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DOE OSTI2015

Fermi orbital self-interaction corrected electronic structure of molecules beyond local density approximation

The correction of the self-interaction error that is inherent to all standard density functional theory calculations is an object of increasing interest. In this article, we apply the very recently developed Fermi-orbital based approach for the self-interaction correction [M. R. Pederson et al., J. Chem. Phys. 140, 121103 (2014) and M. R. Pederson, J. Chem. Phys. 142, 064112 (2015)] to a set of different molecular systems. Our study covers systems ranging from simple diatomic to large organic molecules. We focus our analysis on the direct estimation of the ionization potential from orbital eigenvalues. Further, we show that the Fermi orbital positions in structurally similar molecules appear to be transferable.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2015

Electronic and structural properties at the interface between CuPc and graphene

The electronic and structural properties at Copper phthalocyanine (CuPc)/graphene have been studied using ultraviolet photoemission spectroscopy and first-principles density function theory calculation. The five emission features α, β, γ, δ, and ε originating from the CuPc molecules locate at 1.48, 3.66, 4.98, 6.90, and 9.04 eV, respectively. These features shift in binding energy with the increasing CuPc coverage. The feature α is mostly deriving from Cu 3d orbital with some contributions from C 2p orbital. Further theoretical calculation indicates that the adsorption of CuPc on a top site is the most favorable configuration, and the separation between the adsorbate and graphene is about 3.47 Å. According to the density of states before and after CuPc adsorption, the LUMO of CuPc is slightly occupied, while the Dirac point of graphene slightly shift towards higher energy, suggesting that a small amount of electron transfer from graphene to CuPc upon contact.

74 ATOMIC AND MOLECULAR PHYSICS↗

DOE OSTI2014

Structure, electronic properties, and aggregation behavior of hydroxylated carbon nanotubes

We present a combined experimental and theoretical study to analyze the structure, electronic properties, and aggregation behavior of hydroxylated multiwalled carbon nanotubes (OH–MWCNT). Our MWCNTs have average diameters of ∼2 nm, lengths of approximately 100–300 nm, and a hydroxyl surface coverage θ∼0.1. When deposited on the air/water interface the OH–MWCNTs are partially soluble and the floating units interact and link with each other forming extended foam-like carbon networks. Surface pressure-area isotherms of the nanotube films are performed using the Langmuir balance method at different equilibration times. The films are transferred into a mica substrate and atomic force microscopy images show that the foam like structure is preserved and reveals fine details of their microstructure. Density functional theory calculations performed on model hydroxylated carbon nanotubes show that low energy atomic configurations are found when the OH groups form molecular islands on the nanotube's surface. This patchy behavior for the OH species is expected to produce nanotubes having reduced wettabilities, in line with experimental observations. OH doping yields nanotubes having small HOMO–LUMO energy gaps and generates a nanotube → OH direction for the charge transfer leading to the existence of more hole carriers in the structures. Our synthesized OH–MWCNTs might have promising applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

First-principles simulation of a shocked H-He mixture along the principal Hugoniot

Recent laser-shock experiments on an H–He mixture containing 11% helium (atomic fraction) have suggested the presence of an immiscibility region inside Jupiter. Reflectivity measurements were used as the primary diagnostic of H–He demixing, with discontinuities in the optical reflectivity proposed as a signature of phase separation under conditions relevant to Jupiter's interior. Here, we investigate shock-compressed H–He using ab initio molecular dynamics simulations with optical properties evaluated within the Kubo–Greenwood formalism. The equation of state and ionic configurations were obtained using the thermal Tr 2 SCANL meta-GGA exchange–correlation (XC) functional, while optical properties were computed using the recently developed RS-KDT0 range-separated thermal hybrid XC, which provides state-of-the-art accuracy for band-gap predictions in the warm dense matter regime. The calculated reflectivity shows overall good agreement with experimental measurements; however, no discontinuity is observed at elevated temperatures. Moreover, the reflectivity predictions for the mixed system are consistent with the experimental measurements in the temperature range where the mixture is inferred to be demixed. Furthermore, these results suggest that reflectivity alone may not provide a unique or sensitive diagnostic of H–He demixing at low helium concentrations under these conditions.

