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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Coronae of Stars with Supersolar Elemental Abundances

Coronal elemental abundances are known to deviate from the photospheric values of their parent star, with the degree of deviation depending on the first ionization potential (FIP). This study focuses on the coronal composition of stars with supersolar photospheric abundances. We present the coronal abundances of six such stars: 11 LMi, iota Hor, HR 7291, tau Boo, and alpha Cen A and B. These stars all have high-statistics X-ray spectra, three of which are presented for the first time. The abundances we measured were obtained using the line-resolved spectra of the Reflection Grating Spectrometer (RGS) in conjunction with the higher throughput EPIC-pn camera spectra onboard the XMM-Newton observatory. A collisionally ionized plasma model with two or three temperature components is found to represent the spectra well. All elements are found to be consistently depleted in the coronae compared to their respective photospheres. For 11 LMi and tau Boo no FIP effect is present, while iota Hor, HR 7291, and alpha Cen A and B show a clear FIP trend. These conclusions hold whether the comparison is made with solar abundances or the individual stellar abundances. Unlike the solar corona, where low-FIP elements are enriched, in these stars the FIP effect is consistently due to a depletion of high-FIP elements with respect to actual photospheric abundances. A comparison with solar (instead of stellar) abundances yields the same fractionation trend as on the Sun. In both cases, a similar FIP bias is inferred, but different fractionation mechanisms need to be invoked.

stars: abundances / stars: coronae / stars: genera↗
DOE OSTI2021

Teaching a neural network to attach and detach electrons from molecules

Abstract Interatomic potentials derived with Machine Learning algorithms such as Deep-Neural Networks (DNNs), achieve the accuracy of high-fidelity quantum mechanical (QM) methods in areas traditionally dominated by empirical force fields and allow performing massive simulations. Most DNN potentials were parametrized for neutral molecules or closed-shell ions due to architectural limitations. In this work, we propose an improved machine learning framework for simulating open-shell anions and cations. We introduce the AIMNet-NSE (Neural Spin Equilibration) architecture, which can predict molecular energies for an arbitrary combination of molecular charge and spin multiplicity with errors of about 2–3 kcal/mol and spin-charges with error errors ~0.01e for small and medium-sized organic molecules, compared to the reference QM simulations. The AIMNet-NSE model allows to fully bypass QM calculations and derive the ionization potential, electron affinity, and conceptual Density Functional Theory quantities like electronegativity, hardness, and condensed Fukui functions. We show that these descriptors, along with learned atomic representations, could be used to model chemical reactivity through an example of regioselectivity in electrophilic aromatic substitution reactions.

36 MATERIALS SCIENCE↗
NASA NTRS1972

Population inversion calculations using near resonant charge exchange as a pumping mechanism

Near resonance charge exchange between ions of a large ionization potential gas such as helium or neon and vapors of metals such as zinc, cadmium, selenium, or tellurium has produced laser action in the metal ion gas. The possibility of obtaining population inversions in near resonant charge exchange systems (Xe-Ca, Xe-Mg, Xe-Sr, Xe-Ba, Ar-Mg, N-Ca) was investigated. The analysis is an initial value problem that utilizes rate equations for the densities of relevant levels of the laser gas (Ca, Ba, Mg, or Sr) and an electron energy equation. Electron excitation rates are calculated using the Bohr-Thomson approximation for the cross section. Approximations to experimental values of the electron ionization cross section and the ion-atom charge exchange cross section are used. Preliminary results have been obtained for the Ca-Xe system and show that it is possible to obtain gains greater than 10 to the 14th power/m with inversion times up to 8x10 to the minus 7th power second. A possible charge exchange laser system using a MPD arc plasma accelerator is also described.

