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Quantum self-consistent equation-of-motion method for computing molecular excitation energies, ionization potentials, and electron affinities on a quantum computer
We present a new hybrid quantum algorithm to estimate molecular excited and charged states on near-term quantum computers following any VQE-based ground state estimation.
Long lifetime polarized electron beam production from negative electron affinity GaAs activated with Sb-Cs-O: Trade-offs between efficiency, spin polarization, and lifetime
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The Uranium-Containing and Thorium-Containing Anions Studied by Photoelectron Spectroscopy
An in-depth knowledge of actinide chemistry is fundamental to many aspects of nuclear science and technology, including the synthesis and processing of materials and the remediation of waste disposal sites. Among the actinides, the chemical bonding behaviors of actinium and thorium resemble those of the transition metals; the 5f-electrons of protactinium, uranium, neptunium, and plutonium often play important roles in their bonding; and among the still heavier elements, their bonding tends to mimic the lanthanide elements in terms of electron shielding and their f-electron contributions. Bonding that involves 5f-electrons, however, is especially important, in part because of the significance of uranium and plutonium, but also because these elements are among the few where f-electron participation in bonding is relatively common. This work focused on studying uranium-containing and thorium-containing anions in the gas phase using negative ion photoelectron spectroscopy. Since this technique directly probed valence electrons, it was uniquely positioned to address open questions regarding molecular bonding and electron configurations. A particularly important issue concerned how bonding in actinide-containing molecules was affected by modifications to their actinide atoms’ environment, i.e., due to their interaction with ligands. A closely related question was how actinide atoms’ suborbitals were qualitatively reordered and their energies quantitatively shifted as a result of their ligated environments. These were especially relevant issues in regard to uranium due to it having multiple possible oxidation states (OS) and the potential for 5f electron participation in bonding. The effects of ligands on oxidation states and 5f-orbital energies in uranium bonding was expected to be pronounced. Both ligands and excess electrons were seen as probes of actinide atoms within actinide-containing molecules. Our strategy for advancing knowledge of chemical bonding in the actinide-containing species utilized the synergy between experiments and theory, where in some cases experimental results validated theory and where in others computational results assisted in interpreting experiments. Calculations on actinide systems are terrifically challenging due to large spin-orbit interactions, relativistic effects, and just the sheer number of electrons involved. Even in the simplest species, e.g., U and U2, the most sophisticated, modern calculations carried out by the most experienced theorists often only approximate experimentally-measured values, such as electron affinities. For theory to provide confident predictions that can be used to solve real problems it needed an iterative and ultimately corrective mechanism by which its methods can develop further. Experiments can be used to identify when theory has failed; whereupon the subsequent process of using the experiment-theory interplay can be used to find the cause of the failure. Upon fixing it in one case, different test species can be proposed and studied by the experiment-theory combination to determine whether the problem has been corrected. Thus, experiments not only measure the values of molecular properties, they also provide navigational 3 beacons that keep computations off the reefs in an otherwise dark sea with few reference points. Experimental measurements in the actinide field are not only important, they are in actuality essential to computational progress. While it was not always possible to compare the theoreticallydetermined quantity of interest directly with the same experimentally-measured observable, it was usually possible to compare consequential properties that are both calculable and measurable. In the work completed here electron affinities and electronic state spacings were often