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At least 1,189 records · Page 66
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Structure of 28 Mg and influence of the neutron pf shell

Gamma-ray spectroscopy and lifetime measurements using the Doppler shift attenuation method (DSAM) were performed on the nucleus 28 Mg near the N = 20 “island of inversion,” which was populated using a 12 C ( 18 O, 2p) 28 Mg fusion-evaporation reaction to investigate the impact of shell evolution on its high-lying structure. Three new levels were identified at 7203(3), 7747(2), and 7929.3(12) keV along with several new gamma rays. A newly extracted B(E2; 4$^{+}_{1}$ → 2$^{+}_{1}$) of 42(7) e 2 fm 4 indicates reduced collectivity in the yrast band at high spin, consistent with ab initio symmetry adapted no-core shell model (SA-NCSM) calculations. At high excitation energy, evidence for the population of intruder orbitals was obtained through identification of negative parity levels [I π = (0, 4) - , (4, 5) - ] . Calculations using the SDPF-MU interaction indicate that these levels arise from single neutron excitation to the pf shell and provides evidence for the lowering of these intruder orbitals approaching the island of inversion.

20 ≤ A ≤ 38↗
DOE OSTI2018

Insights on the Alumina–Water Interface Structure by Direct Comparison of Density Functional Simulations with X-ray Reflectivity

Density functional theory molecular dynamics (DFT-MD) simulations are frequently used to predict the interfacial structures and dynamical processes at solid-water interfaces in efforts to gain a deeper understanding of these systems. However, the accuracy of these predictions of interfacial structure has not been rigorously quantified. Here, direct comparisons between large-scale DFT-MD simulations and high-resolution X-ray reflectivity (XR) measurements of the well-defined Al2O3(001)-water interface reveal the relative accuracy of these two methods to describe interfacial structure, a comparison that is enabled by XR’s high sensitivity to atomic-scale displacements. The DFT-MD simulated and XR model-fit structures are qualitatively similar, but XR signals calculated directly from the DFT-MD predictions deviate significantly from the experimental data, revealing discrepancies in these two approaches. Differences in the derived interfacial Al2O3 relaxation profiles of ~0.02 A within the top 5 layers are significant to XR but at the limit of the accuracy of DFT. Further differences are found in the surface hydration layer with a simulated average water layer height ~0.2 A higher than that observed experimentally. This is outside the accuracy of both XR and DFT and is not improved by the inclusion of a phenomenological correction for hydrogen bonding (e.g., Grimme).

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Synergy of semiempirical models and machine learning in computational chemistry

Catalyzed by enormous success in the industrial sector, many research programs have been exploring data-driven, machine learning approaches. Performance can be poor when the model is extrapolated to new regions of chemical space, e.g., new bonding types, new many-body interactions. Another important limitation is the spatial locality assumption in model architecture, and this limitation cannot be overcome with larger or more diverse datasets. The outlined challenges are primarily associated with the lack of electronic structure information in surrogate models such as interatomic potentials. Given the fast development of machine learning and computational chemistry methods, we expect some limitations of surrogate models to be addressed in the near future; nevertheless spatial locality assumption will likely remain a limiting factor for their transferability. Here, we suggest focusing on an equally important effort—design of physics-informed models that leverage the domain knowledge and employ machine learning only as a corrective tool. In the context of material science, we will focus on semi-empirical quantum mechanics, using machine learning to predict corrections to the reduced-order Hamiltonian model parameters. The resulting models are broadly applicable, retain the speed of semiempirical chemistry, and frequently achieve accuracy on par with much more expensive ab initio calculations. These early results indicate that future work, in which machine learning and quantum chemistry methods are developed jointly, may provide the best of all worlds for chemistry applications that demand both high accuracy and high numerical efficiency.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Effects of partial La filling and Sb vacancy defects on CoS b 3 skutterudites

