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At least 991 records · Page 55

Ligand Noninnocence in β-Diketiminate and β-Diketimine Copper Complexes

Metal–ligand cooperative systems have a long precedent in catalysis, with the classification depending on the site of substrate bond cleavage and formation and on redox state changes. Recently, our group reported the participation of a β-diketiminate ligand in chemical bonding to heterocumulenes such as CO 2 and CS 2 by tricopper complexes, leading to cooperative catalysis. Herein, we report the reactivity of these copper clusters, [Cu 3 EL] – (E = S, Se; L = tris(β-diketiminate) cyclophane ligand), toward other electrophiles, viz. alkyl halides and Brønsted acids. We identified a family of ligand-functionalized complexes, Cu 3 EL (R) (R = primary alkyls), and a series of disubstituted products, Cu 3 EL (R) 2 , through single-crystal X-ray diffraction, mass spectrometry, and infrared and UV–visible spectroscopy. Furthermore, as part of mechanistic studies on these alkylation reactions, we evaluated the acid–base reactivity of these complexes and the influence of the backbone substitution on the reduction potential. Implications of these findings for ligand noninnocence and the relevance of the metal core as a cofactor for the ligand’s reactivity are discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NMR Relaxometry and Diffusometry Analysis of Dynamics in Ionic Liquids and Ionogels for Use in Lithium-Ion Batteries

Solvation and transport properties of methlyviologen dichloride in mixtures of choline chloride (ChCl) and ethylene glycol (EG) including the deep eutectic solvent (DES) ethaline were studied through physical property measurements, cyclic voltammetry, and Raman spectroscopy. The transport properties of the solvate structures in ethaline and ChCl:EG mixtures were compared to a well-studied ionic liquid (IL), 1-methyl-1-propylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [PYR13][TFSI] through the lens of hole theory. Exchanging the chloride anion of ethaline with bis(trifuoromethylsufonyl)imide) anion, [TFSI], is found to increase the fluidity of the solvent and promoted stronger solute-solvent interactions. Raman spectroscopy shows that methylviologen is solvated by EG in solutions with ChTFSI but interstitially accommodated in void spaces in both ChCl solutions and [PYR13][TFSI]. Complex solvents such as DESs are regarded as “designer solvents” and we demonstrate that the physical properties and solvation characteristics of these fluids can be varied by anion exchange of hydrogen bond acceptors.

25 ENERGY STORAGE↗

Experimental basis for a Titan probe organic analysis

The recent Voyager flyby of Titan produced evidence for at least nine organic compounds in that atmosphere that are heavier than methane. Several models of Titan's atmosphere, as well as laboratory simulations, suggest the presence of organics considerably more complex that those observed. To ensure that the in situ measurements are definitive with respect to Titan's atmosphere, experiment concepts, and the related instrumentation, must be carefully developed specifically for such a mission. To this end, the possible composition of the environment to be analyzed must be bracketed and model samples must be provided for instrumentation development studies. Laboratory studies to define the optimum flight experiment and sampling strategy for a Titan entry probe are currently being conducted. Titan mixtures are being subjected to a variety of energy sources including high voltage electron from a DC discharge, high current electric shock, and laser detonation. Gaseous and solid products are produced which are then analyzed. Samples from these experiements are also provided to candidate flight experiments as models for instrument development studies. Preliminary results show that existing theoretical models for chemistry in Titan's atmosphere cannot adequetely explain the presence and abundance of all trace gases observed in these experiments.

Mckay, C. P.↗

"2001: A Space Odyssey" Revisited--The Feasibility of 24 Hour Commuter Flights to the Moon Using NTR Propulsion with LUNOX Afterburners