Density functional calculations↗

DOE OSTI2021

Thickness and Spin Dependence of Raman Modes in Magnetic Layered Fe 3 GeTe 2

2D layered Fe 3 GeTe 2 has attracted increasing attention due to its high magnetic ordering temperature and novel physical properties. Lattice dynamics is a fundamental property of Fe 3 GeTe 2 , and its relationships with the number of layers and interlayer spin ordering have not yet been explored in depth. Here, by first-principles density functional theory calculations, the phonon vibrations and Raman intensities of Fe 3 GeTe 2 are systematically studied from the bulk to monolayer structures. Furthermore, the spin-phonon coupling effect is investigated by considering different interlayer magnetic orderings: ferromagnetic and antiferromagnetic. It is found that the frequencies of Raman modes in Fe 3 GeTe 2 exhibit considerable dependence on the layer number and spin ordering. In this work, the results not only reveal the notable spin-phonon interactions in Fe 3 GeTe 2 , but also demonstrate that Raman modes can be utilized for characterizing the sample thickness and interlayer spin ordering in this 2D magnet.

2D magnets↗

DOE OSTI2021

Interstitial Nature of Mn 2+ Doping in 2D Perovskites

Halide perovskites doped with magnetic impurities (such as the transition metals Mn 2+ , Co 2+ , Ni 2+ ) are being explored for a wide range of applications beyond photovoltaics, such as spintronic devices, stable light-emitting diodes, single-photon emitters, and magneto-optical devices. However, despite several recent studies, there is no consensus on whether the doped magnetic ions will predominantly replace the octahedral B-site metal via substitution or reside at interstitial defect sites. Here, by performing correlated nanoscale X-ray microscopy, spatially and temporally resolved photoluminescence measurements, and magnetic force microscopy on the inorganic 2D perovskite Cs 2 PbI 2 Cl 2 , we show that doping Mn 2+ into the structure results in a lattice expansion. The observed lattice expansion contrasts with the predicted contraction expected to arise from the B-site metal substitution, thus implying that Mn 2+ does not replace the Pb 2+ sites. Photoluminescence and electron paramagnetic resonance measurements confirm the presence of Mn 2+ in the lattice, while correlated nano-XRD and X-ray fluorescence track the local strain and chemical composition. Density functional theory calculations predict that Mn 2+ atoms reside at the interstitial sites between two octahedra in the triangle formed by one Cl – and two I – atoms, which results in a locally expanded structure. These measurements show the fate of the transition metal dopants, the local structure, and optical emission when they are doped at dilute concentrations into a wide band gap semiconductor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2015

Type I band alignment in GaAs{sub 81}Sb{sub 19}/GaAs core-shell nanowires

The composition and band gap of the shell that formed during the growth of axial GaAs/GaAs{sub 81}Sb{sub 19}/ GaAs heterostructure nanowires have been investigated by transmission electron microscopy combined with energy dispersion spectroscopy, scanning tunneling spectroscopy, and density functional theory calculations. On the GaAs{sub 81}Sb{sub 19} intermediate segment, the shell is found to be free of Sb (pure GaAs shell) and transparent to the tunneling electrons, despite the (110) biaxial strain that affects its band gap. As a result, a direct measurement of the core band gap allows the quantitative determination of the band offset between the GaAs{sub 81}Sb{sub 19} core and the GaAs shell and identifies it as a type I band alignment.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2024

Spin-Charge-Lattice Coupling across the Charge Density Wave Transition in a Kagome Lattice Antiferromagnet

