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DOE OSTI2022

MOOSE Reactor Module Meshing Enhancements to Support Reactor Physics Analysis

The U.S. Department of Energy Office of Nuclear Energy Advanced Modeling and Simulation (NEAMS) program develops an integrated suite of advanced reactor physics tools built upon the Multiphysics Object-Oriented Simulation Environment (MOOSE) framework. Each code generally requires an input finite element mesh on which the physics solution is calculated, reported, and transferred to other physics codes. The meshing process is often burdensome for the complex geometries present in reactors due to lack of easy-to-use, open-source meshing tools. To address the bottleneck associated with meshing complex geometries found in nuclear reactors, NEAMS initiated the development of the MOOSE Reactor Module starting in FY21. The Reactor Module builds off the existing MOOSE Mesh System to include targeted meshing capabilities such as the ability to generate hexagonal pin cells, assemblies with ducts, rotating control drums, cores, peripheral zones around a core, as well as the automatic labeling (“reporting IDs”) of pin, assembly, and planar zones to simplify post-processing of results. As a Physics Module in MOOSE, the Reactor Module is open-source, available with any MOOSE installation, directly compatible with MOOSE-based tools, and can be invoked from MOOSEbased applications to generate meshes. Functionality from the Reactor Module has been applied to several advanced reactor concepts to demonstrate user workflow improvements and accuracy. The primary objective of the Reactor Module is to improve useability of MOOSEbased tools by streamlining mesh generation and output inspection processes. During FY22, the functionality of the Reactor Module (and accompanying Mesh System) has been expanded based on user needs. First, the Reactor Geometry Mesh Builder capability developed primarily in FY21 has been refactored and merged to the public MOOSE repository. This capability wraps underlying Reactor Module mesh generators into a “Pin – Assembly – Core” workflow appropriate for conventional Cartesian and hexagonal geometries, and notably assigns material IDs during mesh generation stage and generates only the minimal number of blocks needed in order to reduce computational burden. Biasing and boundary layer options have been added to the base mesh generators as required by thermal hydraulics solvers. The reporting ID functionality has been expanded to differentiate ring-wise and azimuthal sectors within a pin for use with depletion algorithms, and VectorPostProcessor and Reporter objects are now available to integrate solution variables across zones based on ID combinations. Functionality to trim hexagonal meshes along the center or periphery has been developed so users may leverage symmetry and reflective boundary conditions to reduce the mesh size. A flexible and powerful tool to fill the space between two sidesets has been introduced to the framework and can be used for transition layers such as stitching two assemblies together with different numbers of pins, or for complex geometries which do not follow conventional Cartesian/hexagonal patterns. Finally, additional verification problems were performed with NEAMS physics tools in complement with existing NEAMS work.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

DOE OSTI2015

Mechanism of Electron Beam Induced Oxide Layer Thickening on Iron–Iron Oxide Core–Shell Nanoparticles

Materials exposed to radiation show structural changes and damages, especially in the nanoscale range. The characterizing equipment involving electron beam (e-beam) radiation for a nanosize imaging process, such as a transmission electron microscope, is no exception, in which the most prominent behavior of native oxide layer thickening has been widely studied. In this paper, we describe the physics behind the growth mechanism of the oxide layer in a core–shell iron/iron oxide nanoparticle (NP) under the impact of e-beam radiation. The particles studied were synthesized via a cluster deposition system. Due to the impact of the e-beam, these particles were observed to grow inward and outward resulting in a total increase of NP size. The theory is connected with experimental evidence to reveal the oxide layer thickening of the NP, which is favored and enhanced by vacancy formation, surface oxidation, and diffusion/void nucleation under the impact of a 200 keV e-beam.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2015

Platinum-coated non-noble metal-noble metal core-shell electrocatalysts

Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.

36 MATERIALS SCIENCE↗

NASA NTRS1978

Fabrication of stainless steel clad tubing

The feasibility of producing stainless steel clad carbon steel tubing by a gas pressure bonding process was evaluated. Such a tube product could provide substantial chromium savings over monolithic stainless tubing in the event of a serious chromium shortage. The process consists of the initial assembly of three component tubesets from conventionally produced tubing, the formation of a strong metallurgical bond between the three components by gas pressure bonding, and conventional cold draw and anneal processing to final size. The quality of the tubes produced was excellent from the standpoint of bond strength, mechanical, and forming properties. The only significant quality problem encountered was carburization of the stainless clad by the carbon steel core which can be overcome by further refinement through at least three different approaches. The estimated cost of clad tubing produced by this process is greater than that for monolithic stainless tubing, but not so high as to make the process impractical as a chromium conservation method.