Chubb, D. L.↗
NASA NTRS1986

Calculated ground state potential surface and excitation energies for the copper trimer

In the context of their relevance to catalysis and to materials science problems, transition metals and transition metal (TM) compounds are currently of considerable interest, and studies have been conducted of the copper trimer, Cu3. The present investigation is concerned with a study of the ground state surface and several groups of excited states in order to improve the understanding of the spectroscopy of Cu3. Differences of the current study from previous investigations are related to an employment of larger basis sets and a more extensive electron correlation. This was done with the objective to obtain a more accurate definition of the ground state surface. Features of the bonding in the copper dimer are considered to obtain a basis for an understanding of the copper trimer. Attention is given to calculational details, the ground state surface, and calculated vertical excitation energies. The results of SCF/SDCI calculations are reported for portions of the ground surface, for two groups of excited states, and for the ionization potential of Cu3.

Walch, S. P.↗
DOE OSTI2020

Etching of Si 3 N 4 induced by electron beam plasma from hollow cathode plasma in a downstream reactive environment

An etching system based on the interaction of electrons extracted from a direct current (DC) hollow-cathode (HC) Ar plasma and injected towards a Si3N4 covered silicon substrate located in the downstream reactive environment created by an additional remote CF 4 /O 2 plasma source was developed and evaluated. By controlling the properties of the injected beam electrons, this approach allows to deliver energy to a surface functionalized by exposure to reactive species, and initiate surface etching. The energy of the primary beam electrons is controlled by the acceleration voltage relative to the HC discharge. Ar atoms flow from the high-pressure HC discharge into the low pressure downstream reactive environment in the process chamber. For an acceleration voltage greater than the ionization potential of Ar and/or process gas species, the energetic primary beam electrons produce a secondary plasma in the process chamber, and can also cause additional dissociation. We have characterized the properties of the secondary plasma and also surface etching of Si 3 N 4 as a function of process parameters, including acceleration voltage (0-80 V), discharge current of the HC discharge (1-2 A), pressure (3.5-20 mTorr), source to substrate distance (1.5 to 5 cm), and feed gas composition (20% and 80% O2 in CF 4 /O 2 ). The electron energy probability function (EEPF) measured with a Langmuir probe about 2.5 cm below the extraction ring suggests several major groups of electrons for this situation, including high energy primary beam electrons with an energy that varies as the acceleration voltage is changed and low energy electrons produced by beam electron-induced ionization of the Ar gas in the process chamber. When a remote CF 4 /O 2 plasma is additionally coupled to the process chamber, Si 3 N 4 surfaces can be functionalized, and by varying the energy of the beam electrons, Si 3 N 4 etching can be induced by electron-neutral synergy effect with plasma-surface interaction. For conditions without beam electron injection, the remote plasma etching rate (ER) of Si 3 N 4 depends strongly on the O 2 concentration in the CF 4 /O 2 processing gas mixture and can be suppressed for O 2 -rich process conditions by the formation of a SiONF passivation layer on the Si 3 N 4 surface. The combination of the HC electron beam source with the remote plasma source (HCEB-RP) makes it possible to induce Si 3 N 4 etching for O 2 -rich remote plasma conditions where remote plasma by itself produces negligible Si 3 N 4 etching. The electron enhanced etching of Si 3 N 4 depends strongly on O 2 /CF 4 mixing ratio reflecting changing arrival rates of O and F species at the surface. Optical emission spectroscopy was used to estimate the ratio of gas phase F and O densities and found to be controlled by the gas mixing ratio and independent of HC EB operating conditions. At this time the detailed sequence of events operative in the etching mechanism is unclear. While the increase of the electron energy is ultimately responsible for initiating surface etching, at present we cannot rule out a role of ions from the simultaneously produced secondary plasma in plasma surface interaction mechanisms.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

The Physics of the Coronal-line Region for Galaxies in Mapping Galaxies at Apache Point Observatory