The prospects for "24 hour" commuter flights to the Moon, similar to that portrayed in 2001: A Space Odyssey but on a more Spartan scale, are examined using two near term, "high leverage" technologies--liquid oxygen (LOX)-augmented nuclear thermal rocket (NTR) propulsion and "lunar-derived" oxygen (LUNOX) production. Ironrich volcanic glass, or "orange soil," discovered during the Apollo 17 mission to Taurus-Littrow, has produced a 4% oxygen yield in recent NASA experiments using hydrogen reduction. LUNOX development and utilization would eliminate the need to transport oxygen supplies from Earth and is expected to dramatically reduce the size, cost and complexity of space transportation systems. The LOX-augmented NTR concept (LANTR) exploits the high performance capability of the conventional liquid hydrogen (LH2)-cooled NTR and the mission leverage provided by LUNOX in a unique way, LANTR utilizes the large divergent section of its nozzle as an "afterburner" into which oxygen is injected and supersonically combusted with nuclear preheated hydrogen emerging front the engine's choked sonic throat--essentially "scramjet propulsion in reverse." By varying the oxygen-to-hydrogen mixture ratio, the LANTR engine can operate over a wide range of thrust and specific impulse (Isp) values while the reactor core power level remains relatively constant. The thrust augmentation feature of LANTR means that "big engine" performance can be obtained using smaller, more affordable, easier to test NTR engines. The use of high-density LOX in place of low-density LH2 also reduces hydrogen mass and tank volume resulting in smaller space vehicles. An implementation strategy and evolutionary lunar mission architecture is outlined which requires only Shuttle C or "in-line" Shuttle-derived launch vehicles, and utilizes conventional NTR-powered lunar transfer vehicles (LTVs), operating in an "expendable mode" initially, to maximize delivered surface payload on each mission. The increased payload is dedicated to installing "modular" LUNOX production units with the intent of supplying LUNOX to lunar landing vehicles (LLVS) and then LTVs at the earliest possible opportunity. Once LUNOX becomes available in low lunar orbit (LLO), monopropellant NTRs would be outfitted with an oxygen propellant module, feed system and afterburner nozzle for "bipropellant" operation. Transition to a "reusable" mission architecture now occurs with smaller, LANTR-powered LTVs delivering approximately 400% more payload on each piloted round trip mission than earlier expendable "all LH2" NTR systems. As initial lunar outposts grow to eventual lunar settlements and LUNOX production capacity increases, the LANTR concept can enable a rapid "commuter" shuttle capable of 24 hour "one way" trips to and from the Moon, A vast deposit of"iron-rich" volcanic glass beads identified at just one candidate site--located at the southeastern edge of Mare Serenitatis--could supply, sufficient LUNOX to support daily commuter flights to the Moon for the next 9000 years!

Borowski, Stanley K.↗

2001: A Space Odyssey Revisited: The Feasibility of 24 Hour Commuter Flights to the Moon Using NTR Propulsion with LUNOX Afterburners

The prospects for 24 hour commuter flights to the Moon, similar to that portrayed in 2001: A Space Odyssey but on a more Spartan scale, are examined using two near term, high leverage technologies: liquid oxygen (LOX)-augmented nuclear thermal rocket (NTR) propulsion and lunar-derived oxygen (LUNOX) production. Iron-rich volcanic glass, or orange soil, discovered during the Apollo 17 mission to Taurus-Littrow, has produced a 4 percent oxygen yield in recent NASA experiments using hydrogen reduction. LUNOX development and utilization would eliminate the need to transport oxygen supplies from Earth and is expected to dramatically reduce the size, cost and complexity of space transportation systems. The LOX-augmented NTR concept (LANTR) exploits the high performance capability of the conventional liquid hydrogen (LH2)-cooled NTR and the mission leverage provided by LUNOX in a unique way. LANTR utilizes the large divergent section of its nozzle as an afterburner into which oxygen is injected and supersonically combusted with nuclear preheated hydrogen emerging from the engine's choked sonic throat, essentially scramjet propulsion in reverse. By varying the oxygen-to-hydrogen mixture ratio, the LANTR engine can operate over a wide range of thrust and specific impulse (Isp) values while the reactor core power level remains relatively constant. The thrust augmentation feature of LANTR means that big engine performance can be obtained using smaller, more affordable, easier to test NTR engines. The use of high-density LOX in place of low density LH2 also reduces hydrogen mass and tank volume resulting in smaller space vehicles. An implementation strategy and evolutionary lunar mission architecture is outlined which requires only Shuttle C or in-line Shuttle-derived launch vehicles, and utilizes conventional NTR-powered lunar transfer vehicles (LTVs), operating in an expendable mode initially, to maximize delivered surface payload on each mission. The increased payload is dedicated to installing modular LUNOX production units with the intent of supplying LUNOX to lunar landing vehicles (LLVs) and then LTVs at the earliest possible opportunity. Once LUNOX becomes available in low lunar orbit (LLO), monopropellant NTRs would be outfitted with an oxygen propellant module, feed system and afterburner nozzle for bipropellant operation. Transition to a reusable mission architecture now occurs with smaller, LANTR-powered LTVs delivering ~400% more payload on each piloted round trip mission than earlier expendable all LH2 NTR systems. As initial lunar outposts grow to eventual lunar settlements and LUNOX production capacity increases, the LANTR concept can enable a rapid commuter shuttle capable of 24 hour one way trips to and from the Moon. A vast deposit of iron-rich volcanic glass beads identified at just one candidate site located at the southeastern edge of Mare Serenitatis could supply sufficient LUNOX to support daily commuter flights to the Moon for the next 9000 years!

