The initial microscale mechanisms and materials interfacial process responsible for hydration of calcium silicates are poorly understood even in model systems. The lack of a measured microscale chemical signature has confounded understanding of growth mechanisms and kinetics for microreaction volumes. Here, we use Raman and optical spectroscopies to quantify hydration and environmental carbonation of tricalcium silicates across length and time scales. We show via spatially resolved chemical analysis that carbonate formation during the initial byproduct in microscale reaction volumes is significant, even for subambient CO2 levels. We propose that the competition between carbonation and hydration is enhanced strongly in microscale reaction volumes by increased surface-to-volume ratio relative to macroscale volumes, and by increased concentration of dissolved Ca2+ ions under poor hydration conditions that promote evaporation. This in situ analysis provides the first direct correlation between microscale interfacial hydration and carbonation environments and chemically defined reaction products in cementitious materials.

As the most abundant engineered material on Earth, concrete is essential to the physical infrastructure of all modern societies. There are no known materials that can replace concrete in terms of cost and availability. There are, however, environmental concerns, including the significant CO2 emissions associated with cement production, which create new incentives for university–industry collaboration to address concrete sustainability. Herein, we examine one aspect of this challenge—the translation of scientific understanding at the microscale into industrial innovation at the macroscale—by seeking improvements in cement-paste processing, performance, and sustainability through control of the mechanisms that govern microstructure development. Specifically, we consider modeling, simulation, and experimental advances in fracture, dissolution, precipitation, and hydration of cement paste precursors, as well as properties of the hardened cement paste within concrete. The aim of such studies is to optimize the chemical reactivity, mechanical performance, and other physical properties of cement paste to enable more sustainable processing routes for this ubiquitous material.

Classical molecular dynamics (MD) simulations in conjunction with optical absorption and AFM/nano-Raman experiments are employed to relate the molecular-scale arrangement and conjugation of poly-3-hexylthiophene (P3HT) adsorbed onto single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs). Taken together our results demonstrate the templating role of carbon nanotubes in increasing the π-conjugation length of the P3HT at the P3HT/carbon nanotube interface. The MD simulations show that SWNTs and MWNTs, due to their inherent 1-dimensional (1D) cylindrical shape and π-conjugation, planarize the P3HT molecules adsorbed at their surface and thus quench their torsional disorder, regardless of the P3HT conformation and nanotube chirality. This effect is more significant for higher SWNT weight fractions in the sample (since it is an interface effect). We investigated this effect experimentally by acquiring nano-Raman spectra in regions of high-MWNT/low-P3HT content in addition to optical absorption spectra of P3HT-SWNT composites with different SWNT concentrations . The increase in the P3HT conjugation is confirmed by a shift of a P3HT feature in the Raman spectrum when going from P3HT-rich to SWNT-rich areas in the mixture. The significance of this work for charge transfer at the P3HT-SWNT interface in bulk-heterojunction solar cells is discussed.

This paper first presents the fixed-node diffusion and reptation quantum Monte Carlo (QMC) assessment of density functional theory (DFT) description of weak molecular interactions within several exchange-correlation (XC) approximations. The case of Benzene-molecule complex was studied with a number of small molecules. We found that the binding energy for the set of complexes depend significantly on XC approximation employed although its trend appears rather consistent. Analysis of the reduced density gradient revealed that the binding energy trend among different XC approximation is highly correlated with the exchange enhancement factor behaviors at large reduced density gradients. Our findings point to the importance of accurate exchange energy functional in describing the weak interactions, in addition to the more obvious correlation part in DFT description.

We then present DFT investigation on molecular interaction of NO3 toward a single-wall carbon nanotube (CNT). We aim to explain the atomistic processes that are responsible for the recently observed CNT conductance changes in the redox process. We found that molecular physisorption and chemisorption to be energetically stable states, and the chemisorbed configuration becomes less endothermic with an increased oxidation state of the CNT. Our results also show that the dissociative incorporation of the molecule can become highly favored energetically in the process. This chemical state may play an important role of the occasionally-observed CNT conductance irreversibility in the experiment.