Laser Powder Bed Fusion of Molybdenum and Mo-0.1SiC Studied by Positron Annihilation Lifetime Spectroscopy and Electron Backscatter Diffraction Methods.

Positron annihilation lifetime spectroscopy (PALS) has been used for the first time to investigate the microstructure of additively manufactured molybdenum. Despite the wide applicability of positron annihilation spectroscopy techniques to the defect analysis of metals, they have only been used sparingly to monitor the microstructural evolution of additively manufactured metals. Molybdenum and molybdenum with a dilute addition (0.1 wt%) of nano-sized silicon carbide, prepared via laser powder bed fusion (LPBF) at four different scan speeds: 100, 200, 400, and 800 mm/s, were studied by PALS and compared with electron backscatter diffraction analysis. The aim of this study was to clarify the extent to which PALS can be used to identify microstructural changes resulting from varying LPBF process parameters. Grain sizes and misorientation results do not correlate with positron lifetimes indicating the positrons are sampling regions within the grains. Positron annihilation spectroscopy identified the presence of dislocations and nano-voids not revealed through electron microscopy techniques and correlated with the findings of SiO2 nanoparticles in the samples prepared with silicon carbide. The comparison of results indicates the usefulness of positron techniques to characterize nano-structure in additively manufactured metals due to the significant increase in atomic-level information.

Valence and charge-transfer optical properties for some SinCm (m, n ≤ 12) clusters: Comparing TD-DFT, complete-basis-limit EOMCC, and benchmarks from spectroscopy.

Accurate optical characterization of the closo-Si12C12 molecule is important to guide experimental efforts toward the synthesis of nano-wires, cyclic nano-arrays, and related array structures, which are anticipated to be robust and efficient exciton materials for opto-electronic devices. Working toward calibrated methods for the description of closo-Si12C12 oligomers, various electronic structure approaches are evaluated for their ability to reproduce measured optical transitions of the SiC2, Si2Cn (n = 1-3), and Si3Cn (n = 1, 2) clusters reported earlier by Steglich and Maier [Astrophys. J. 801, 119 (2015)]. Complete-basis-limit equation-of-motion coupled-cluster (EOMCC) results are presented and a comparison is made between perturbative and renormalized non-iterative triples corrections. The effect of adding a renormalized correction for quadruples is also tested. Benchmark test sets derived from both measurement and high-level EOMCC calculations are then used to evaluate the performance of a variety of density functionals within the time-dependent density functional theory (TD-DFT) framework. The best-performing functionals are subsequently applied to predict valence TD-DFT excitation energies for the lowest-energy isomers of SinC and Sin-1C7-n (n = 4-6). TD-DFT approaches are then applied to the SinCn (n = 4-12) clusters and unique spectroscopic signatures of closo-Si12C12 are discussed. Finally, various long-range corrected density functionals, including those from the CAM-QTP family, are applied to a charge-transfer excitation in a cyclic (Si4C4)4 oligomer. Approaches for gauging the extent of charge-transfer character are also tested and EOMCC results are used to benchmark functionals and make recommendations.

The closo-Si12C12 molecule from cluster to crystal: Effects of hydrogenation and oligomerization on excited states.

Excited state properties of chain and cyclic oligomers of closo-Si12C12 moieties are calculated using time-dependent density functional theory methods. Ultraviolet, visible, and near-infrared photo-absorption properties are described for oligomers that form by linking closo-Si12C12 monomer moieties through Si-Si bonds. Natural transition orbitals for electron and hole states of stationary-state excitons in oligomers were compared to understand how exciton states are influenced by oligomer structure. Depending on the structure, some prominent excited states have large electron-hole charge separation while others do not; some exhibit exciton delocalization while others do not. With increasing oligomer length, the character of the transition between silicon and carbon regions tends to be maintained. And the extent of exciton delocalization and charge separation for an excitation is strongly influenced by the number and types of Si-Si links between oligomer units. We find that cyclic quadramers have spectroscopy properties akin to those of J-aggregates, including the tendency to collapse oligomer excitation transition energies into a narrow single peak. Hydrogenation influences some excited state distributions and energies. Phase behaviors reveal electron state or hole state equivalence in certain molecules that are differently hydrogenated, illustrating the potential for near-resonant exciton transfer between adjacent donor and acceptor species.