Kovach, C. W.↗

DOE OSTI2025

Multiphase Processing of the Water-Soluble and Insoluble Phases of Biomass Burning Organic Aerosol

Biomass burning is one of the most significant sources of organic aerosol in the atmosphere. Biomass burning organic aerosol (BBOA) has been observed to undergo liquid– liquid phase separation (LLPS) to give core–shell morphology with the hydrophobic phase encapsulating the hydrophilic phase, potentially impacting the evolution of light-absorbing components, i.e., brown carbon (BrC), through multiphase processes. Here, we demonstrate how multiphase processing differs between the watersoluble (i.e., hydrophilic) and insoluble (i.e., hydrophobic) phases of BBOA in terms of reactive uptake of ozone in a coated-wall flow tube. Effects of relative humidity (RH) and ultraviolet (UV) irradiation were investigated. Experimental timeseries were used to inform simulations using multilayer kinetic modeling. Among non-irradiated thin films, the uptake coefficient was greatest for the water-soluble phase at 75% RH (3 × 10 –5 , corresponding to a diffusion coefficient of BrC, D BrC , of 3 × 10 –9 cm 2 s –1 ) and least for the same phase at 0% RH (1 × 10 –5 , corresponding to D BrC of 1 × 10 –10 cm 2 s –1 ). The uptake coefficient for the water-insoluble phase fell between these two (about 1.5 × 10 –5 ), regardless of RH, and the corresponding D BrC increased only slightly (8 × 10 –10 cm 2 s –1 at 0% RH to 9 × 10 –10 cm 2 s –1 at 75% RH). The uptake coefficients of both phases at 0% RH decreased significantly after UV irradiation, consistent with a transition from viscous liquid to solid and supported by qualitative microscopy observations. Modeling multiphase ozone oxidation of primary BrC components in the atmosphere demonstrated, first, that LLPS may extend the lifetime of water-soluble BBOA encapsulated by water-insoluble species by a factor of 1.5 at moderate to high RH and, also, that UV irradiation may extend the lifetime of both phases by more than a factor of 2.5.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2017

Effects of hydrologic connectivity and land use on floodplain sediment accumulation at the Savannah River Site, South Carolina.

Floodplains, and the sediment accumulating naturally on them,are important to maintain stream water quality and serve as sinks for organic and inorganic carbon. Newer theories contend that land use and hydrologic connectivity (water-mediated transport of matter, energy, and/or organisms within or between elements of the hydrologic cycle) play important roles in determining sediment accumulation on floodplains. This study hypothesizes that changes in hydrologic connectivity have a greater impact on floodplain sediment accumulation than changes in land use. Nine sediment cores from seven sub-basins were collected from the Savannah River Site (SRS), South Carolina, and processed for grain-size, radionuclide dating (7Be, 137Cs, 210Pb), particulate organic carbon (POC), and microscopy. Historical records, including aerial and satellite imagery,were used to identify anthropogenic disturbances in the sub-basins, as well as to calculate the percentages of natural vegetation land cover at the SRS in 1951, and 2014. LiDAR and field survey data identified 251 flow impediments, measured elevation, and recorded standard stream characteristics (e.g., bank height) that canaffect hydrologic connectivity. Radionuclide dating was used to calculate sediment mass accumulation rates (MARs) and linear accumulation rates (LARs) for each core. Results indicate that sedimentation rates have increased across all SRS sub-basins over the past 40-50 years, shortly after site restoration and recovery efforts began.Findings show that hydrologic connectivity proxies (i.e., stream characteristics and impediments) have stronger relationships to MARs and LARs than the land use proxy (i.e., vegetation cover), confirming the hypothesis. Asstream channel depth and the number of impediments increase,floodplain sedimentation rates also increase. This knowledge can help future stream restoration efforts by focusing resources to more efficiently attain stated goals, particularly in terms of floodplain sediment retention.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2016