sensitive consequential parameters. Reasonable agreement between measured and computational values signaled that a calculation that was very likely to be on-track. We had established collaborative relationships with five computational groups, all of which have expertise in computational actinide chemistry. Their PI’s are L. Cheng, D. Dixon, L. Gagliardi, K. Peterson, and B. Vlaisavljevich. Our close interaction with our theory partners led to us suggesting systems to them and them to us. This reciprocal interaction between our experimental and their computational results was among the most important strengths of this work and was a thread woven throughout. Even though anion photoelectron spectroscopic studies are conducted on anions, much of the information that they provide, pertains to the electronic structure of the neutral counterparts of those anions; among these are electron affinities and electronically excited state spacings. Our experimental tools included several specialized ion sources for forming the anionic species of interest, a mass spectrometer for identifying and mass-selecting them, and an anion photoelectron spectrometer for determining their electron affinities (EA) and characterizing the electronic states of the selected anions’ neutral counterparts. Anion photoelectron spectroscopy is conducted by crossing a mass-selected beam of anions with a fixed-frequency laser beam and energy-analyzing the resultant photodetached electrons. The photodetachment process is governed by the energyconserving relationship: hν = EBE + EKE, where hν is the photon’s energy, EBE is the electron binding (photodetachment transition) energy, and EKE is the electron’s kinetic energy. In our apparatus mass-selection is accomplished via time-of-flight mass spectrometry (TOF-MS), electron energy analysis is achieved with either a magnetic bottle or by velocity mapped imaging. Photodetachment of electrons from anions is implemented via either Nd:YAG or excimer lasers. The photodetachment transition energy, i.e., the EBE, between the ground vibrational and electronic state of an anion and the ground vibrational and electronic state of that anion’s neutral counterpart is the adiabatic electron affinity (EA) of that neutral molecule. Likewise, photodetachment transitions between the ground vibrational and electronic state of an anion and the various electronically-excited states of that anion’s corresponding neutral map the electronic spectrum of that neutral species, i.e., the spectral spacings in the photoelectron spectrum are a mirror image of the neutral’s electronic spectrum. It was, of course, crucial to be able to form the anionic species of interest. There, we had a particularly broad field of anion sources from which to choose. These included several variants of pulsed laser vaporization (LV), laser photoemission, infrared desorption plus photoemission, pulsed arc discharge (PACIS), electrospray ionization (ESI), and Rydberg electron transfer (RET). Each of these anion sources were readily combined with, i.e., connected to, the anion photoelectron spectroscopic portion of our apparatus as described above. Among the sources that utilize lasers, visible light for LV sources as well as IR for desorption sources are provided by Nd:YAG lasers. Ultraviolet photons are provided by both Nd:YAG and excimer lasers, whereas the excitation wavelengths for RET experiments come from two Nd:YAG-pumped dye lasers.
Tuning the Electronic Properties of Graphane via Hydroxylation: An Ab Initio Study
The thermodynamic stability of hydroxylated graphane, that is, fully sp 3 graphene derivatives coordinated with -H and -OH groups, has been recently demonstrated by ab initio calculations. Within the density functional theory approach, we investigate the electronic property modifications of graphane by progressive hydroxylation, that is, by progressively substituting -H with -OH groups. When 50% of graphane is hydroxylated, the energy bandgap reaches its largest value of 6.68 eV. The electronic affinity of 0.8 eV for graphane can widely change in the 0.28–1.60 eV range depending on the geometric configuration. Hydroxylated graphane has two interfaces with vacuum, hence its electron affinity can be different on each interface with the formation of an intrinsic dipole perpendicular to the monolayer. We envisage the possibility of using hydroxylated graphane allotropes with tunable electronic affinity to serve as interfacial layers in 2D material-based heterojunctions.