Predictive coupled-cluster isomer orderings for some SinCm (m, n ≤ 12) clusters: A pragmatic comparison between DFT and complete basis limit coupled-cluster benchmarks.

The accurate determination of the preferred Si12C12 isomer is important to guide experimental efforts directed towards synthesizing SiC nano-wires and related polymer structures which are anticipated to be highly efficient exciton materials for the opto-electronic devices. In order to definitively identify preferred isomeric structures for silicon carbon nano-clusters, highly accurate geometries, energies, and harmonic zero point energies have been computed using coupled-cluster theory with systematic extrapolation to the complete basis limit for set of silicon carbon clusters ranging in size from SiC3 to Si12C12. It is found that post-MBPT(2) correlation energy plays a significant role in obtaining converged relative isomer energies, suggesting that predictions using low rung density functional methods will not have adequate accuracy. Utilizing the best composite coupled-cluster energy that is still computationally feasible, entailing a 3-4 SCF and coupled-cluster theory with singles and doubles extrapolation with triple-ζ (T) correlation, the closo Si12C12 isomer is identified to be the preferred isomer in the support of previous calculations [X. F. Duan and L. W. Burggraf, J. Chem. Phys. 142, 034303 (2015)]. Additionally we have investigated more pragmatic approaches to obtaining accurate silicon carbide isomer energies, including the use of frozen natural orbital coupled-cluster theory and several rungs of standard and double-hybrid density functional theory. Frozen natural orbitals as a way to compute post-MBPT(2) correlation energy are found to be an excellent balance between efficiency and accuracy.

Nanomechanical Characterization of Bacillus anthracis Spores by Atomic Force Microscopy.

UNLABELLED: The study of structures and properties of bacterial spores is important to understanding spore formation and biological responses to environmental stresses. While significant progress has been made over the years in elucidating the multilayer architecture of spores, the mechanical properties of the spore interior are not known. Here, we present a thermal atomic force microscopy (AFM) study of the nanomechanical properties of internal structures of Bacillus anthracis spores. We developed a nanosurgical sectioning method in which a stiff diamond AFM tip was used to cut an individual spore, exposing its internal structure, and a soft AFM tip was used to image and characterize the spore interior on the nanometer scale. We observed that the elastic modulus and adhesion force, including their thermal responses at elevated temperatures, varied significantly in different regions of the spore section. Our AFM images indicated that the peptidoglycan (PG) cortex of Bacillus anthracis spores consisted of rod-like nanometer-sized structures that are oriented in the direction perpendicular to the spore surface. Our findings may shed light on the spore architecture and properties. IMPORTANCE: A nanosurgical AFM method was developed that can be used to probe the structure and properties of the spore interior. The previously unknown ultrastructure of the PG cortex of Bacillus anthracis spores was observed to consist of nanometer-sized rod-like structures that are oriented in the direction perpendicular to the spore surface. The variations in the nanomechanical properties of the spore section were largely correlated with its chemical composition. Different components of the spore materials showed different thermal responses at elevated temperatures.

The closo-Si12C12 molecule from cluster to crystal: A theoretical prediction.

The structure of closo-Si12C12 is unique among stable SinCm isomers (n, m > 4) because of its high symmetry, π-π stacking of C6 rings and unsaturated silicon atoms at symmetrical peripheral positions. Dimerization potential surfaces reveal various dimerization reactions that form between two closo-Si12C12 molecules through Si-Si bonds at unsaturated Si atoms. As a result the closo-Si12C12 molecule is capable of polymerization to form stable 1D polymer chains, 2D crystal layers, and 3D crystals. 2D crystal structures formed by side-side polymerization satisfy eight Si valences on each monomer without large distortion of the monomer structure. 3D crystals are formed by stacking 2D structures in the Z direction, preserving registry of C6 rings in monomer moiety.