Screening sensitivity analysis of a PWR fuel assembly FEM structural model

Within the present project, computational methods to describe the static mechanical response of PWR fuel assemblies (FA) in the reactor core are developed. For this purpose a structural model of a PWR fuel assembly has been implemented with the Finite Element Method (FEM) using the ANSYS APDL Mechanical code. The purpose of the model is to investigate the long-term creep deformation of the fuel assemblies in the reactor core, commonly known as fuel assembly bow. FA bow is considered to be a complex process with a large number of influencing mechanisms and many only roughly known boundary conditions. Uncertainty and sensitivity analyses are a common way to investigate the predictive power and reliability of such complex models. Hence, as a first approach to understand the importance of the many model parameters, a qualitative sensitivity analysis of the model was conducted using the screening method proposed by Morris. In the first part of the paper, the FA structural model and its principal parameters are presented. The second part presents first the different simulation experiments used for the screening analyses. Based on the model description, relevant input parameters are then identified and a typical range of values is determined. The sensitivity analysis is performed in two subsequent steps. First, the model is screened for influential stiffness parameters with the objective of stiffening the FA structure. Second, the influence of the uncertain boundary conditions and material models on the FA creep deformation is tested. For the considered FA design it is concluded that the influence of the involved uncertainties is comparable to the influence of the parameters which can increase the stiffness. An integral approach accounting for these uncertainties is hence necessary to predict FA bow reliably in order to take additional measures for a further reduction of FA bow amplitudes. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

DOE OSTI2015

DEEP CHANDRA, HST-COS, AND MEGACAM OBSERVATIONS OF THE PHOENIX CLUSTER: EXTREME STAR FORMATION AND AGN FEEDBACK ON HUNDRED KILOPARSEC SCALES

We present new ultraviolet, optical, and X-ray data on the Phoenix galaxy cluster (SPT-CLJ2344-4243). Deep optical imaging reveals previously undetected filaments of star formation, extending to radii of ∼50–100 kpc in multiple directions. Combined UV-optical spectroscopy of the central galaxy reveals a massive (2 × 10{sup 9} M{sub ⊙}), young (∼4.5 Myr) population of stars, consistent with a time-averaged star formation rate of 610 ± 50 M{sub ⊙} yr{sup −1}. We report a strong detection of O vi λλ1032,1038, which appears to originate primarily in shock-heated gas, but may contain a substantial contribution (>1000 M{sub ⊙} yr{sup −1}) from the cooling intracluster medium (ICM). We confirm the presence of deep X-ray cavities in the inner ∼10 kpc, which are among the most extreme examples of radio-mode feedback detected to date, implying jet powers of 2–7 × 10{sup 45} erg s{sup −1}. We provide evidence that the active galactic nucleus inflating these cavities may have only recently transitioned from “quasar-mode” to “radio-mode,” and may currently be insufficient to completely offset cooling. A model-subtracted residual X-ray image reveals evidence for prior episodes of strong radio-mode feedback at radii of ∼100 kpc, with extended “ghost” cavities indicating a prior epoch of feedback roughly 100 Myr ago. This residual image also exhibits significant asymmetry in the inner ∼200 kpc (0.15R{sub 500}), reminiscent of infalling cool clouds, either due to minor mergers or fragmentation of the cooling ICM. Taken together, these data reveal a rapidly evolving cool core which is rich with structure (both spatially and in temperature), is subject to a variety of highly energetic processes, and yet is cooling rapidly and forming stars along thin, narrow filaments.

79 ASTRONOMY AND ASTROPHYSICS↗

NASA NTRS1986

Tethered Satellite System (TSS) core equipment

To date, three Tethered Satellite System (TSS) missions of the Italian provided scientific satellite orbiting in the ionosphere connected to U.S. Space Shuttle is foreseen. The first mission will use an electrically conductive tether of 20 km deployed upward from the orbiter flying at 300 km altitude. This mission will allow investigation of the TSS electrodynamic interaction with the ionosphere due to the high voltage induced across the two terminators of the system during its motion throughout the geomagnetic field. The second mission will use a dielectric tether of 100 km deployed downward from the Orbiter flying at 230 km altitude. Tethered-vehicle access to altitude as low as 120 to 150 km from the Orbiter would permit direct long term observation of phenomena in the lower thermosphere and determination of other dynamical physical processes. The third mission would use the same configuration of the first electrodynamic mission with the complete Core Equipment. Study of power generation by tethered systems would be possible by operating the Core Equipment in the inverted current mode. This mode of operation would allow ion current collection upon the TSS satellite by controlling its potential with respect to the ambient ionospheric plasma. The main requirements of the Core Equipment configuration to date foreseen for the first TSS electrodynamic mission is described. Besides the Core Equipment purposes, its hardware and operational sub-modes of operation are described.