Borowski, Stanley↗

Ascent and eruption of basaltic magma on the earth and moon

The ascent and emplacement of basaltic magma on the earth and moon is modeled by the application of geological and physical observations and constraints. Relatively simple mathematical models of the motion of gas/liquid mixtures are shown to be adequate in the treatment of basaltic eruptions, provided that allowance is made for the coalescence of gas bubbles and that realistic geological and petrochemical constraints are applied to the numerical values of variables. Because gas exsolution from magmas on the earth and moon commonly occur at depths of less than 2 km, it is generally convenient to consider separately the rise of bubble-free magmatic liquid at depth in a planetary crust and the more complex motions occurring near the surface with gas exsolution.

Wilson, L.↗

Determination of Mineral Type, Abundance, and Grain Size with Remotely Obtained Reflectance Spectra

To derive the abundances of minerals in a surface composed of more then one mineral in an intimate mixture, the bidirectional reflectance spectrum must be measured at several angles of incidence and emission. From these measurements, the scattering parameters may be derived, and the effective single scattering albedo can be computed from the models. If the scattering parameters are not derived, and the particles scatter anisotropically, then the computed effective single scattering albedo has been computed, the solution to the model is a nonlinear least squares problem with three unknowns per particle type. The solution is feasible when the complex indices of refraction and the densities of each mineral component are known. The unknowns are: the grain size of each particle type, the mass fraction of each particle type, and a grain internal scattering coefficient that describes grain imperfections.

Clark, R. N.↗

Experimental Study of Nonane and Nonane/Hexanol Fuel Droplet Combustion in Microgravity

In this presentation we review experiments carried out on nonane droplets, and a nonane/hexanol droplet, burning in microgravity to promote spherical symmetry. The nonane/hexanol combination was selected for the following reasons: 1) the spherically symmetric burning history of nonane and nonane/hexanol mixtures has not been previously studied; 2) measurements of the burning history of pure nonane droplets in air extend the existing data base of spherical droplet flames of soot-producing fuels which are useful for testing detailed chemical kinetic models of the spherically symmetric droplet burning process; 3) nonane and hexanol have almost identical boiling points so heterogeneous nucleation on a support fiber is unlikely; 4) hexanol does not have a strong propensity for water vapor absorption; 5) hexanol produces less soot than nonane so that mixtures of nonane and hexanol should show an effect of composition on soot formation. The far-field gas was atmospheric pressure air at room temperature. The evolution of droplet diameter was measured using high speed cine photography of spark-ignited droplets within a confined volume in a drop tower. The importance of soot formation during droplet combustion is derived from the fact that soot is the basic component of the particulate emission process that occurs in spray combustion. The complexity of soot formation motivates a one-dimensional transport condition which is advantageous for modeling. Recent numerical studies of droplet combustion have assumed spherical symmetry when incorporating such aspects as detailed chemistry and radiation, though soot formation itself has not yet been included in any droplet combustion modeling effort. If radiation is not important as would be the case for'small' droplets (i.e., droplets with initial diameters less than about ]mm), soot formation can lead to a nonlinear burning process and a time-varying burning rate, (non-linear burning of a non-sooting fuel like methanol is due to water vapor absorption on the droplet. The classical quasi-steady droplet burning theory predicts a linear evolution of droplet diameter in scaled coordinates for any fuel type.