Optoelectronic property comparison for isostructural Cu 2 BaGeSe 4 and Cu 2 BaSnS 4 solar absorbers
To target mitigation of anti-site defect formation in Cu 2 ZnSnS 4–x Se x , a new class of chalcogenides, for which Ba or Sr (group 2) replace Zn (group 12), has recently been introduced for prospective solar absorber application. Cu 2 BaGeSe 4 (CBGSe) and Cu 2 BaSnS 4 (CBTS) are two such compounds, which share a common trigonal crystal structure (P3 1 space group) and similar quasi-direct band gap (~2 eV). While CBTS-based films have already been studied, there are no reports yet on films and solar cells based on related CBGSe. To identify key differences and similarities in the electronic properties between these two materials, electronic characteristics (e.g., carrier concentration, mobility, electron affinity, defect levels, recombination, and charge carrier kinetics) of vacuum-deposited CBGSe and CBTS films are compared using a variety of characterization methods. Hall effect measurements reveal that CBGSe films have relatively higher hole carrier concentration and lower mobility (3 × 10 15 cm –3 , 0.6 cm 2 V –1 s –1 ) compared to CBTS (5 × 10 12 cm –3 , 3.5 cm 2 V –1 s –1 ). Photoelectron spectroscopy yields low electron affinity values for both CBGSe (3.7 eV) and CBTS (3.3 eV), pointing to the necessity of pursuing low electron affinity buffer materials for both types of absorbers. At low temperatures, CBGSe films show free-exciton photoluminescence, as well as pronounced deep-level emission at ~1.4 eV, while CBTS films exhibit a strong bound-exciton signal with noticeably less intense deep-level emission than for CBGSe. Charge carrier kinetics, transport, and recombination properties of both types of films are also analyzed using optical-pump terahertz-probe spectroscopy and time-resolved microwave conductivity. The first CBGSe prototype solar cells (using chemical bath deposited CdS as a buffer layer) show a maximum of 1.5% efficiency with ~0.62 V open-circuit voltage. Furthermore, the measured properties point to possible limiting factors for CBGSe and related films for PV and optoelectronics and provide insights on possible approaches for improvement within this multinary chalcogenide family.
Anion photoelectron spectroscopy and chemical bonding of ThS 2 – and ThSO –
Anion photoelectron spectra of ThSO – and ThS 2 – were recorded using the third (355 nm) harmonic of an Nd-YAG laser; these provided the measured vertical detachment energies of each anion. The experiments are supported by extensive coupled cluster calculations on ThSO, ThSO – , ThS 2 , and ThS 2 – , as well as the oxygen congeners ThO 2 and ThO 2 – . The ab initio calculations, which included complete basis set extrapolations, spin–orbit effects using four-component coupled cluster, and higher-order correlation contributions through CCSDT(Q), yielded an adiabatic electron affinity for ThO 2 – that was within 0.02 eV of the previously determined experimental value. The singly occupied molecular orbital (SOMO) in all three anions corresponds primarily to the 7s orbital on Th. Successive substitution of S for each O in ThO 2 leads to larger electron affinities and smaller bond angles in the neutral molecules, but larger angles in the anions. As demonstrated by Franck–Condon simulations of the spectra using the CCSD(T) spectroscopic constants, substitution of O by S significantly complicates the resulting detachment spectra due to the lower vibrational frequencies in the sulfur species. Altogether the calculated vertical detachment energies are in very good agreement with the experiment. In addition to the adiabatic electron affinities of each species, atomization energies and heats of formation have also been determined via the FPD approach with expected uncertainties of 1–2 kcal/mol.
The H•/H– Redox Couple and Absolute Hydration Energy of H–
A supermolecule-continuum approach with water clusters up to n = 16 H2O molecules has been used to predict the absolute hydration free energies at 298 K ($\Delta$G hyd ) of both hydrogen (H•) and hydride (H - ) to be 4.6 and -78 ± 2 kcal/mol, respectively. These values are combined with a high accuracy prediction of the gas phase electron affinity ($\Delta$G gas,298K = -16.9 kcal/mol) to determine the aqueous electron affinity of H• of 99.5 ± 2 kcal/mol, which yields a reduction potential for H• vs SHE of -0.03 ± 0.15 V. This value is in agreement within 0.2 V with most estimates obtained using a wide variety of approaches. The results of this study can be used to improve the absolute hydricity scale in water which provides additional insights into how a putative hydride interacts with solvent, but do not change the ability to predict the relative reactivity of two species using relative hydricity scales.
Steady-state junction current distribution in p-n GaN diodes measured using low-energy electron microscopy (LEEM)
Here, we report on the measurement of the lateral distribution of the junction current of an electrical biased p-n GaN diode by electron emission microscopy using a low-energy electron microscope. The vacuum level at the surface of the diode was lowered by deposition of cesium to achieve negative electron affinity, allowing overflow electrons at the surface of the biased diodes to be emitted and their spatial distribution imaged. The results were compared to the literature, and a good match with analytical solutions by Joyce and Wemple was obtained.