Theoretical investigation of stabilities and optical properties of Si12C12 clusters.

By sorting through hundreds of globally stable Si12C12 isomers using a potential surface search and using simulated annealing, we have identified low-energy structures. Unlike isomers knit together by Si-C bonds, the lowest energy isomers have segregated carbon and silicon regions that maximize stronger C-C bonding. Positing that charge separation between the carbon and silicon regions would produce interesting optical absorption in these cluster molecules, we used time-dependent density functional theory to compare the calculated optical properties of four isomers representing structural classes having different types of silicon and carbon segregation regions. Absorptions involving charge transfer between segregated carbon and silicon regions produce lower excitation energies than do structures having alternating Si-C bonding for which frontier orbital charge transfer is exclusively from separated carbon atoms to silicon atoms. The most stable Si12C12 isomer at temperatures below 1100 K is unique as regards its high symmetry and large optical oscillator strength in the visible blue. Its high-energy and low-energy visible transitions (1.15 eV and 2.56 eV) are nearly pure one-electron silicon-to-carbon transitions, while an intermediate energy transition (1.28 eV) is a nearly pure carbon-to-silicon one-electron charge transfer.

Nanoscale structural and mechanical analysis of Bacillus anthracis spores inactivated with rapid dry heating.

Effective killing of Bacillus anthracis spores is of paramount importance to antibioterrorism, food safety, environmental protection, and the medical device industry. Thus, a deeper understanding of the mechanisms of spore resistance and inactivation is highly desired for developing new strategies or improving the known methods for spore destruction. Previous studies have shown that spore inactivation mechanisms differ considerably depending upon the killing agents, such as heat (wet heat, dry heat), UV, ionizing radiation, and chemicals. It is believed that wet heat kills spores by inactivating critical enzymes, while dry heat kills spores by damaging their DNA. Many studies have focused on the biochemical aspects of spore inactivation by dry heat; few have investigated structural damages and changes in spore mechanical properties. In this study, we have inactivated Bacillus anthracis spores with rapid dry heating and performed nanoscale topographical and mechanical analysis of inactivated spores using atomic force microscopy (AFM). Our results revealed significant changes in spore morphology and nanomechanical properties after heat inactivation. In addition, we also found that these changes were different under different heating conditions that produced similar inactivation probabilities (high temperature for short exposure time versus low temperature for long exposure time). We attributed the differences to the differential thermal and mechanical stresses in the spore. The buildup of internal thermal and mechanical stresses may become prominent only in ultrafast, high-temperature heat inactivation when the experimental timescale is too short for heat-generated vapor to efficiently escape from the spore. Our results thus provide direct, visual evidences of the importance of thermal stresses and heat and mass transfer to spore inactivation by very rapid dry heating.

Searching for stable Si(n)C(n) clusters: combination of stochastic potential surface search and pseudopotential plane-wave Car-Parinello simulated annealing simulations.

To find low energy Si(n)C(n) structures out of hundreds to thousands of isomers we have developed a general method to search for stable isomeric structures that combines Stochastic Potential Surface Search and Pseudopotential Plane-Wave Density Functional Theory Car-Parinello Molecular Dynamics simulated annealing (PSPW-CPMD-SA). We enhanced the Sunders stochastic search method to generate random cluster structures used as seed structures for PSPW-CPMD-SA simulations. This method ensures that each SA simulation samples a different potential surface region to find the regional minimum structure. By iterations of this automated, parallel process on a high performance computer we located hundreds to more than a thousand stable isomers for each Si(n)C(n) cluster. Among these, five to 10 of the lowest energy isomers were further optimized using B3LYP/cc-pVTZ method. We applied this method to Si(n)C(n) (n = 4-12) clusters and found the lowest energy structures, most not previously reported. By analyzing the bonding patterns of low energy structures of each Si(n)C(n) cluster, we observed that carbon segregations tend to form condensed conjugated rings while Si connects to unsaturated bonds at the periphery of the carbon segregation as single atoms or clusters when n is small and when n is large a silicon network spans over the carbon segregation region.