Understanding spin and lattice excitations in a metallic magnetic ordered system forms the basis to unveil the magnetic and lattice exchange couplings and their interactions with itinerant electrons. Kagome lattice antiferromagnet FeGe is interesting because it displays a rare charge density wave (CDW) deep inside the antiferromagnetic ordered phase that interacts with the magnetic order. Here, we use neutron scattering to study the evolution of spin and lattice excitations across the CDW transition 𝑇 CDW in FeGe. While spin excitations below ∼100 meV can be well described by spin waves of a spin-1 Heisenberg Hamiltonian, spin excitations at higher energies are centered around the Brillouin zone boundary and extend up to ∼180 meV consistent with quasiparticle excitations across spin-polarized electron-hole Fermi surfaces. Furthermore, 𝑐-axis spin wave dispersion and Fe-Ge optical phonon modes show a clear hardening below 𝑇 CDW due to spin-charge-lattice coupling but with no evidence of a phonon Kohn anomaly. By comparing our experimental results with density functional theory calculations in absolute units, we conclude that FeGe is a Hund’s metal in the intermediate correlated regime where magnetism has contributions from both itinerant and localized electrons arising from spin polarized electronic bands near the Fermi level.

charge density waves↗

DOE OSTI2016

Dual role of monolayer MoS{sub 2} in enhanced photocatalytic performance of hybrid MoS{sub 2}/SnO{sub 2} nanocomposite

The enhanced photocatalytic performance of various MoS{sub 2}-based nanomaterials has recently been observed, but the role of monolayer MoS{sub 2} is still not well elucidated at the electronic level. Herein, focusing on a model system, hybrid MoS{sub 2}/SnO{sub 2} nanocomposite, we first present a theoretical elucidation of the dual role of monolayer MoS{sub 2} as a sensitizer and a co-catalyst by performing density functional theory calculations. It is demonstrated that a type-II, staggered, band alignment of ∼0.49 eV exists between monolayer MoS{sub 2} and SnO{sub 2} with the latter possessing the higher electron affinity, or work function, leading to the robust separation of photoexcited charge carriers between the two constituents. Under irradiation, the electrons are excited from Mo 4d orbitals to SnO{sub 2}, thus enhancing the reduction activity of latter, indicating that the monolayer MoS{sub 2} is an effective sensitizer. Moreover, the Mo atoms, which are catalytically inert in isolated monolayer MoS{sub 2}, turn into catalytic active sites, making the monolayer MoS{sub 2} to be a highly active co-catalyst in the composite. The dual role of monolayer MoS{sub 2} is expected to arise in other MoS{sub 2}-semiconductor nanocomposites. The calculated absorption spectra can be rationalized by available experimental results. These findings provide theoretical evidence supporting the experimental reports and pave the way for developing highly efficient MoS{sub 2}-based photocatalysts.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2016

Tuning electrocatalytic activity of Pt monolayer shell by bimetallic Ir-M (M=Fe, Co, Ni or Cu) cores for the oxygen reduction reaction

Here, platinum monolayer electrocatalyst are known to exhibit excellent oxygen reduction reaction (ORR) activity depending on the type of substrate used. Here we demonstrate a relationship between the ORR electrocatalytic activity and the surface electronic structure of Pt monolayer shell induced by various IrM bimetallic cores (M=Fe, Co, Ni or Cu). The relationship is rationalized by comparing density functional theory calculations and experimental results. For an efficient Pt monolayer electrocatalyst, the core should induce sufficient contraction to the Pt shell leading to a downshift of the d-band center with respect to the Fermi level. Depending on the structure of the IrM, relative to that of pure Ir, this interaction not only alters the electronic and geometric structure but also induces segregation effects. Combined these effects significantly enhance the ORR activities of the Pt monolayer shell on bimetallic Ir cores electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Identification and characterization of deep nitrogen acceptors in β-Ga 2 O 3 using defect spectroscopies