Over the past decade, the open frame ("cagey") structure of CoSb 3 skutterudite has invited intensive filling studies with various rare-earth elements for delivering state-of-the-art mid-temperature thermoelectric performance. In order to rationalize previously reported experimental results and provide new insight into the underexplored roles of La fillers and Sb vacancies, ab initio density functional theory studies, along with semi-classical Boltzmann transport theory calculations, are performed for pristine CoSb 3 of different lattice settings and La-filled CoSb 3 with and without Sb s mono- and di-vacancy defects. We examine the effects of van der Waals (vdW) interactions, spin-orbit coupling (SOC), spin polarization, partial La-filling, and Sb vacancy defects on the structural, electronic, and thermoelectric properties. The vdW interactions profoundly affect the lattice constant, which in turn affects the band gap. The SOC shows minor effects on the electronic and thermoelectric properties. The peculiar quasi-Dirac band in the pristine CoSb 3 largely survives La filling but not Sb vacancies, which instead introduce dispersive bands in the band gap region. Importantly, the band structure, density of states, and Fermi surface of La-filled CoSb 3 are significantly spin polarized, giving rise to spin-dependent thermoelectric properties. Seebeck coefficients directly calculated as a function of chemical potential are interpreted in connection with the electronic structures. Temperature-dependent Seebeck coefficients derived for the experimentally studied materials agree well with available experimental data. Seebeck coefficients obtained as a function of charge carrier concentration corroborate a thermoelectrically favorable role at high filling fractions played by the electron/hole pockets on the Fermi surface associated with the degenerate valleys/hills in the conduction/valence bands, respectively. Our results serve to advance the understanding of CoSb 3 skutterudite, a class of materials with important fundamental and application implications for thermoelectrics and spintronics.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Analysis of a Li-Ion Nanobattery with Graphite Anode Using Molecular Dynamics Simulations

In this work, molecular dynamics simulations were performed of the initial charging of a Li-ion nanobattery with a graphite anode and lithium hexaflourphosphate (LiPF 6 ) salt dissolved in ethylene carbonate (CO 3 C 2 H 4 ) solvent as the electrolyte solution. The charging was achieved through the application of external electric fields simulating voltage sources. A variety of force fields were combined to simulate the materials of the nanobattery, including the solid electrolyte interphase, metal collectors, and insulator cover. Some of the force field parameters were estimated using ab initio methods and others were taken from the literature. We studied the behavior of Li-ions traveling from cathode to anode through electrolyte solutions of concentrations 1.15 and 3.36 M. Time-dependent variables such as energy, temperature, volume, polarization, and mean square displacement are reported; a few of these variables, as well as others such as current, resistance, current density, conductivity, and resistivity are reported as a function of the external field and charging voltage. A solid electrolyte interphase (SEI) layer was also added to the model to study the mechanism behind the diffusion of the Li-ions through the SEI. As the battery is charged, the depletion of Li atoms in the cathode and their accumulation in the anode follow a linear increase of the polarizability in the solvent, until reaching a saturation point after which the charging of the battery stops, i.e., the energy provided by the external source decays to very low levels. Lastly, the nanobattery model containing the most common materials of a commercial lithium-ion battery is very useful to determine atomistic information that is difficult or too expensive to obtain experimentally; available data shows consistency with our results.

25 ENERGY STORAGE↗
DOE OSTI2019

X-ray diffraction, Mössbauer spectroscopy, neutron diffraction, optical absorption and ab-initio calculation of magnetic process in orthorhombic YFe x Cr (1-x) O 3 (0 ≤ x ≤ 1) compounds