Avedisian, C. T.↗

"2001: A Space Odyssey" Revisited: The Feasibility of 24 Hour Commuter Flights to the Moon Using NTR Propulsion with LUNOX Afterburners

The prospects for "24 hour" commuter flights to the Moon. similar to that portrayed in 2001: A Space Odyssey but on a more Spartan scale. are examined using two near term. "high leverage" technologies-liquid oxygen (LOX)-augmented nuclear thermal rocket (NTR) propulsion and "lunar-derived" oxygen (LUNOX) production. Iron-rich volcanic glass. or "orange soil," discovered during the Apollo 17 mission to Taurus-Littrow. has produced a 4% oxygen yield in recent NASA experiments using hydrogen reduction. LUNOX development and utilization would eliminate the need to transport oxygen supplies from Earth and is expected to dramatically reduce the size, cost and complexity of space transportation systems. The LOX-augmented NTR concept (LANTR) exploits the high performance capability of the conventional liquid hydrogen (LH2)-cooled NTR and the mission leverage provided by LUNOX in a unique way. LANTR utilizes the large divergent section of its nozzle as an "afterburner" into which oxygen is injected and supersonically combusted with nuclear preheated hydrogen emerging from the engine's choked sonic throat-essentially "scramjet propulsion in reverse." By varying the oxygen-to-hydrogen mixture ratio, the LANTR engine can operate over a wide range of thrust and specific impulse (Isp) values while the reactor core power level remains relatively constant. The thrust augmentation feature of LANTR means that "big engine" performance can be obtained using smaller. more affordable. easier to test NTR engines. The use of high-density LOX in place of low-density LH2 also reduces hydrogen mass and tank volume resulting in smaller space vehicles. An implementation strategy and evolutionary lunar mission architecture is outlined which requires only Shuttle C or "in-line" Shuttle-derived launch vehicles, and utilizes conventional NTR-powered lunar transfer vehicles (LTVs), operating in an "expendable mode" initially, to maximize delivered surface payload on each mission. The increased payload is dedicated to installing "modular" LUNOX production units with the intent of supplying LUNOX to lunar landing vehicles (LLVs) and then LTVs at the earliest possible opportunity. Once LUNOX becomes available in low lunar orbit (LLO), monopropellant NTRs would be outfitted with an oxygen propellant module, feed system and afterburner nozzle for "bipropellant" operation. Transition to a "reusable" mission architecture now occurs with smaller, LANTR-powered LTVs delivering approximately 400% more payload on each piloted round trip mission than earlier expendable "all LH2" NTR systems. As initial lunar outposts grow to eventual lunar settlements and LUNOX production capacity increases, the LANTR concept can enable a rapid "commuter" shuttle capable of 24 hour "one way" trips to and from the Moon. A vast deposit of "iron-rich" volcanic glass beads identified at just one candidate site - located at the southeastern edge of Mare Serenitatis - could supply sufficient LUNOX to support daily commuter flights to the Moon for the next 9000 years'.

Borowski, Stanley K.↗

Simulation of Complex Cracking in Plain Weave C/SiC Composite under Biaxial Loading

Finite element analysis is performed on a mesh, based on computed geometry of a plain weave C/SiC composite with assumed internal stacking, to reveal the pattern of internal damage due to biaxial normal cyclic loading. The simulation encompasses intertow matrix cracking, matrix cracking inside the tows, and separation at the tow-intertow matrix and tow-tow interfaces. All these dissipative behaviors are represented by traction-separation cohesive laws. Not aimed at quantitatively predicting the overall stress-strain relation, the simulation, however, does not take the actual process of fiber debonding into account. The fiber tows are represented by a simple rule-of-mixture model where the reinforcing phase is a hypothetical one-dimensional material. Numerical results indicate that for the plain weave C/SiC composite, 1) matrix-crack initiation sites are primarily determined by large intertow matrix voids and interlayer tow-tow contacts, 2) the pattern of internal damage strongly depends on the loading path and initial stress, 3) compressive loading inflicts virtually no damage evolution. KEY WORDS: ceramic matrix composite, plain weave, cohesive model, brittle failure, smeared crack model, progressive damage, meso-mechanical analysis, finite element.