The ability to achieve highly resistive beta-phase gallium oxide (β-Ga 2 O 3 ) layers and substrates is critical for β-Ga 2 O 3 high voltage and RF devices. To date, the most common approach involves doping with iron (Fe), which generates a moderately deep acceptor-like defect state located at E C -0.8 eV in the β-Ga 2 O 3 bandgap. Recently, there has been growing interest in alternative acceptors, such as magnesium (Mg) and nitrogen (N), due to their predicted deeper energy levels, which could avoid inadvertent charge modulation during device operation. In this work, a systematic study that makes direct correlations between the introduction of N using ion implantation and the observation of a newly observed deep level at E C -2.9 eV detected by deep-level optical spectroscopy (DLOS) is presented. The concentration of this state displayed a monotonic dependence with N concentration over a range of implant conditions, as confirmed by secondary ion mass spectrometry (SIMS). With a near 1:1 match in absolute N and E C -2.9 eV trap concentrations from SIMS and DLOS, respectively, which also matched the measured removal of free electrons from capacitance-voltage studies, this indicates that N contributes a very efficiently incorporated compensating defect. Density functional theory calculations confirm the assignment of this state to be an N (0/-1) acceptor with a configuration of N occupying the oxygen site III [N O(III) ]. The near ideal efficiency for this state to compensate free electrons and its location toward the midgap region of the β-Ga 2 O 3 bandgap demonstrates the potential of N doping as a promising approach for producing semi-insulating β-Ga 2 O 3 .

36 MATERIALS SCIENCE↗

DOE OSTI2023

Signatures of van Hove singularities in the anisotropic in-plane optical conductivity of the topological semimetal Nb 3 ⁢SiTe 6

In this work, we present a temperature-dependent infrared spectroscopy study on the layered topological semimetal Nb 3 ⁢SiTe 6 combined with density-functional theory calculations of the electronic band structure and optical conductivity. Our results reveal an anisotropic behavior of the in-plane (ac-plane) optical conductivity, with three pronounced excitations located at around 0.15, 0.28, and 0.41 eV for the polarization of the incident radiation along the c axis. These excitations are well reproduced in the theoretical spectra. Based on the ab initio results, the excitations around 0.15 and 0.28 eV are interpreted as fingerprints of van Hove singularities in the electronic band structure and compared to the findings for other topological semimetals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2016

Density functional study on the mechanism for the highly active palladium monolayer supported on titanium carbide for the oxygen reduction reaction

The adsorption, diffusion, and dissociation of O{sub 2} on the palladium monolayer supported on TiC(001) surface, MLPd/TiC(001), are investigated using ab initio density functional theory calculations. Strong adhesion of palladium monolayer to the TiC(001) support, accompanied by a modification of electronic structure of the supported palladium, is evidenced. Compared with Pt(111) surface, the MLPd/TiC(001) can enhance the adsorption of O{sub 2}, leading to comparable dissociation barrier and a smaller diffusion barrier of O{sub 2}. Whilst the adsorption strength of atomic O (the dissociation product of O{sub 2}) on MLPd/TiC(001) is similar to that on the Pt(111) surface, possessing high mobility, our theoretical results indicate that MLPd/TiC(001) may serve as a good catalyst for the oxygen reduction reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Spin density stabilization of local distortions induced by a monovacancy in δ -Pu

Density functional theory calculations elucidate crystallographic and electronic structural responses of the fcc delta phase of plutonium (δ-Pu) to point defects. Discussed are responses that vary from a defect exhibiting a local structural instability common in fcc metals to an unusual defect structure that mimics properties similar to the monoclinic α phase. In the prior case, the existence of a self-vacancy when ionic relaxation is allowed induces in the fcc lattice a local tetragonal instability in nearest-neighbor atoms, slight electronic charge increase, and a spin-density decrease. However, in the latter case, after ionic relaxation, the defect is not recognizable as the structure of a vacant site common to many simple fcc metals, but is a complex extended defect involving neighboring atoms to collectively exhibit loss of lattice symmetry through formation of short Pu-Pu bonds and associated narrow bands at the Fermi energy. Partial density of states (PDOS) indicates that these narrow bands form as spectral weighting from the less energetic 6d electronic states is shifted to the 5f electronic states by means of the spin density, which occupies states at the Fermi energy. Finally, the PDOS of a 5f system exhibiting narrow bands at the Fermi energy is associated with the formation of an unusual defect structure in the lattice.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Adsorption of Dimethyl Methylphosphonate on MoO 3 : The Role of Oxygen Vacancies