Thermal effects on surface structures and properties of Bacillus anthracis spores on nanometer scales.

Bacterial spores, one of the hardiest forms of life known, can survive severe environmental stresses such as high temperature. Using thermal atomic force microscopy (AFM), we show that the surface structures and properties of Bacillus anthracis spores when exposed to elevated temperatures undergo substantial changes on nanometer scales. Thermal-blister-like nanostructures, which grow in size with increasing temperature, are formed on the spore surface when it is heated by a thermal tip. Although thermal damage to the spore surface is persistent upon cooling heat-treated spores to room temperature, thermal effects on surface properties of the spores are complex. The thermally induced nanostructures show a lower surface-tip adhesion and a higher modulus than the surrounding spore surface. The overall trend is for the adhesion to decrease with increasing temperature. However, the adhesion of heat-treated spores may be smaller than, equal to, or larger than that of untreated spores, depending upon the degree of surface damage induced by heat. Although the overall spore dimensions show few changes during and after heat treatment, the size of the spore substructures decreases significantly. In addition, we demonstrate a nanoscratch AFM method for imaging the subsurface structures of spores.

Evaluating the abnormal ossification in tibiotarsi of developing chick embryos exposed to 1.0ppm doses of platinum group metals by spectroscopic techniques.

Platinum group metals (PGMs), i.e., palladium (Pd), platinum (Pt) and rhodium (Rh), are found at pollutant levels in the environment and are known to accumulate in plant and animal tissues. However, little is known about PGM toxicity. Our previous studies showed that chick embryos exposed to PGM concentrations of 1mL of 5.0ppm (LD50) and higher exhibited severe skeletal deformities. This work hypothesized that 1.0ppm doses of PGMs will negatively impact the mineralization process in tibiotarsi. One milliliter of 1.0ppm of Pd(II), Pt(IV), Rh(III) aqueous salt solutions and a PGM-mixture were injected into the air sac on the 7th and 14th day of incubation. Control groups with no-injection and vehicle injections were included. On the 20th day, embryos were sacrificed to analyze the PGM effects on tibiotarsi using four spectroscopic techniques. 1) Micro-Raman imaging: Hyperspectral Raman data were collected on paraffin embedded cross-sections of tibiotarsi, and processed using in-house-written MATLAB codes. Micro-Raman univariate images that were created from the ν1(PO4(3-)) integrated areas revealed anomalous mineral inclusions within the bone marrow for the PGM-mixture treatment. The age of the mineral crystals (ν(CO3(2-))/ν1(PO4(3-))) was statistically lower for all treatments when compared to controls (p≤0.05). 2) FAAS: The percent calcium content of the chemically digested tibiotarsi in the Pd and Pt groups changed by ~45% with respect to the no-injection control (16.1±0.2%). 3) Micro-XRF imaging: Abnormal calcium and phosphorus inclusions were found within the inner longitudinal sections of tibiotarsi for the PGM-mixture treatment. A clear increase in the mineral content was observed for the outer sections of the Pd treatment. 4) ICP-OES: PGM concentrations in tibiotarsi were undetectable (<5ppb). The spectroscopic techniques gave corroborating results, confirmed the hypothesis, and explained the observed pathological (skeletal developmental abnormalities) and histological changes (tibiotarsus ischemia and nuclear fragmentation in chondrocytes).

Glass transitions in nanoscale heated volumes of thin polystyrene films.