The fundamental nature and extent of the coronal-line region (CLR), which may serve as a vital tracer for active galactic nucleus (AGN) activity, remain unresolved. Previous studies suggest that the CLR is produced by AGNdriven outflows and occupies a distinct region between the broad-line region and the narrow-line region, which places it tens to hundreds of parsecs from the galactic center. Here, we investigate 10 coronal line (CL; ionization potential ≳100 eV) emitting galaxies from the Sloan Digital Sky Survey IV Mapping Galaxies at Apache Point Observatory (MaNGA) catalog with emission from one or more CLs detected at ≥5$σ$ above the continuum in at least 10 spaxels—the largest such MaNGA catalog. We find that the CLR is far more extended, reaching out to 1.3–23 kpc from the galactic center. We crossmatch our sample of 10 CL galaxies with the largest existing MaNGA AGN catalog and identify seven in it; two of the remaining three are galaxy mergers and the final one is an AGN candidate. Further, we measure the average CLR electron temperatures as ranging between 12,331 and 22,530 K, slightly above the typical threshold for pure AGN photoionization (~20,000 K) and indicative of shocks (e.g., merger induced or from supernova remnants) in the CLR. In conclusion, we reason that ionizing photons emitted by the central continuum source (i.e., AGN photoionization) primarily generate the CLs, and that energetic shocks are an additional ionization mechanism that likely produce the most extended CLRs we measure.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

On the nature of droplet production in DC glows with a liquid anode: mechanisms and potential applications

The interactions between plasma and liquid solutions give rise to the formation of chemically reactive species useful for many applications, but the mass transport in the interfacial region is usually limited and not fully understood. In this work, we report on the observation and explanation of droplet ejection at the plasma–liquid interface of a one-atmosphere glow discharge with the liquid anode. The impact of droplets emission on plasma properties is also analyzed by spectroscopy. The process, which is an efficient mass and charge transport mechanism, apparently occurs during discharge operation and thus constitutes a feedback vehicle between the discharge and the liquid. Distinctive from the well-known Talyor cone droplets associated with liquid cathodes, the observed droplets originate from the bubbles due to electrolysis and solvated air which does not require strong electric field at liquid surface. Instead, the droplets are ejected by bubble cavity rupture at the plasma–liquid interface and their size, initial speed are strongly dependent on the gravity, inertia and capillarity. Further, the droplets emerge near the plasma attachment and are subsequently vaporized, emitting intense UV and visible light, which originated from excited OH radicals and sodium derived from the liquid electrolyte. Spectroscopy analysis confirmed that the bursting droplets generally reduce the gas temperature while their effects on electron density depend on the composition of the liquid anode. Results also show that droplets from NaCl solution increase the plasma electron density due to the lower ionization potential of sodium. These findings reveal a new mechanism for discharge maintenance and mass transport as well as suggest a simple approach to dispersing plasma-activated liquid into the gas phase and thus enhancing plasma–liquid interaction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS2004

Identification of Interplanetary Coronal Mass Ejections at 1 AU Using Multiple Solar Wind Plasma Composition Anomalies

We investigate the use of multiple simultaneous solar wind plasma compositional anomalies, relative to the composition of the ambient solar wind, for identifying interplanetary coronal mass ejection (ICME) plasma. We first summarize the characteristics of several solar wind plasma composition signatures (O(+7)/O(+6), Mg/O, Ne/O, Fe charge states, He/p) observed by the ACE and WIND spacecraft within the ICMEs during 1996 - 2002 identsed by Cane and Richardson. We then develop a set of simple criteria that may be used to identify such compositional anomalies, and hence potential ICMEs. To distinguish these anomalies from the normal variations seen in ambient solar wind composition, which depend on the wind speed, we compare observed compositional signatures with those 'expected' in ambient solar wind with the same solar wind speed. This method identifies anomalies more effectively than the use of fixed thresholds. The occurrence rates of individual composition anomalies within ICMEs range from approx. 70% for enhanced iron and oxygen charge states to approx. 30% for enhanced He/p (> 0.06) and Ne/O, and are generally higher in magnetic clouds than other ICMEs. Intervals of multiple anomalies are usually associated with ICMEs, and provide a basis for the identification of the majority of ICMEs. We estimate that Cane and Richardson, who did not refer to composition data, probably identitied approx. 90% of the ICMEs present. However, around 10% of their ICMEs have weak compositional anomalies, suggesting that the presence of such signatures does not provide a necessary requirement for an ICME. We note a remarkably similar correlation between the Mg/O and O(7)/O(6) ratios in hourly-averaged data both within ICMEs and the ambient solar wind. This 'universal' relationship suggests that a similar process (such as minor ion heating by waves inside coronal magnetic field loops) produces the first-ionization potential bias and ion freezing-in temperatures in the source regions of both ICMEs and the ambient solar wind.