Franck-Condon electron emission from polar semiconductor photocathodes
An analytical formulation of (optical-)phonon-mediated and momentum-resonant Franck-Condon emission of photoexcited electrons from polar semiconductors is shown to be very consistent with (i) the observed emission properties of a cesiated GaAs(001) photocathode at 808 nm [J. Phys. D: Appl. Phys. 54, 205301 (2021)] and (ii) the measured spectral emission properties of a GaN(0001) photocathode from just below its bandgap energy to 5 eV. The theoretical analysis in the parabolic band approximation predicts the form of both the quantum efficiency and mean transverse energy of photoemission as a function of the photocathode’s electron affinity and the electron temperature in the vicinity of its emission face. The good agreement between theory and experimental data also suggests that sub-10-nm rms surface roughness effects are not significant for polar semiconductor photocathodes.
Top Stack Optimization for Cu 2 BaSn(S, Se) 4 Photovoltaic Cell Leads to Improved Device Power Conversion Efficiency beyond 6%
Earth-abundant and air-stable Cu 2 BaSnS 4-x Se x (CBTSSe) and related thin-film absorbers are regarded as prospective options to meet the increasing demand for low-cost solar cell deployment. Devices based on vacuum-deposited CBTSSe absorbers have achieved record power conversion efficiency (PCE) of 5.2 % based on a conventional device structure using CdS buffer and i-ZnO/ITO window layers, with open-circuit voltage (V OC ) posing the major bottleneck for improving solar cell performance. The current study demonstrates a >20 % improvement in V OC (from 0.62 V to 0.75 V) and corresponding enhancement in PCE (from 5.1 % to 6.2 % without anti-reflection coating; to 6.5 % with MgF 2 anti-reflection coating) for solution-deposited CBTSSe solar cells. This performance improvement is realized by introducing an alternative successive ionic layer adsorption and reaction (SILAR)-deposited Zn 1-x Cd x S buffer combined with sputtered Zn 1-x Mg x O/Al-doped ZnO window/top contact layer, which offer lower electron affinities relative to the conventional CdS/i-ZnO/ITO stack and better matching with the low electron affinity of CBTSSe. A combined experimental (temperature- and light intensity-dependent V OC measurements) and device simulation (SCAPS-1D) evaluation points to the importance of addressing relative band offsets for both the buffer and window layers relative to the absorber in mitigating interfacial recombination and optimizing CBTSSe solar cell performance.
Low-Energy Electron Elastic Total Cross Sections for Ho, Er, Tm, Yb, Lu, and Hf Atoms
The robust Regge-pole methodology wherein is fully embedded the essential electron-electron correlation effects and the vital core polarization interaction has been used to explore negative ion formation in the large lanthanide Ho, Er, Tm, Yb, Lu, and Hf atoms through the electron elastic total cross sections (TCSs) calculations. These TCSs are characterized generally by dramatically sharp resonances manifesting ground, metastable, and excited negative ion formation during the collisions, Ramsauer-Townsend minima, and shape resonances. The novelty and generality of the Regge-pole approach is in the extraction of the negative ion binding energies (BEs) of complex heavy systems from the calculated electron TCSs. The extracted anionic BEs from the ground state TCSs for Ho, Er, Tm, Yb, Lu, and Hf atoms are 3.51 eV, 3.53 eV, 3.36 eV, 3.49 eV, 4.09 eV and 1.68 eV, respectively. The TCSs are presented and the extracted from the ground; metastable and excited anionic states BEs are compared with the available measured and/or calculated electron affinities. We conclude with a remark on the existing inconsistencies in the meaning of the electron affinity among the various measurements and/or calculations in the investigated atoms and make a recommendation to resolve the ambiguity.