Cheng, Ron-Bin↗

Discovering Dinuclear Dioxygen-Bridged Cobalt(III) Complexes for Selective Binding of O 2 from Air

The design and development of dioxygen activation in porous crystalline materials is a useful avenue for exploring selective adsorption of O 2 that shows significant potential to enable separations of O 2 and N 2 from air. Porous materials featuring redox-active metal centers have received attention regarding selective O 2 adsorption via chemisorption. Drawing inspiration from a dinuclear cobalt material ([(Co(III) 2 (bpbp)O 2 ) 2 bdc](PF 6 ) 4 (CSD code: GAMVIB; bpbp – = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolato; bdc 2– = 1,4-benzenedicarboxylato)) that displays reversible and selective O 2 adsorption, we focus on searching for potential O 2 -selective materials with dinuclear cobalt clusters that have dioxygen-bridged Co(III) complexes. We combine structure screening with a high-level hybrid periodic density functional theory (DFT) workflow to investigate O 2 and N 2 adsorption in materials from validated crystal structure databases (e.g., the CSD database). These calculations identify multiple materials that are predicted to have superior O 2 binding capability relative to GAMVIB. Grand Canonical Monte Carlo (GCMC) simulations based on DFT-developed force fields were performed for selected candidates to estimate the adsorption performance for O 2 /N 2 mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formulation of the density eigenvalue problem in neutron transport for relevant engineering applications

A new formulation of the density eigenvalue problem for the neutron transport equation is presented. This new eigenvalue, named ζ eigenvalue can be introduced freely in the transport model, acting on a selected portion of the phase space. Despite its broader applications and its connection with the nature of the transport operator, the ζ eigenvalue has been presented here mainly as a design-oriented technique for the efficient evaluation of the critical concentration for a specific nuclide (or mixture of nuclides). This new eigenvalue is particularly adequate to study the definition of the material composition in the criticality design process of a multiplying system. The method is then applied for the study of classical problems such as the critical moderation ratio and the poison concentration to control the reactor. Some results are presented in one dimensional configuration using the multi- group spherical harmonics approach. This eigenvalue formulation proves to be a convenient and useful way to attain criticality, also for complex, realistic systems.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Advances in Hyperspectral Image Classification Methods for Vegetation and Agricultural Cropland Studies