Richardson, I. G.↗
DOE OSTI2020

Molecular-Scale Characterization of Photoinduced Charge Separation in Mixed-Dimensional InSe–Organic van der Waals Heterostructures

Layered indium selenide (InSe) is an emerging two-dimensional semiconductor that has shown significant promise for high-performance transistors and photodetectors. The range of optoelectronic applications for InSe can potentially be broadened by forming mixed-dimensional van der Waals heterostructures with zero-dimensional molecular systems that are widely employed in organic electronics and photovoltaics. Here, we report the spatially resolved investigation of photoinduced charge separation between InSe and two molecules (C 70 and C 8 -BTBT) using scanning tunneling microscopy combined with laser illumination. We experimentally and computationally show that InSe forms type-II and type-I heterojunctions with C 70 and C 8 -BTBT, respectively, due to an interplay of charge transfer and dielectric screening at the interface. Laser-excited scanning tunneling spectroscopy reveals a ~0.25 eV decrease in the energy of the lowest unoccupied molecular orbital of C 70 with optical illumination. Furthermore, photoluminescence spectroscopy and Kelvin probe force microscopy indicate that electron transfer from InSe to C 70 in the type-II heterojunction induces a photovoltage that quantitatively matches the observed downshift in the tunneling spectra. In contrast, no significant changes are observed upon optical illumination in the type-I heterojunction formed between InSe and C 8 -BTBT. Density functional theory calculations further show that, despite the weak coupling between the molecular species and InSe, the band alignment of these mixed-dimensional heterostructures strongly differs from the one suggested by the ionization potential and electronic affinities of the isolated components. Self-energy-corrected density functional theory indicates that these effects are the result of the combination of charge redistribution at the interface and heterogeneous dielectric screening of the electron–electron interactions in the heterostructure. In addition to providing specific insight for mixed-dimensional InSe–organic van der Waals heterostructures, this work establishes a general experimental methodology for studying localized charge transfer at the molecular scale that is applicable to other photoactive nanoscale systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1996

Spectra of High-Ionization Seyfert 1 Galaxies: Implications for the Narrow-Line Region