Solid Electrolyte Interphase Formation at the Ionic Liquid Electrolyte—Lithium-Metal Interface Using an Ab Initio Molecular Dynamics Approach
An interfacial study is performed using ab initio molecular dynamics (AIMD) simulations to elucidate the electrochemical interfacial stability of an ionic liquid (IL) as component of an electrolyte in contact with a Li-metal anode when an additive, vinylene carbonate (VC), is added to the electrolyte. The IL electrolyte is composed of 1-butyl-1-methylpyrrolidinium bis(fluoro-sulfonyl)-imide (PYR14 + FSI − ) with lithium bis(trifluoromethane-sulfonyl)imide salt (Li + TFSI − ) in a 8:2 concentration ratio. Reactions observed at the interface electrolyte/Li-metal during the AIMD simulations are verified by electronic structure calculations using density functional theory calculations considering a continuum solvent model. We found that the addition of VC to the IL prevents further reduction of the counter-ion TFSI − and retards reduction of FSI − in comparison to the case when the additive VC is absent. The PYR14 + reduction is never observed with or without the additive. The 1st, 2nd, and 3rd electron affinities of the PYR14 + are −0.08, −0.36 and −3.65 eV, indicating little to large repulsive behavior against electrons. The opposite is observed for the two negative ions, FSI − and TFSI − , which yield 1st electron affinities of 1.73 and 1.83 eV, respectively. Reactions obtained under open circuit conditions. Dissociation mechanisms are presented for all IL components reduced at the IL/Li-metal interface.
Monte Carlo modeling of spin-polarized photoemission from p -doped bulk GaAs
Here, the anticorrelation between quantum efficiency (QE) and electron spin polarization (ESP) from a ρ-doped GaAs activated to negative electron affinity is studied in detail using an ensemble Monte Carlo approach. The photoabsorption, momentum and spin relaxation during transport, and tunneling of electrons through the surface potential barrier are modeled to identify fundamental mechanisms, which limit the efficiency of GaAs spin-polarized electron sources. In particular, we study the response of QE and ESP to various parameters, such as the photoexcitation energy, doping density, and electron affinity level. Our modeling results for various transport and emission characteristics are in good agreement with available experimental data. Our findings show that the behavior of both QE and ESP at room temperature can be fully explained by the bulk relaxation mechanisms and the time that electrons spend in the material before being emitted.
Intrinsic emittance properties of an Fe-doped β-Ga 2 O 3 (010) photocathode: Ultracold electron emission at 300 K and the polaron self-energy
Measurements of the spectral emission properties of an iron-doped a β-Ga 2 O 3 (010) photocathode at 300 K reveal the presence of an ultracold contribution to the total electron beam emission with a 6 meV mean transverse energy (MTE) in the 3.5–4.4 eV photon energy range (282–354 nm). This extreme sub-thermal photoemission signal is consistent with direct emission of electrons photoexcited from the Fe dopant states into the low effective mass and positive electron affinity primary conduction band, and it is superimposed on a stronger signal with a larger MTE associated with an (optical)phonon-mediated momentum-resonant Franck–Condon (FC) emission process from a thermally populated and negative electron affinity upper conduction band. For photon energies above 4.5 eV, a transition from a long to a short transport regime is forced by an absorption depth reduction to below 100 nm and both MTE signals exhibit spectral trends consistent with phonon-mediated FC emission if the polaron formation self-energy is included in the temperature of the initial thermalized photoexcited electron distribution.
