to make parabolic trough collectors economically competitive with traditional power generation schemes.

Electronic Properties of Vinylene-Linked Heterocyclic Conducting Polymers: Predictive Design and Rational Guidance from DFT Calculations

The band structure and electronic properties in a series of vinylene-linked heterocyclic conducting polymers are investigated using density functional theory (DFT). In order to accurately calculate electronic band gaps, we utilize hybrid functionals with fully periodic boundary conditions to understand the effect of chemical functionalization on the electronic structure of these materials. The use of predictive first-principles calculations coupled with simple chemical arguments highlights the critical role that aromaticity plays in obtaining a low band gap polymer. Contrary to some approaches which erroneously attempt to lower the band gap by increasing the aromaticity of the polymer backbone, we show that being aromatic (or quinoidal) in itself does not ensure a low band gap. Rather, an iterative approach which destabilizes the ground state of the parent polymer toward the aromatic ↔ quinoidal level crossing on the potential energy surface is a more effective way of lowering the band gap in these conjugated systems. Our results highlight the use of predictive calculations guided by rational chemical intuition for designing low band gap polymers in photovoltaic materials.

Improved Synthesis of Bis(borano)hypophosphite Salts

A synthesis of the bis(borano)hypophosphite anion with various counterions has been developed to make use of more benign and commercially available reagents. This method avoids the use of potentially dangerous reagents used by previous methods and gives the final products in good yield. Details of the crystal structure determination of the sodium salt in space group Ama2 are given using a novel computational technique combined with Rietveld refinement.

Thermal Property Testing of Nitrate Thermal Storage Salts in the Solid-Phase

Implementation of molten salt compounds as the heat transfer fluid and energy storage medium provides specific benefits to energy collection and conversion. Nitrate salts have been identified as a strong candidate for energy transfer and storage and have been demonstrated for use in these applications over time. As nitrate salts have solidification temperatures above ambient, concern for recovery from salt freezing events has instigated efforts to understand and predict this behavior. Accurate information of salt property behavior in the solid-phase is necessary for understanding recovery from a freeze event as well as for phase change thermal energy storage applications. Thermal properties for three representative salts (that span the range of melting temperatures from approximately 90–221 °C), have been obtained. These properties include specific heat, coefficient of thermal expansion, and thermal conductivity. Specific heat and thermal conductivity were measured using differential scanning calorimetry.Copyright

Distance Dependent Quenching and Gamma-Ray Spectroscopy in Tin-Loaded Polystyrene Scintillators

In this work, we report the synthesis and inclusion of rationally designed organotin compounds in polystyrene matrices as a route towards plastic scintillators capable of gamma-ray spectroscopy. Tin loading ratios of up to 15% w/w have been incorporated, resulting in photopeak energy resolution values as low as 10.9% for 662 keV gamma-rays. Scintillator constituents were selected based upon a previously reported distance-dependent quenching mechanism. Data obtained using UV-Vis and photoluminescence measurements are consistent with this phenomenon and are correlated with the steric and electronic properties of the respective organotin complexes. We also report fast scintillation decay behavior that is comparable to the quenched scintillators 0.5% trans-stilbene doped bibenzyl and the commercial plastic scintillator BC-422Q-1%. These observations are discussed in the context of practical considerations such as optical transparency, ease-of-preparation/scale-up, and total scintillator cost.

Thermal characterization and model free kinetics of aged epoxies and foams using TGA and DSC methods.

Two classes of materials, poly(methylene diphenyl diisocyanate) or PMDI foam, and cross-linked epoxy resins, were characterized using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), to help understand the effects of aging and %E2%80%9Cbake-out%E2%80%9D. The materials were evaluated for mass loss and the onset of decomposition. In some experiments, volatile materials released during heating were analyzed via mass spectroscopy. In all, over twenty materials were evaluated to compare the mass loss and onset temperature for decomposition. Model free kinetic (MFK) measurements, acquired using variable heating rate TGA experiments, were used to calculate the apparent activation energy of thermal decomposition. From these compiled data the effects of aging, bake-out, and sample history on the thermal stability of materials were compared. No significant differences between aged and unaged materials were detected. Bake-out did slightly affect the onset temperature of decomposition but only at the highest bake-out temperatures. Finally, some recommendations for future handling are made.