We present line profiles and profile parameters for the Narrow-Line Regions (NLRs) of six Seyfert 1 galaxies with high-ionization lines: MCG 8-11-11, Mrk 79, Mrk 704, Mrk 841, NGC 4151, and NGC 5548. The sample was chosen primarily with the goal of obtaining high-quality [Fe VII] lambda6087 and, when possible, [Fe X] lambda6374 profiles to determine if these lines are more likely formed in a physically distinct 'coronal line region' or are formed throughout the NLR along with lines of lower critical density (n(sub cr)) and/or Ionization Potential (IP). We discuss correlations of velocity shift and width with n(sub cr) and IP. In some objects, lines of high IP and/or n(sub cr) are systematically broader than those of low IP/n(sub cr). Of particular interest, however, are objects that show no correlations of line width with either IP or n(sub cr). In these objects, lines of high and low IP/n(sub cr), are remarkably similar, which is difficult to reconcile with the classical picture of the NLR, in which lines of high and low IP/n(sub cr) are formed in physically distinct regions. We argue for similar spatial extents for the flux in lines with similar profiles. Here, as well as in a modeling-oriented companion paper, we develop further an idea suggested by Moore & Cohen that objects that do and do not show line width correlations with IP/n(sub cr) can both be explained in terms of a single NLR model with only a small difference in the cloud column density distinguishing the two types of object. Overall, our objects do not show correlations between the Full Width at Half-Maximum (FWHM) and IP and/or n(sub cr). The width must be defined by a parameter that is sensitive to extended profile wings in order for the correlations to result. We present models in which FWHM correlations with IP and/or n(sub cr) result only after simulating the lower spectral resolution used in previous observational studies. The models that simulate the higher spectral resolution of our observational study produce line width correlations only if the width is defined by a parameter that is more sensitive to extended profile wings than is the FWHM. Our sample of six objects is in effect augmented by incorporating the larger sample (16 objects) of Veilleux into some of our discussion. This paper focuses on new interpretations of NLR emission-line spectra and line profiles that stem directly from the observations. Paper 2 focuses on modeling and complements this paper by illustrating explicitly the effects that spatial variations in electron density, ionization parameter, and column density have on model profiles. By comparing model profiles with the observed profiles presented here, as well as with those presented by Veilleux, Paper 2 yields insight into how the electron density, ionization parameter, and column density likely vary throughout the NLR.

Moore, David↗
DOE OSTI2024

Organic Molecules Mimic Alkali Metals Enabling Spontaneous Harpoon Reactions with Halogens

Abstract The harpoon mechanism has been a milestone in molecular reaction dynamics. Until now, the entity from which electron harpooning occurs has been either alkali metal atoms or non‐metallic analogs in their excited states. In this work, we demonstrate that a common organic molecule, octamethylcalix[4] pyrrole (omC4P), behaves just like alkali metal atoms, enabling the formation of charge‐separated ionic bonding complexes with halogens omC4P + ⋅ X − ( X =F−I, SCN) via the harpoon mechanism. Their electronic structures and chemical bonding were determined by cryogenic photoelectron spectroscopy of the corresponding anions and confirmed by theoretical analyses. The omC4P + ⋅ X − could be visualized to form from the reactants omC4P+ X via electron harpooning from omC4P to X at a distance defined by the energy difference between the ionization potential of omC4P and electron affinity of X .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ground and excited electronic structures of electride and alkalide units: The cases of Metal-Tren, -Azacryptand, and -TriPip222 complexes

A systematic electronic structure analysis was conducted for M(L) n molecular electrides and their corresponding alkalide units M(L) n @M' (M/M' = Na, K; L = Tren, Azacryptand, TriPip222; n = 1, 2). All complexes belong to the “superalkali” category due to their low ionization potentials. The saturated molecular electrides display M+(L) n - form with a greatly diffuse quasispherical electron cloud. They were identified as “superatoms” considering the contours of populating atomic-type molecular orbitals. The observed superatomic Aufbau order of M(Tren) 2 is 1S, 1P, 1D, 1F, 2S, 2P, and 1G and it is consistent with those of M(Azacryptand) and M(TriPip222) up to the analyzed 1F level. Their excitation energies decrease gradually moving from M(Tren) 2 to M(Azacryptand) and to M(TriPip222). The studied alkalide complexes carry [M(L) n ] + @M' - ionic structure and their dissociation energies vary in the sequence of K(L) n @Na > Na(L) n @Na > K(L) n @K > Na(L) n @K. Similar to molecular electrides, the anions of alkalide units occupy electrons in diffuse Rydberg-like orbitals. In this work, excited states of [M(L) n @M'] 0/+/- and their trends are also analyzed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Linear Dichroism of the Optical Properties of SnS and SnSe Van der Waals Crystals