Dimethyl methylphosphonate (DMMP) is a common chemical warfare agent simulant and is widely used in adsorption studies. To further increase the understanding of DMMP interactions with metal oxides, ambient pressure X-ray photoelectron spectroscopy was used here to study the adsorption of DMMP on MoO 3 , including the effects of oxygen vacancies, surface hydroxyl groups, and adsorbed molecular water. Density functional theory calculations were used to aid in the interpretation of the APXPS results. An inherent lack of Lewis acid metal sites results in weak interactions of DMMP with MoO 3 . Adsorption is enhanced by the presence of oxygen vacancies, hydroxyl groups, and molecular water on the MoO 3 surface, as measured by photoelectron spectroscopy. Computational results agree with these findings and suggest the formation of methanol through several possible pathways, but all require a proton transferred from a hydroxyl group on the surface.

36 MATERIALS SCIENCE↗

DOE OSTI2016

Buffer-eliminated, charge-neutral epitaxial graphene on oxidized 4H-SiC (0001) surface

Buffer-eliminated, charge-neutral epitaxial graphene (EG) is important to enhance its potential in device applications. Using the first principles Density Functional Theory calculations, we investigated the effect of oxidation on the electronic and structural properties of EG on 4H-SiC (0001) surface. Our investigation reveals that the buffer layer decouples from the substrate in the presence of both silicate and silicon oxy-nitride at the interface, and the resultant monolayer EG is charge-neutral in both cases. The interface at 4H-SiC/silicate/EG is characterized by surface dangling electrons, which opens up another route for further engineering EG on 4H-SiC. Dangling electron-free 4H-SiC/silicon oxy-nitride/EG is ideal for achieving charge-neutral EG.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2014

Quantum modelling of hydrogen chemisorption on graphene and graphite

The chemisorption of hydrogen on graphene or graphite is studied within a quantum formalism involving a subsystem coupled to a phonon bath. The subsystem includes the hydrogen atom approaching the surface perpendicularly right on top of a carbon atom which puckers out of the surface. The bath includes the acoustic and optical phonon modes vibrating perpendicularly to the surface. Couplings between subsystem and bath are obtained with a periodic density functional theory calculation. Trapping probabilities are obtained as a function of the hydrogen atom kinetic energy. These results are discussed in the light of the experimental hydrogenation studies performed on graphite by Zecho et al. [J. Chem. Phys. 117, 8486 (2002)] and on graphene by Haberer et al. [Adv. Mater. 23, 4497 (2011)].

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Photoinduced charge transfer in Zn(II) and Au(III)-ligated symmetric and asymmetric bacteriochlorin dyads: A computational study

The excited-state properties and photoinduced charge-transfer (CT) kinetics in a series of symmetrical and asymmetrical Zn- and Au-ligated meso–meso-connected bacteriochlorin (BChl) complexes are studied computationally. BChl derivatives, which are excellent near-IR absorbing chromophores, are found to play a central role in bacterial photosynthetic reaction centers but are rarely used in artificial solar energy harvesting systems. The optical properties of chemically linked BChl complexes can be tuned by varying the linking group and involving different ligated metal ions. We investigate charge transfer in BChl dyads that are either directly linked or through a phenylene ring (1,4- phenylene) and which are ligating Zn or Au ions. The directly linked dyads with a nearly perpendicular arrangement of the BChl units bear markedly different properties than phenylene linked dyads. In addition, we find that the dielectric dependence of the intramolecular CT rate is very strong in neutral Zn-ligated dyads, whereas cationic Au-ligated dyads show negligible dielectric dependence of the CT rate. Rate constants of the photo induced CT process are calculated at the semiclassical Marcus level and are compared to fully quantum mechanical Fermi’s golden rule based values. The rates are calculated using a screened range separated hybrid functional that offers a consistent framework for addressing environment polarization. We study solvated systems in two solvents of a low and a high scalar dielectric constant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