Hyperspectral data are becoming more widely available via sensors on airborne and unmanned aerial vehicle (UAV) platforms, as well as proximal platforms. While space-based hyperspectral data continue to be limited in availability, multiple spaceborne Earth-observing missions on traditional platforms are scheduled for launch, and companies are experimenting with small satellites for constellations to observe the Earth, as well as for planetary missions. Land cover mapping via classification is one of the most important applications of hyperspectral remote sensing and will increase in significance as time series of imagery are more readily available. However, while the narrow bands of hyperspectral data provide new opportunities for chemistry-based modeling and mapping, challenges remain. Hyperspectral data are high dimensional, and many bands are highly correlated or irrelevant for a given classification problem. For supervised classification methods, the quantity of training data is typically limited relative to the dimension of the input space. The resulting Hughes phenomenon, often referred to as the curse of dimensionality, increases potential for unstable parameter estimates, overfitting, and poor generalization of classifiers. This is particularly problematic for parametric approaches such as Gaussian maximum likelihood–based classifiers that have been the backbone of pixel-based multispectral classification methods. This issue has motivated investigation of alternatives, including regularization of the class covariance matrices, ensembles of weak classifiers, development of feature selection and extraction methods, adoption of nonparametric classifiers, and exploration of methods to exploit unlabeled samples via semi-supervised and active learning. Data sets are also quite large, motivating computationally efficient algorithms and implementations. This chapter provides an overview of the recent advances in classification methods for mapping vegetation using hyperspectral data. Three data sets that are used in the hyperspectral classification literature (e.g., Botswana Hyperion satellite data and AVIRIS airborne data over both Kennedy Space Center and Indian Pines) are described in Section 3.2 and used to illustrate methods described in the chapter. An additional high-resolution hyperspectral data set acquired by a SpecTIR sensor on an airborne platform over the Indian Pines area is included to exemplify the use of new deep learning approaches, and a multiplatform example of airborne hyperspectral data is provided to demonstrate transfer learning in hyperspectral image classification. Classical approaches for supervised and unsupervised feature selection and extraction are reviewed in Section 3.3. In particular, nonlinearities exhibited in hyperspectral imagery have motivated development of nonlinear feature extraction methods in manifold learning, which are outlined in Section 3.3.1.4. Spatial context is also important in classification of both natural vegetation with complex textural patterns and large agricultural fields with significant local variability within fields. Approaches to exploit spatial features at both the pixel level (e.g., co-occurrence–based texture and extended morphological attribute profiles [EMAPs]) and integration of segmentation approaches (e.g., HSeg) are discussed in this context in Section 3.3.2. Recently, classification methods that leverage nonparametric methods originating in the machine learning community have grown in popularity. An overview of both widely used and newly emerging approaches, including support vector machines (SVMs), Gaussian mixture models, and deep learning based on convolutional neural networks is provided in Section 3.4. Strategies to exploit unlabeled samples, including active learning and metric learning, which combine feature extraction and augmentation of the pool of training samples in an active learning framework, are outlined in Section 3.5. Integration of image segmentation with classification to accommodate spatial coherence typically observed in vegetation is also explored, including as an integrated active learning system. Exploitation of multisensor strategies for augmenting the pool of training samples is investigated via a transfer learning framework in Section 3.5.1.2. Finally, we look to the future, considering opportunities soon to be provided by new paradigms, as hyperspectral sensing is becoming common at multiple scales from ground-based and airborne autonomous vehicles to manned aircraft and space-based platforms.

Pasolli, Edoardo↗

Four-Coordinate Fe N 2 and Imido Complexes Supported by a Hemilabile NNC Heteroscorpionate Ligand

Inspired by mechanistic proposals for N 2 reduction at the nitrogenase FeMo cofactor, we report herein a new, strongly σ-donating heteroscorpionate ligand featuring two weak-field pyrazoles and an alkyl donor. This ligand supports four-coordinate Fe(I)-N 2 , Fe(II)-Cl, and Fe(III)-imido complexes, which we have characterized using a variety of spectroscopic and computational methods. Structural and quantum mechanical analysis reveal the nature of the Fe–C bonds to be essentially invariant between the complexes, with conversion between the (formally) low-valent Fe-N 2 and high-valent Fe-imido complexes mediated by pyrazole hemilability. This presents a useful strategy for substrate reduction at such low-coordinate centers and suggests a mechanism by which FeMoco might accommodate the binding of both π-acidic and π-basic nitrogenous substrates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Perspective on Technical Lignin Fractionation

Technical lignin extracted from pulping and biorefining processes provides a class of complex and polydisperse phenolic polymers. Preparation of lignin with lower structural complexity and polydispersity through lignin fractionation is one of the primary solutions to engineer lignin into a value-added material. Sequential lignin fraction by pH controlled precipitation from 12 to 1 is one of the primary developed methods. Partial solubility of lignin in organic solvents is another promising method for lignin fractionation. Organic solvents with different polarity and solubility factors are able to fractionate lignin, yielding a more homogeneous chemical structure. As a modification of the lignin fractionation process using solvents, water/organic solvents mixture, such as propan-2-one, alcohols, and acetic acid, from room to high temperature has been proposed as a greener method for lignin fractionation. Using membrane technology is another promising method and current results indicate a good potential for lignin recovery and fractionation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-throughput reaction discovery for Cs–Pb–Br nanocrystal synthesis