Abstract Tin monochalcogenides SnS and SnSe, belonging to a family of Van der Waals crystals isoelectronic to black phosphorus, are known as environmentally friendly materials promising for thermoelectric conversion applications. However, they exhibit other desired functionalities, such as intrinsic linear dichroism of the optical and electronic properties originating from strongly anisotropic orthorhombic crystal structures. This property makes them perfect candidates for polarization‐sensitive photodetectors working in near‐infrared spectral range. A comprehensive study of the SnS and SnSe crystals is presented, performed by means of optical spectroscopy and photoemission spectroscopy, supported by ab initio calculations. The studies reveal the high sensitivity of the optical response of both materials to the incident light polarization, which is interpreted in terms of the electronic band dispersion and orbital composition of the electronic bands, dictating the selection rules. From the photoemission investigation the ionization potential, electron affinity and work function are determined, which are parameters crucial for the design of devices based on semiconductor heterostructures.

Chemistry↗
DOE OSTI2022

Titanium Carbide MXene Hole Contacts for CdTe Photovoltaics

CdTe is a high‐efficiency thin‐film photovoltaic technology that has seen tremendous commercial success over the past decade. Yet despite the improvement of other device characteristics, the fabrication of an ohmic hole back contact layer has remained a challenge due to the high ionization potential of CdTe, which limits the external potential that can be feasibly reached even as other characteristics of the device improve. MXenes, a family of 2D materials with rapidly growing scientific and commercial interest, offer a promising route to forming low‐cost, low‐barrier contacts due to their demonstrated high work function, metallic conductivity, and facile solution processing from benign solvents. Here, it is shown that Ti 3 C 2 T x MXene films processed from an aqueous colloidal dispersion can perform as a highly efficient hole contact material for CdTe solar cells, resulting in high power‐conversion efficiencies. The role of the Schottky barrier formation in Ti 3 C 2 T x ‐contacted CdTe devices is probed, and potential pathways for the future development of this potent combination of materials are elucidated. The modularity of the expansive MXene family of materials presents a promising strategy for developing next‐generation hole contacts for CdTe solar cells.

14 SOLAR ENERGY↗
DOE OSTI2025

Automated workflow for non-empirical Wannier-localized optimal tuning of range-separated hybrid functionals

Here, we introduce an automated workflow for generating non-empirical Wannier-localized optimally-tuned screened range-separated hybrid (WOT-SRSH) functionals. WOT-SRSH functionals have been shown to yield highly accurate fundamental band gaps, band structures, and optical spectra for bulk and 2D semiconductors and insulators. Our workflow automatically and efficiently determines the WOT-SRSH functional parameters for a given crystal structure and composition, approximately enforcing the correct screened long-range Coulomb interaction and an ionization potential ansatz. In contrast to previous manual tuning approaches, our tuning procedure relies on a new search algorithm that only requires a few hybrid functional calculations with minimal user input. We demonstrate our workflow on 23 previously studied semiconductors and insulators, reporting the same high level of accuracy. By automating the tuning process and improving its computational efficiency, the approach outlined here enables applications of the WOT-SRSH functional to compute spectroscopic and optoelectronic properties for a wide range of materials.