Bonifazi, C.↗

DOE OSTI2022

13 C-metabolic flux analysis of Clostridium ljungdahlii illuminates its core metabolism under mixotrophic culture conditions

Carbon dioxide-fixing acetogenic bacteria (acetogens) utilizing the Wood-Ljungdahl Pathway (WLP) play an important role in CO 2 fixation in the biosphere and in the development of biological processes – alone or in cocultures, under both autotrophic and mixotrophic conditions – for production of chemicals and fuels. To date, limited work has been reported in experimentally validating and quantifying reaction fluxes of their core metabolic pathways. Here, the core metabolic model of the acetogen Clostridium ljungdahlii was interrogated using 13 C-metabolic flux analysis ( 13 C-MFA), which required the development of a new defined culture medium. Autotrophic, heterotrophic, and mixotrophic growth in defined medium was possible by adding 1 mM methionine to replace yeast extract. Our 13 C-MFA found an incomplete TCA cycle and inactive core pathways/reactions, notably those of the oxidative pentose phosphate pathway, Entner-Doudoroff pathway, and malate dehydrogenase. 13 C-MFA during mixotrophic growth using the parallel tracers [1– 13 C]fructose, [1,2– 13 C]fructose, [1,2,3– 13 C]fructose, and [U– 13 C]asparagine found that externally supplied CO 2 contributed the majority of carbon consumed. All internally-produced CO 2 from the catabolism of asparagine and fructose was consumed by the WLP. While glycolysis of fructose was active, it was not a major contributor to overall production of ATP, NADH, and acetyl-CoA. Gluconeogenic reactions were active despite the availability of organic carbon. Asparagine was catabolized equally via conversion to threonine and subsequent cleavage to produce acetaldehyde and glycine, and via deamination to fumarate and then the anaplerotic conversion of malate to pyruvate. Both pathways for asparagine catabolism produced acetyl-CoA, either directly via pyruvate or indirectly via the WLP. Cofactor stoichiometry based on our data predicted an essentially zero flux through the ferredoxin-dependent transhydrogenase (Nfn) reaction. Instead, nearly all of NADPH generated from the hydrogenase reaction was consumed by the WLP. Reduced ferredoxin produced by the hydrogenase reaction and glycolysis was mostly used for ATP generation via the RNF/ATPase system, with the remainder consumed by the WLP. NADH produced by RNF/ATPase was entirely consumed via the WLP.

13C metabolic flux analysis↗

DOE OSTI2024

Radiation Dose Modeling for Niowave’s Accelerator Driven Uranium Target Assembly 3

Molybdenum-99 is a high-value radionuclide commonly used for medical purposes within the United States. The National Nuclear Security Administration (NNSA) seeks to reliably produce the radioisotope 99 Mo without the use of highly enriched uranium. NNSA’s Office of Material Management and Minimization (M3) provides funding and government laboratory expertise to private companies to expedite the production process domestically and currently funds designs that use low-enriched uranium or other 99 Mo production pathways. Several production designs are being explored across the industry, including uranium fission and photonuclear conversion of 100 Mo targets. Niowave Inc. seeks to produce 99 Mo via a high-energy electron accelerator that strikes a lead-bismuth eutectic target that ultimately produces a consistent neutron flux. The neutron flux then interacts in a subcritical reactor core configuration to produce fission in low-enriched or natural uranium targets. These fissionable targets are then processed to extract 99 Mo. The purpose of this work is to estimate the neutron and photon dose response across Niowave’s proposed facility for worker safety during operation. Owing to the size of the proposed Niowave facility and necessary shielding, unbiased Monte Carlo radiation transport is impractical, and variance reduction methods are required. This work focuses on the weight window variance reduction method to produce high confidence dose response results within a Monte Carlo radiation transport code. Specifically, an adjoint-informed weight window methodology was created to improve the dose response estimates for accelerator-driven subcritical reactor designs. This adjoint-informed methodology was implemented for Niowave’s proposed design and improved dose results at far-field locations across the facility. Acceptable dose rate contours for the proposed facility were generated across the facility and are presented in this work.