High-throughput reaction discovery is necessary to understand complex reaction spaces for inorganic nanocrystal synthesis. Here, we implemented a high-throughput continuous flow millifluidic reactor to perform reaction discovery for Cs–Pb–Br nanocrystal synthesis using a ligand assisted reprecipitation (LARP)-type approach. 3D-printed flow resistors enable the screening of up to 16 different mixing ratios within a single 90 s run, allowing for >270 different precursor concentration ratios to be quickly tested to explore the phase space that results in CsPbBr 3 , Cs 4 PbBr 6 , a biphasic mixture, or no product. To construct a full phase map from these high-throughput experiments, a neural network was trained and validated to predict the product composition (~500 000 points in precursor concentration space). The phase map predicts product composition/phase as a function of Cs–Pb–Br feed ratio. As a result, this approach demonstrates how high-throughput flow chemistry can be used in tandem with machine learning to rapidly explore nanocrystal reaction spaces in flow.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excited-state electronic structure of molecules using many-body Green’s functions: Quasiparticles and electron–hole excitations with VOTCA-XTP

Here, we present the open-source VOTCA-XTP software for the calculation of the excited-state electronic structure of molecules using many-body Green’s function theory in the GW approximation with the Bethe–Salpeter equation (BSE). This work provides a summary of the underlying theory and discusses the details of its implementation based on Gaussian orbitals, including resolution-of-identity techniques and different approaches to the frequency integration of the self-energy or acceleration by offloading compute-intensive matrix operations using graphics processing units in a hybrid OpenMP/Cuda scheme. A distinctive feature of VOTCA–XTP is the capability to couple the calculation of electronic excitations to a classical polarizable environment on an atomistic level in a coupled quantum- and molecular-mechanics (QM/MM) scheme, where a complex morphology can be imported from Molecular Dynamics simulations. The capabilities and limitations of the GW–BSE implementation are illustrated with two examples. First, we study the dependence of optically active electron–hole excitations in a series of diketopyrrolopyrrole-based oligomers on molecular-architecture modifications and the number of repeat units. Second, we use the GW–BSE/MM setup to investigate the effect of polarization on localized and intermolecular charge-transfer excited states in morphologies of low-donor content rubrene–fullerene mixtures. These showcases demonstrate that our implementation currently allows us to treat systems with up to 2500 basis functions on regular shared-memory workstations, providing accurate descriptions of quasiparticle and coupled electron–hole excited states of various characters on an equal footing.

74 ATOMIC AND MOLECULAR PHYSICS↗

Influence of ion-pairing reagents on the separation of intact glycoproteins using hydrophilic-interaction liquid chromatography - high-resolution mass spectrometry

Hydrophilic-interaction liquid chromatography (HILIC) of intact proteins offers high-resolution separations of glycoforms of glycoproteins differing in the number of (neutral) glycans. However, to obtain efficient separations it is essential that the positively charged sites of the proteins are shielded by acidic (negative) ion-pair reagents (IPRs), so as to enhance the contribution of the hydroxyl groups of the (neutral) sugars in the glycoprotein. Here, we studied the influence of various IPRs that differ in physico-chemical properties, such as hydrophobicity and acidity, on the capillary-scale HILIC separation of intact (glyco)proteins. We evaluated the use of fluoroacetic acid (MFA), difluoroacetic acid (DFA), trifluoroacetic acid (TFA), and heptafluorobutyric acid (HFBA) as diluents for sample preparation, as solvents for sample loading on a reversed-phase trap prior to the HILIC separation, and as mobile-phase components for HILIC and HILIC-MS. To reduce the contribution of ion-exchange interaction with the (silica-based) stationary phase, we used an acrylamide-based monolithic column. We studied the influence of the different IPRs on each step of the separation of a mixture of proteins of different size and hydrophilicity and on the separation of the five glycoforms of ribonuclease B. The content of IPR in the sample was shown not to affect the separation and the MS detection. However, a low content of TFA and DFA in the mobile phase is favourable, as it reduces adduct formation and leads to higher signal intensity. The optimized HILIC conditions successfully resolved nine major glycoforms groups of a ~40 kDa glycoprotein horseradish peroxidase (HRP), as an example of a complex glycoprotein.

59 BASIC BIOLOGICAL SCIENCES↗