Th 2 O – , Th 2 Au – , and Th 2 AuO 1,2 – Anions: Photoelectron Spectroscopic and Computational Characterization of Energetics and Bonding
The observation and characterization of the anions: Th 2 O – , Th 2 Au – , and Th 2 AuO 1,2 – is reported. These species were studied through a synergetic combination of anion photoelectron spectroscopy and ab initio correlated molecular orbital theory calculations at the CCSD(T) level with large correlation-consistent basis sets. To better understand the energetics and bonding in these anions and their corresponding neutrals, a range of smaller diatomic to tetratomic species were studied computationally. Correlated molecular orbital theory calculations at the CCSD(T) level showed that in most of these cases, there are close-lying anions and neutral clusters with different geometries and spin states and are consistent with the experimentally observed spectra. Thus, comparison of experimentally determined and computationally predicted vertical detachment energies and electron affinities for different optimized geometries and spin states shows excellent agreement to within 0.1 eV. The structures for both the neutrals and anions have a significant ionic component to the bonding because of the large electron affinity of the Au atom and modest ionization potentials for Th 2 , Th 2 O, and Th 2 O 2 . The analysis of the bonding for the Th–Th bonds from the molecular orbitals is consistent with this ionic model. The results show that there is a wide variation in the bond distance from 2.7 to 3.5 Å for the Th–Th bonds all of which are less than twice the atomic radius of Th of 3.6 Å. The bond distances encompass bond orders from 4 to 0. Furthermore, there can be different bond orders for the same bond distance depending on the nature of the ionic bonding suggesting that one may not be able to correlate the bond order with the bond distance in these types of clusters. In addition, the presence of an Au atom may provide a unique probe of the bonding in such clusters because of its ability to accept an electron from clusters with modest ionization potentials.
Probing the electronic structure and spectroscopy of pyrrolyl and imidazolyl radicals using high-resolution photoelectron imaging of cryogenically cooled anions
High-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled pyrrolide and imidazolide anions are used to probe the electronic structure and spectroscopy of pyrrolyl and imidazolyl radicals. The high-resolution data allow the ground state vibronic structures of the two radicals to be completely resolved, yielding accurate electron affinities of 2.1433 ± 0.0008 eV and 2.6046 ± 0.0006 eV for pyrrolyl and imidazolyl radicals, respectively. Fundamental frequencies for eight vibrational modes of pyrrolyl and ten vibrational modes of imidazolyl are measured, including several nonsymmetric Franck–Condon-forbidden modes. Two electronic excited states are also observed for the two radicals, displaying diffuse spectral features in both systems. The observations of nonsymmetric vibrational modes in the ground states and the diffuse excited state features provide strong evidence for vibronic couplings between the ground state and the two close-by excited states. The 2-pyrrolide isomer is also observed as a minor species from the electrospray ionization source and the electron affinity of 2-pyrrolyl is measured to be 1.6690 ± 0.0030 eV along with five vibrational frequencies. Even though the HOMOs of both pyrrolide and imidazolide anions are p orbitals, photodetachment spectroscopy reveals completely different threshold behaviors for the two anions: a d-wave-dominated spectrum for pyrrolide and an s-wave-dominated spectrum for imidazolide. Furthermore, the current study provides a wealth of electronic and spectroscopic information, which is ideal to compare with more accurate vibronic coupling calculations for these two important radicals, as well as interesting information about the photodetachment dynamics of the two anions.
Anion Resonances and Photoelectron Spectroscopy of the Tetracenyl Anion
The photoelectron spectroscopy of the tetracenyl anion using slow electron velocity-map imaging (SEVI) of cryogenically cooled ions is presented here. The total photodetachment yield as a function of photon energy is used to reveal a rich manifold of anion excited states above the detachment threshold. The lowest energy anionic resonance has a sufficiently long lifetime to yield a vibrationally resolved absorption spectrum that can be directly compared with theoretical predictions. Excitation of this state mostly results in electron detachment via thermionic emission. The total photodetachment yield spectrum is used to select photon wavelengths that minimize the indirect detachment signal to allow acquisition of vibrationally-resolved photoelectron spectra that can inform on the neutral tetracenyl radical. Assignment of spectral features corresponding to the ground and first excited state of the neutral 12-tetracenyl isomer is made with the aid of Franck-Condon simulations. This yields adiabatic electron affinity and term energies that differ significantly from the previously reported values. Weak features corresponding to the ground state of the minor 2-teracenyl and 1-tetracenyl isomers are also identified, which allows for the experimental determination of their electron affinities for the first time.