Gant, Stephen E. [University of California, Berkel↗
DOE OSTI2020

Wide Band Gap Chalcogenide Semiconductors

Wide band gap semiconductors are essential for today’s electronic devices and energy applications because of their high optical transparency, controllable carrier concentration, and tunable electrical conductivity. The most intensively investigated wide band gap semiconductors are transparent conductive oxides (TCOs), such as tin-doped indium oxide (ITO) and amorphous In–Ga–Zn–O (IGZO), used in displays and solar cells, carbides (e.g., SiC) and nitrides (e.g., GaN) used in power electronics, and emerging halides (e.g., γ-CuI) and 2D electronic materials (e.g., graphene) used in various optoelectronic devices. Compared to these prominent materials families, chalcogen-based (Ch = S, Se, Te) wide band gap semiconductors are less heavily investigated but stand out because of their propensity for p-type doping, high mobilities, high valence band positions (i.e., low ionization potentials), and broad applications in electronic devices such as CdTe solar cells. This manuscript provides a review of wide band gap chalcogenide semiconductors. First, we outline general materials design parameters of high performing transparent semiconductors, as well as the theoretical and experimental underpinnings of the corresponding research methods. We proceed to summarize progress in wide band gap (EG > 2 eV) chalcogenide materials—namely, II–VI MCh binaries, CuMCh 2 chalcopyrites, Cu 3 MCh 4 sulvanites, mixed-anion layered CuMCh(O,F), and 2D materials—and discuss computational predictions of potential new candidates in this family, highlighting their optical and electrical properties. Then, we finally review applications—for example, photovoltaic and photoelectrochemical solar cells, transistors, and light emitting diodes—that employ wide band gap chalcogenides as either an active or passive layer. Overall, by examining, categorizing, and discussing prospective directions in wide band gap chalcogenides, this Review aims to inspire continued research on this emerging class of transparent semiconductors and thereby enable future innovations for optoelectronic devices.

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

Quantitative Account of the Bonding Properties of a Rubredoxin Model Complex [Fe(SCH3)4]q, q = -2, -1, +2, +3

Iron-sulfur clusters play important roles in biology as parts of electron transfer chains and catalytic cofactors. Here, we report a detailed computational analysis of a structural model of the simplest natural iron-sulfur cluster of rubredoxin and its cationic counterparts. Specifically, we report results for the ground and low-lying electronically excited states of the complex [Fe(SCH3)4]2-/1-/2+/3+, using Multi-Reference (CASSCF, MRCISD), and Coupled Cluster [CCSD(T)] methodology in order to provide accurate adiabatic reduction energies, dissociation energies and insights into the bonding analysis. The nature of the Fe-S chemical bond and the magnitude of the ionization potentials in the anionic and cationic [Fe(SCH3)4] complexes offer a physical rationale for the relative stabilization, structure and speciation of these complexes. Anionic and cationic complexes present different types of chemical bonds: prevalently ionic in [Fe(SCH3)4]2-/1- complexes and covalent in [Fe(SCH3)4]2+/3+ complexes. The ionic bonds result in an energy gain for the transition [Fe(SCH3)4]2-®[Fe(SCH3)4]- (i.e., FeII®FeIII) of 1.5 eV, while the covalent bonds result in an energy loss for the transition [Fe(SCH3)4]2+®[Fe(SCH3)4]3+ of 16.6 eV, almost half of the IP of Fe2+. The ionic vs covalent bond character influences the Fe-S bond strength and length, i.e., ionic Fe-S bonds are longer than covalent ones by about 0.2 Å (for FeII) and 0.04 Å (for FeII). Finally, the average Fe-S heterolytic bond strength is 6.7 eV (FeII) and 14.6 (FeIII) eV at the RCCSD(T) level of theory.

Tzeli, Demeter↗
DOE OSTI2025

Slimmer Geminals For Accurate F12 Electronic Structure Models

The Slater-type F12 geminal length scales originally tuned for the second-order Mo̷ller-Plesset F12 method are too large for higher-order F12 methods formulated using the SP (diagonal fixed-coefficient spin-adapted) F12 ansatz. The new geminal parameters reported herein reduce the basis set incompleteness errors (BSIEs) of absolute coupled-cluster singles and doubles F12 correlation energies by a significant─and increase with the cardinal number of the basis─margin. The effect of geminal reoptimization is especially pronounced for the cc-pVXZ-F12 basis sets (specifically designed for use with F12 methods) relative to their conventional aug-cc-pVXZ counterparts. The BSIEs of relative energies are less affected, but substantial reductions can be obtained, especially for atomization energies and ionization potentials with the cc-pVXZ-F12 basis sets. The new geminal parameters are therefore recommended for all applications of high-order F12 methods, such as coupled-cluster F12 methods and transcorrelated F12 methods.

Powell, Samuel R. [Virginia Polytechnic Inst. and ↗