Glass transitions in confined polystyrene films on a silicon substrate were studied using atomic force microscopy incorporating a thermal tip. Three-dimensional spatial nanoconfinements were achieved by controlling size and boundary conditions of small heated volumes of polymer nanostrands drawn from the polymer surface with the thermal tip, using appropriate loads and temperatures at the tip-polymer contact. Finite element analysis was performed to model mechanical contact and thermal transport, including the effects of contact radius, film thickness, and load on temperature and pressure distributions in the confined volume at the contact. The glass transition temperature (T(g)) was measured by observing the softening of polymers with increasing temperature. The measured surface T(g) exhibited a strong size dependence, while the subsurface T(g) increased with decreasing the distance to the substrate. A large increase in the surface T(g) was observed when the radius of contact was reduced below about 10 nm. The increase in the glass transition temperature at the surface was attributed to the presence of surface and line tension at the nanometer contact, while the enhanced T(g) near the substrate was attributed to the pinning effects that reduces the mobility of the polymer molecules in the film over several hundreds of nanometers away from the polymer-substrate interface.

Assessment of the accuracy of shape-consistent relativistic effective core potentials using multireference spin-orbit configuration interaction singles and doubles calculations of the ground and low-lying excited states of U(4+) and U(5+).

Multireference spin-orbit configuration interaction calculations were used to determine the accuracy of 60-, 68-, and 78-electron shape-consistent relativistic effective core potentials (RECPs) for uranium V and VI ground and low-lying excited states. Both 5f(n) and (5f6d)(n), (n = 1, 2) reference spaces were investigated using correlation-consistent double-zeta quality basis sets. Accuracy was assessed against gas-phase experimental spectra. The 68-electron RECP calculations yielded low relative and rms errors and predicted the empirical ordering of states most consistently.

Modeling positrons in molecular electronic structure calculations with the nuclear-electronic orbital method.

The nuclear-electronic orbital (NEO) method was modified and extended to positron systems for studying mixed positronic-electronic wavefunctions, replacing the mass of the proton with the mass of the positron. Within the modified NEO framework, the NEO-HF (Hartree-Fock) method provides the energy corresponding to the single-configuration mixed positronic-electronic wavefunction, minimized with respect to the molecular orbitals expressed as linear combinations of Gaussian basis functions. The electron-electron and electron-positron correlation can be treated in the NEO framework with second-order perturbation theory (NEO-MP2) or multiconfigurational methods such as the full configuration interaction (NEO-FCI) and complete active space self-consistent-field (NEO-CASSCF) methods. In addition to implementing these methods for positronic systems, strategies for calculating electron-positron annihilation rates using NEO-HF, NEO-MP2, and NEO-FCI wavefunctions were also developed. To apply the NEO method to the positronium hydride (PsH) system, positronic and electronic basis sets were optimized at the NEO-FCI level and used to compute NEO-MP2 and NEO-FCI energies and annihilation rates. The effects of basis set size on NEO-MP2 and NEO-FCI correlation energies and annihilation rates were compared. Even-tempered electronic and positronic basis sets were also optimized for the e+LiH molecule at the NEO-MP2 level and used to compute the equilibrium bond length and vibrational energy.

Surface stress influences on nanopatterns formed in polystyrene films using a force-modulated nanohammer.

Two-dimensional lattices of nanodots can be reproducibly produced on polymer surfaces by a biaxial stress field generated using a force-modulated atomic force microscope tip as a nanohammer. Molecular sized super-lattice nanostructures were previously formed by a combination of fundamental and harmonic modulation of surface stress waves in different scanning directions. We find that similar super-lattice structures can be formed in polystyrene films using only fundamental force modulation by taking advantage of elastic interactions between nearby nanoridges. Influences of the initial nanoridge size and the molecular weight of polystyrene on the formation of simple lattice patterns and complex nanometer-scale super-lattice patterns were studied.