07 ISOTOPE AND RADIATION SOURCES↗

DOE OSTI2017

Chemical evolution of groundwater in the Wilcox aquifer of the northern Gulf Coastal Plain, USA

The Wilcox aquifer is a major groundwater resource in the northern Gulf Coastal Plain (lower Mississippi Valley) of the USA, yet the processes controlling water chemistry in this clastic aquifer have received relatively little attention. The current study combines analyses of solutes and stable isotopes in groundwater, petrography of core samples, and geochemical modeling to identify plausible reactions along a regional flow path ∼300 km long. The hydrochemical facies evolves from Ca-HCO{sub 3} upgradient to Na-HCO{sub 3} downgradient, with a sequential zonation of terminal electron-accepting processes from Fe(III) reduction through SO{sub 4}{sup 2−} reduction to methanogenesis. In particular, decreasing SO{sub 4}{sup 2−} and increasing δ{sup 34}S of SO{sub 4}{sup 2−} along the flow path, as well as observations of authigenic pyrite in core samples, provide evidence of SO{sub 4}{sup 2−} reduction. Values of δ{sup 13}C in groundwater suggest that dissolved inorganic carbon is contributed both by oxidation of sedimentary organic matter and calcite dissolution. Inverse modeling identified multiple plausible sets of reactions between sampled wells, which typically involved cation exchange, pyrite precipitation, CH{sub 2}O oxidation, and dissolution of amorphous Fe(OH){sub 3}, calcite, or siderite. These reactions are consistent with processes identified in previous studies of Atlantic Coastal Plain aquifers. Contrasts in groundwater chemistry between the Wilcox and the underlying McNairy and overlying Claiborne aquifers indicate that confining units are relatively effective in limiting cross-formational flow, but localized cross-formational mixing could occur via fault zones. Consequently, increased pumping in the vicinity of fault zones could facilitate upward movement of saline water into the Wilcox.

58 GEOSCIENCES↗

DOE OSTI2016

Effects of molecular rotation after ionization and prior to fragmentation on observed recoil-frame photoelectron angular distributions in the dissociative photoionization of nonlinear molecules

Experimental angle-resolved photoelectron-photoion coincidence experiments measure photoelectron angular distributions (PADs) in dissociative photoionization (DPI) in the reference frame provided by the momenta of the emitted heavy fragments. By extension of the nomenclature used with DPI of diatomic molecules, we refer to such a PAD as a recoil-frame PAD (RFPAD). When the dissociation is fast compared to molecular rotational and bending motions, the emission directions of the heavy fragments can be used to determine the orientation of the bonds that are broken in the DPI at the time of the ionization, which is known as the axial-recoil approximation (ARA). When the ARA is valid, the RFPADs correspond to molecular-frame photoelectron angular distributions (MFPADs) when the momenta of a sufficient number of the heavy fragments are determined. When only two fragments are formed, the experiment cannot measure the orientation of the fragments about the recoil axes so that the resulting measured PAD is an azimuthally averaged RFPAD (AA-RFPAD). In this paper we consider how the breakdown of the ARA due to rotation will modify the observed RFPADs for DPI processes in nonlinear molecules for ionization by light of arbitrary polarization. This model is applied to the core C $1s$ DPI of ${\mathrm{CH}}_{4}$, with the results compared to experimental measurements and previous theoretical calculations done within the ARA. The published results indicate that there is a breakdown in the ARA for two-fragment events where the heavy-fragment kinetic energy release was less than 9 eV. Finally, including the breakdown of the ARA due to rotation in our calculations gives very good agreement with the experimental AA-RFPAD, leading to an estimate of upper bounds on the predissociative lifetimes as a function of the kinetic energy release of the intermediate ion states formed in the DPI process.

74 ATOMIC AND MOLECULAR PHYSICS↗

NASA NTRS2005

Cosmic Ray Propagation through the Magnetic Fields of the Galaxy with Extended Halo

In this project we perform theoretical studies of 3-dimensional cosmic ray propagation in magnetic field configurations of the Galaxy with an extended halo. We employ our newly developed Markov stochastic process methods to solve the diffusive cosmic ray transport equation. We seek to understand observations of cosmic ray spectra, composition under the constraints of the observations of diffuse gamma ray and radio emission from the Galaxy. The model parameters are directly are related to properties of our Galaxy, such as the size of the Galactic halo, particle transport in Galactic magnetic fields, distribution of interstellar gas, primary cosmic ray source distribution and their confinement in the Galaxy. The core of this investigation is the development of software for cosmic ray propagation models with the Markov stochastic process approach. Values of important model parameters for the halo diffusion model are examined in comparison with observations of cosmic ray spectra, composition and the diffuse gamma-ray background. This report summarizes our achievement in the grant period at the Florida Institute of Technology. Work at the co-investigator's institution, the University of New Hampshire, under a companion grant, will be covered in detail by a separate report.