YFe x Cr (1-x) O 3 (0 ≤ x ≤ 1) compounds prepared by autocombustion were studied with X-ray and neutron powder diffraction, Mössbauer spectroscopy and ab-initio electronic structure calculations to try to understand the interplay of magnetic order and structural parameters as a function of doping in this multiferroic material. All samples exhibit the orthorhombic nuclear structure (space group symmetry Pnma) and the cell parameters vary continuously as a function of doping. In the neutron powder diffraction patterns it was observed that in addition to the Pnma nuclear structure peaks reflections are seen in all samples which arise from magnetic order. These peaks can be indexed using the nuclear unit cell indicating an ordering vector of k = (0,0,0). Using representational analysis and Rietveld refinements the magnetic structure was determined to be Pn’ma’ and the mean magnetic moment per transition metal atom was observed to decrease continuously from Fe to Cr. For compounds with x > 0.25 a weak ferromagnetic contribution is also present which is due to a small canting of the moments out of the basal plane. The Mössbauer spectra corroborate the NPD results with all samples showing single magnetic sextets at 4.2 K. The energy gap and the main direct interband transition of the endmember samples were obtained by optical absorption measurements. These optical data were analyzed with the help of DFT band structure calculation using the GGA-PBE + U approximation.

Salazar-Rodriquez, Roberto↗
DOE OSTI2015

Collisional excitation of NH(X{sup 3}Σ{sup −}) by Ne: Potential energy surface, scattering calculations, and comparison with experiments

We present a new three-dimensional potential energy surface (PES) for the NH(X{sup 3}Σ{sup −})–Ne van der Waals system, which explicitly takes into account the NH vibrational motion. Ab initio calculations of the NH–Ne PES were carried out using the open-shell single- and double-excitation coupled cluster approach with non-iterative perturbational treatment of triple excitations [RCCSD(T)]. The augmented correlation-consistent quadruple zeta (aug-cc-pVQZ) basis set was employed. Mid-bond functions were also included in order to improve the accuracy in the van der Waals well. Using this new PES, we have studied the collisional excitation of NH(X{sup 3}Σ{sup −}) by Ne. Close-coupling calculations of the collisional excitation cross sections of the fine-structure levels of NH by Ne are performed for energies up to 3000 cm{sup −1}, which yield, after thermal average, rate coefficients up to 350 K. The propensity rules between fine-structure levels are reported, and it is found that F-conserving cross sections are larger than F-changing cross sections even if the propensity rules are not as strong as for the NH–He system. The calculated rate coefficients are compared with available experimental measurements at room temperature and a fairly good agreement is found between experimental and theoretical data, confirming the good quality of the scattering calculations and also the accuracy of the potential energy surface used in this work.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

MechElastic: A Python library for analysis of mechanical and elastic properties of bulk and 2D materials

We report the MechElastic Python package evaluates the mechanical and elastic properties of bulk and 2D materials using the elastic coefficient matrix ( C ij ) obtained from any ab-initio density-functional theory (DFT) code. The current version of this package reads the output of VASP, ABINIT, and Quantum Espresso codes (but it can be easily generalized to any other DFT code) and performs the appropriate post-processing of elastic constants as per the requirement of the user. This program can also detect the input structure's crystal symmetry and test the mechanical stability of all crystal classes using the Born-Huang criteria. Various useful material-specific properties such as elastic moduli, longitudinal and transverse elastic wave velocities, Debye temperature, elastic anisotropy, 2D layer modulus, hardness, Pugh's ratio, Cauchy's pressure, Kleinman's parameter, and Lame's coefficients, can be estimated using this program. Another existing feature of this program is to employ the ELATE package (2016) [29] and plot the spatial variation of several elastic properties such as Poisson's ratio, linear compressibility, shear modulus, and Young's modulus in three dimensions. Further, the MechElastic package can plot the equation of state (EOS) curves for energy and pressure for a variety of EOS models such as Murnaghan, Birch, Birch-Murnaghan, and Vinet, by reading the inputted energy/pressure versus volume data obtained via numerical calculations or experiments. This package is particularly useful for the high-throughput analysis of elastic and mechanical properties of materials.

2D materials↗
DOE OSTI2026

Er Al :Al 2 ⁢O 3 for telecom-band photonics: Electronic structure and optical properties

Er-doped Al 2 ⁢O 3 is a promising host for telecom-band integrated photonics. Here, in this study, we combine ab initio calculations with a symmetry-resolved analysis to elucidate substitutional Er on the Al site (Er Al ) in 𝛼−Al 2 ⁢O 3 . First-principles relaxations confirm the structural stability of Er Al . We then use the local trigonal crystal-field symmetry to classify the Er-derived impurity levels by irreducible representations and to derive polarization-resolved electric-dipole selection rules, explicitly identifying the symmetry-allowed 𝑓−𝑑 hybridization channels. Kubo-Greenwood absorption spectra computed from Kohn-Sham states quantitatively corroborate these symmetry predictions. Furthermore, we connect the calculated intra-4⁢𝑓 line strengths to Judd-Ofelt theory, clarifying the role of 4⁢𝑓−5⁢𝑑 admixture in enabling optical activity. Notably, we predict a characteristic absorption near 1.47 µ⁢m (telecom band), relevant for on-chip amplification and emission. To our knowledge, a symmetry-resolved first-principles treatment of Er:Al 2 ⁢O 3 with an explicit Judd-Ofelt interpretation has not been reported, providing a transferable framework for tailoring rare-earth dopants in wide-band-gap oxides for integrated photonics. Our results for the optical spectra are in good agreement with experimental data. The resulting symmetry-based selection rules translate directly to polarization-dependent coupling in Al 2 ⁢O 3 integrated photonic waveguides and resonators, enabling device-level design of TE/TM-mode interaction with Er emitters in the 1.5-µ⁢m telecom band.

Er-doped Al2O3↗
DOE OSTI2016

Photoionisation study of Xe.CF{sub 4} and Kr.CF{sub 4} van-der-Waals molecules

We report on photoionization studies of Xe.CF{sub 4} and Kr.CF{sub 4} van-der-Waals complexes produced in a supersonic expansion and detected using synchrotron radiation and photoelectron-photoion coincidence techniques. The ionization potential of CF{sub 4} is larger than those of the Xe and Kr atoms and the ground state of the Rg.CF{sub 4}{sup +} ion correlates with Rg{sup +} ({sup 2}P{sub 3/2}) + CF{sub 4}. The onset of the Rg.CF{sub 4}{sup +} signals was found to be only ∼0.2 eV below the Rg ionization potential. In agreement with experiment, complementary ab initio calculations show that vertical transitions originating from the potential minimum of the ground state of Rg.CF{sub 4} terminate at a part of the potential energy surfaces of Rg.CF{sub 4}{sup +}, which are approximately 0.05 eV below the Rg{sup +} ({sup 2}P{sub 3/2}) + CF{sub 4} dissociation limit. In contrast to the neutral complexes, which are most stable in the face geometry, for the Rg.CF{sub 4}{sup +} ions, the calculations show that the minimum of the potential energy surface is in the vertex geometry. Experiments which have been performed only with Xe.CF{sub 4} revealed no Xe.CF{sub 4}{sup +} signal above the first ionization threshold of Xe, suggesting that the Rg.CF{sub 4}{sup +} ions are not stable above the first dissociation limit.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2024

Accurate Infrared Line Lists for 20 Isotopologues of CS 2 at Room Temperature

To facilitate atmospheric and spectroscopic studies of carbon disulfide, or CS 2 , in both planetary and exoplanetary atmospheres, we adopt the “Best Theory + Reliable High-resolution Experiment” algorithm to generate semiempirical IR line lists for the 20 most abundant CS 2 isotopologues, denoted as Ames-296K. The IR lists are computed using the Ames-1 potential energy surface, refined using the experimental transition set and an ab initio dipole moment surface fitted from CCSD(T)/aug-cc-pV(T/Q/5+d)Z dipoles extrapolated to a one-particle basis set limit. The IR lists cover the range of 0–10,000 cm -1 , with an S 296K cutoff at 10 -31 cm -1 /molecule·cm -2 (abundance included). A “natural” IR line list at 296 K includes about 10 million lines of the 20 isotopologues, with their intensities scaled by the corresponding abundances. The zero-point energy, partition functions, and abundances are reported for each isotopologue. The energy levels in the global effective Hamiltonian model for 12 C 32 S 2 are adopted to improve the line position accuracy. This new IR list for the main isotopologue is denoted as A+I.296K. Reliable HITRAN2020 line positions are also utilized to improve the accuracy of the 32 S 12 C 34 S, 32 S 12 C 33 S, and 32 S 13 C 32 S isotopologue line lists. The final composite line list is validated against Pacific Northwest National Laboratory experimental cross sections, showing excellent agreement. The agreement supports the quality of the composite line list and the power of synergy between experiment and theory. The new data are proposed for use in updating and expanding the CS 2 data in HITRAN and other high-resolution IR databases. Supplementary files are available in Zenodo and AHED.