Zhang, Ming↗

DOE OSTI2016

Nonsequential double ionization with mid-infrared laser fields

Using a full-dimensional Monte Carlo classical ensemble method, we present a theoretical study of atomic nonsequential double ionization (NSDI) with mid-infrared laser fields, and compare with results from near-infrared laser fields. Unlike single-electron strong-field processes, double ionization shows complex and unexpected interplays between the returning electron and its parent ion core. As a result of these interplays, NSDI for mid-IR fields is dominated by second-returning electron trajectories, instead of first-returning trajectories for near-IR fields. Here, some complex NSDI channels commonly happen with near-IR fields, such as the recollision-excitation-with-subsequent-ionization (RESI) channel, are virtually shut down by mid-IR fields. Besides, the final energies of the two electrons can be extremely unequal, leading to novel e-e momentum correlation spectra that can be measured experimentally.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2025

Optimization of distributed compute resources utilization in the CMS Global Pool

The CMS Submission Infrastructure is the primary system for managing computing resources for CMS workflows, including data processing, simulation, and analysis. It integrates geographically distributed resources from Grid, HPC, and cloud providers into federated pools managed by HTCondor and Glidein- WMS, for a total of around 500k CPU cores. This system dynamically manages workloads based on priorities defined by the collaboration. Additionally, CMS scheduling strategies must be flexible to handle multiple concurrent workloads while considering changing processing demands and resource availability from various providers.Efficient utilization of vast amounts of distributed compute resources is a key element for the success of the scientific programs of the LHC experiments. Optimizing the system is essential to maximize resource efficiency and fully utilize the distributed computing power. The CMS Submission Infrastructure team thus systematically investigates sources of inefficiency in workload scheduling to reduce their impact. In addition, a strategy of pilot overloading has been introduced to compensate for other inefficiency sources, thereby optimizing resource utilization and enhancing computational throughput.

Mascheroni, Marco [UC, San Diego (main)]↗

NASA NTRS2006

Grain Surface Chemistry and the Composition of Interstellar Ices

Submicron sized dust grains are an important component of the interstellar medium. In particular they provide surface where active chemistry can take place. At the low temperatures (-10 K) of the interstellar medium, colliding gas phase species will stick, diffuse, react, and form an icy mantle on these dust grains. This talk will review the principles of grain surface chemistry and delineate important grain surface routes, focusing on reactions involving H, D, and O among each other and with molecules such as CO. Interstellar ice mantles can be studied through the fundamental vibrations of molecular species in the mid-infrared spectra of sources embedded in or located behind dense molecular clouds. Analysis of this type of data has provided a complex view of the composition of these ices and the processes involved. Specifically, besides grain surface chemistry, the composition of interstellar ices is also affected by thermal processing due to nearby newly formed stars. This leads to segregation between different ice components as well as outgassing. The latter results in the formation of a so-called Hot Core region with a gas phase composition dominated by evaporated mantle species. Studies of such regions provide thus a different view on the ice composition and the chemical processes involved. Interstellar ices can also be processed by FUV photons and high energy cosmic ray ions. Cosmic ray processing likely dominates the return of accreted species to the gas phase where further gas phase reactions can take place. These different chemical routes towards molecular complexity in molecular clouds and particularly regions of star formation will be discussed.

Tielens, A. G. G. M.↗

DOE OSTI2015

On sulfur core level binding energies in thiol self-assembly and alternative adsorption sites: An experimental and theoretical study

Characteristic core level binding energies (CLBEs) are regularly used to infer the modes of molecular adsorption: orientation, organization, and dissociation processes. Here, we focus on a largely debated situation regarding CLBEs in the case of chalcogen atom bearing molecules. For a thiol, this concerns the case when the CLBE of a thiolate sulfur at an adsorption site can be interpreted alternatively as due to atomic adsorption of a S atom, resulting from dissociation. Results of an investigation of the characteristics of thiol self-assembled monolayers (SAMs) obtained by vacuum evaporative adsorption are presented along with core level binding energy calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) obtained by evaporation on Au display an unconventional CLBE structure at about 161.25 eV, which is close to a known CLBE of a S atom on Au. Adsorption and CLBE calculations for sulfur atoms and BDMT molecules are reported and allow delineating trends as a function of chemisorption on hollow, bridge, and atop sites and including the presence of adatoms. These calculations suggest that the 161.25 eV peak is due to an alternative adsorption site, which could be associated to an atop configuration. Therefore, this may be an alternative interpretation, different from the one involving the adsorption of atomic sulfur resulting from the dissociation process of the S–C bond. Calculated differences in S(2p) CLBEs for free BDMT molecules, SH group sulfur on top of the SAM, and disulfide are also reported to clarify possible errors in assignments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