Exoplanet atmospheric composition↗
DOE OSTI2016

Ice Ih anomalies: Thermal contraction, anomalous volume isotope effect, and pressure-induced amorphization

Ice Ih displays several anomalous thermodynamic properties such as thermal contraction at low temperatures, an anomalous volume isotope effect (VIE) rendering the volume of D{sub 2}O ice greater than that of H{sub 2}O ice, and a pressure-induced transition to the high-density amorphous (HDA) phase. Furthermore, the anomalous VIE increases with temperature, despite its quantum-mechanical origin. Here, embedded-fragment ab initio second-order many-body perturbation (MP2) theory in the quasiharmonic approximation (QHA) is applied to the Gibbs energy of an infinite, proton-disordered crystal of ice Ih at wide ranges of temperatures and pressures. The quantum effect of nuclei moving in anharmonic potentials is taken into account from first principles without any empirical or nonsystematic approximation to either the electronic or vibrational Hamiltonian. MP2 predicts quantitatively correctly the thermal contraction at low temperatures, which is confirmed to originate from the volume-contracting hydrogen-bond bending modes (acoustic phonons). It qualitatively reproduces (but underestimates) the thermal expansion at higher temperatures, caused by the volume-expanding hydrogen-bond stretching (and to a lesser extent librational) modes. The anomalous VIE is found to be the result of subtle cancellations among closely competing isotope effects on volume from all modes. Consequently, even ab initio MP2 with the aug-cc-pVDZ and aug-cc-pVTZ basis sets has difficulty reproducing this anomaly, yielding qualitatively varied predictions of the sign of the VIE depending on such computational details as the choice of the embedding field. However, the temperature growth of the anomalous VIE is reproduced robustly and is ascribed to the librational modes. These solid-state MP2 calculations, as well as MP2 Born–Oppenheimer molecular dynamics, find a volume collapse and a loss of symmetry and long-range order in ice Ih upon pressure loading of 2.35 GPa or higher. Concomitantly, rapid softening of acoustic phonons is observed starting around 2 GPa. They constitute a computational detection of a mechanical instability in ice Ih and the resulting pressure-induced amorphization to HDA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Quantitative Infrared Absorption Spectra and Vibrational Assignments of Crotonaldehyde and Methyl Vinyl Ketone Using Gas-Phase Mid-Infrared, Far-Infrared, and Liquid Raman Spectra: s-cis vs s-trans Composition Confirmed via Temperature Studies and ab Initio Methods

Methyl vinyl ketone (MVK) and crotonaldehyde are chemical isomers; both are also important species in tropospheric chemistry. We report quantitative vapor-phase infrared spectra of crotonaldehyde and MVK vapors over the 540-6500 cm-1 range. Vibrational assignments of all fundamental modes are made for both molecules based on far- and mid-infrared vapor-phase spectra, liquid Raman spectra, along with density functional theory and ab initio MP2 and high energy-accuracy compound theoretical models (W1BD). Theoretical results indicate that at room temperature the crotonaldehyde equilibrium mixture is approximately 97% s-trans and only 3% s-cis conformer. Nearly all observed bands are thus associated with the s-trans conformer, but a few appear to be uniquely associated the s-cis conformer, notably ν16c at 730.90 cm-1, which displays a substantial intensity increase with temperature (62% upon going from 5 to 50 oC). The intensity of the corresponding mode of the s-trans conformer decreases with temperature. Under the same conditions, the MVK equilibrium mixture is approximately 69% s-trans conformer and 31% s-cis. W1BD calculations indicate that for MVK this is one of those (rare) cases where there are comparable populations of both conformers, ~doubling the number of observed bands and exacerbating the vibrational assignments. We uniquely assign the bands associated with both the MVK s-cis conformer as well as those of the s-trans, thus completing the vibrational analyses of both conformers from the same set of experimental spectra. Integrated band intensities are reported for both molecules along with global warming potential values. Using the quantitative IR data, potential bands for atmospheric monitoring are also discussed.

Lindenmaier, Rodica↗
DOE OSTI2015

Modeling the high-energy electronic state manifold of adenine: Calibration for nonlinear electronic spectroscopy

Pump-probe electronic spectroscopy using femtosecond laser pulses has evolved into a standard tool for tracking ultrafast excited state dynamics. Its two-dimensional (2D) counterpart is becoming an increasingly available and promising technique for resolving many of the limitations of pump-probe caused by spectral congestion. The ability to simulate pump-probe and 2D spectra from ab initio computations would allow one to link mechanistic observables like molecular motions and the making/breaking of chemical bonds to experimental observables like excited state lifetimes and quantum yields. From a theoretical standpoint, the characterization of the electronic transitions in the visible (Vis)/ultraviolet (UV), which are excited via the interaction of a molecular system with the incoming pump/probe pulses, translates into the determination of a computationally challenging number of excited states (going over 100) even for small/medium sized systems. A protocol is therefore required to evaluate the fluctuations of spectral properties like transition energies and dipole moments as a function of the computational parameters and to estimate the effect of these fluctuations on the transient spectral appearance. In the present contribution such a protocol is presented within the framework of complete and restricted active space self-consistent field theory and its second-order perturbation theory extensions. The electronic excited states of adenine have been carefully characterized through a previously presented computational recipe [Nenov et al., Comput. Theor. Chem. 1040–1041, 295-303 (2014)]. A wise reduction of the level of theory has then been performed in order to obtain a computationally less demanding approach that is still able to reproduce the characteristic features of the reference data. Foreseeing the potentiality of 2D electronic spectroscopy to track polynucleotide ground and excited state dynamics, and in particular its expected ability to provide conformational dependent fingerprints in dimeric systems, the performances of the selected reduced level of calculations have been tested in the construction of 2D electronic spectra for the in vacuo adenine monomer and the unstacked adenine homodimer, thereby exciting the L{sub b}/L{sub a} transitions with the pump pulse pair and probing in the Vis to near ultraviolet spectral window.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Ab initio modeling of 2D layered organohalide lead perovskites

A number of 2D layered perovskites A{sub 2}PbI{sub 4} and BPbI{sub 4}, with A and B mono- and divalent ammonium and imidazolium cations, have been modeled with different theoretical methods. The periodic structures have been optimized (both in monoclinic and in triclinic systems, corresponding to eclipsed and staggered arrangements of the inorganic layers) at the DFT level, with hybrid functionals, Gaussian-type orbitals and dispersion energy corrections. With the same methods, the various contributions to the solid stabilization energy have been discussed, separating electrostatic and dispersion energies, organic-organic intralayer interactions and H-bonding effects, when applicable. Then the electronic band gaps have been computed with plane waves, at the DFT level with scalar and full relativistic potentials, and including the correlation energy through the GW approximation. Spin orbit coupling and GW effects have been combined in an additive scheme, validated by comparing the computed gap with well known experimental and theoretical results for a model system. Finally, various contributions to the computed band gaps have been discussed on some of the studied systems, by varying some geometrical parameters and by substituting one cation in another’s place.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Data for "Plasmon-driven exciton formation in a non-equilibrium Fermi liquid"

This repository contains source data for key plots presented in the manuscript "Plasmon-driven exciton formation in a non-equilibrium Fermi liquid." Experimental data that was analyzed in Igor Pro 8 are presented as the .pxp files used to generate individual sub-plots. Electronic spectral function calculations are provided as .txt files, in which consecutive rows refer to the meshgrid x coordinate, y coordinate, spectral function (and, where relevant, axis-projected local angular momentum). We additionally include the Wannier model and DFT-obtained bulk band structure on which the Wannier model was based. Files are named as the number of the figure in the manuscript to which they correspond, with additional details included where necessary. Details of file names: 2a_DOS_Lxz_Ek_KGM_40layer_xnum_800kpt_tot.txt: Density of states, xz-axis projected local orbital angular momentum, for 800 points along the K-Gamma-M path, for a 40-layer model. 2c_composite_y.pxp: ARPES (angle-resolved photoemission spectroscopy) spectra along the ky axis, including both a scan near the Fermi level and a scan at high kinetic energies. 2d_LCP_RCP_diff_Sect_20K.pxp: difference between ARPES constant energy cuts at T=20 K at E0 + 0.23 eV taken with left- and right-circularly polarized photons. The polarization-integrated intensity at the constant energy cut is also included. 2e_DOS_L45_E11pt79_m0pt25to0pt25_xnum_800kpt_tot.txt: Density of states, xz-projected local orbital angular momentum, and corresponding k-points in two dimensions from ab-initio electronic structure calculations for a constant-energy cut. 3a_[x]_[y]ps: ARPES cut under excitation at a fluence of x uJ/cm2, measured y ps after photoexcitation. Measurements were performed at 9 K. 3b_[x]: Energy distribution curves under excitation at a fluence x uJ/cm2 at selected delay times after photoexcitation. 4a_ImSigma_vs_temperature.pxp: Imaginary self energy (extracted from ARPES linewidths) at different energies above E0 for selected lattice temperatures. 4b_EELS_lowE.pxp: Electron energy loss spectrum over a low energy range 5b_diff_55m15.pxp: Difference between momentum-integrated Tr-ARPES traces at 55 uJ/cm2 and 15 uJ/cm2 photoexcitation. Time-dependent intensity at each energy level has been normalized to a maximum of 1 for each individual fluence prior to subtraction. 5d_invtau_at_EX_vs_fluence.pxp: decay rate at a specified energy EX for different excitation fluences, from single exponential fits. NOTE: Analyses based on the Wannier model presented here should cite both the associated Article and this dataset. For all other files in the repository, citing the dataset alone is sufficient.

Acharya, Rishi [University of Illinois] (ORCID:000↗
DOE OSTI2015

The stereo-dynamics of collisional autoionization of ammonia by helium and neon metastable excited atoms through molecular beam experiments

A combined analysis of both new (energy spectra of emitted electrons) and previously published (ionization cross sections) experimental data, measured under the same conditions and concerning electronically excited lighter noble gas –NH{sub 3} collisional autoionization processes, is carried out. Such an analysis, performed by exploiting a formulation of the full potential energy surface both in the real and imaginary parts, provides direct information on energetics, structure, and lifetime of the intermediate collision complex over all the configuration space. The marked anisotropy in the attraction of the real part, driving the approach of reagents, and the selective role of the imaginary component, associated to the charge transfer coupling between entrance and exit channels, suggests that reactive events occur almost exclusively in the molecular hemisphere containing the nitrogen lone pair. Crucial details on the stereo-dynamics of elementary collisional autoionization processes are then obtained, in which the open shell nature of the disclosed ionic core of metastable atom plays a crucial role. The same analysis also suggests that the strength of the attraction and the anisotropy of the interaction increases regularly along the series Ne{sup *}({sup 3}P), He{sup *}({sup 3}S), He{sup *}({sup 1}S)–NH{sub 3}. These findings can be ascribed to the strong rise of the metastable atom electronic polarizability (deformability) along the series. The obtained results can stimulate state of the art ab initio calculations focused on specific features of the transition state (energetics, structure, lifetime, etc.) which can be crucial for a further improvement of the adopted treatment and to better understand the nature of the leading interaction components which are the same responsible for the formation of the intermolecular halogen and hydrogen bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