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Coherent coupling of defect spins with surrounding nuclei along with the endowment to read out the latter, are basic requirements for an application in quantum technologies. We show that negatively charged boron vacancies (VB-) in electron-irradiated hexagonal boron nitride (hBN) meet these prerequisites. We demonstrate Hahn-echo coherence of the VB- electron spin with a characteristic decay time Tcoh = 15 us, close to the theoretically predicted limit of 18 us for spin defects in hBN. Modulation in the MHz range superimposed on the Hahn-echo decay curve are shown to be induced by coherent coupling of the VB- spin with the three nearest 14N nuclei through a nuclear quadrupole interaction of 2.11 MHz. Supporting DFT calculation confirm that the electron-nuclear coupling is confined to the defective layer. Our findings allow an in-depth understanding of the electron-nuclear interactions of the VB- defect in hBN and demonstrate its strong potential in quantum technologies.

International audience; The nitrogen-vacancy (NV) center in 3C-SiC, the analog of the NV center in diamond, has recently emerged as a solid-state qubit with competitive properties and significant technological advantages. Combining first-principles calculations and magnetic resonance spectroscopy we provide thorough insight in its magneto-optical properties. By applying resonantly excited electron paramagnetic resonance spectroscopy, we identified the zero-phonon absorption line of the 3 A 2 → 3 E transition at 1289 nm (within the telecom Oband) and measured its phonon sideband, the analysis of which reveals a Huang-Rhys factor of S = 2.85 and a Debye-Waller factor of 5.8 %. The low temperature spin-lattice relaxation time was found to be exceptionally long (T 1 = 17 s at 4 K). All these properties make NV in 3C-SiC a strong competitor for qubit application. In addition, the strong variation of the zero-field splitting in the range of 4K to 380K allows its application for nanoscale thermal sensing.

We study the interplay of chemisorbed hydrogen and physisorbed PbPc molecules on epitaxial graphene by means of surface transport and density functional theory. While the adsorption of atomic hydro...

N-Heterocyclic carbenes (NHCs) are promising modifiers and anchors for surface functionalization and offer some advantages over thiol-based systems. Because of their strong binding affinity and high electron donation, NHCs can dramatically change the properties of the surfaces to which they are bonded. Highly ordered NHC monolayers have so far been limited to metal surfaces. Silicon, however, remains the element of choice in semiconductor devices and its modification is therefore of utmost importance for electronic industries. Here, a comprehensive study on the adsorption of NHCs on silicon is presented. We find covalently bound NHC molecules in an upright adsorption geometry and demonstrate the formation of highly ordered monolayers exhibiting good thermal stability and strong work function reductions. The structure and ordering of the monolayers is controlled by the substrate geometry and reactivity and in particular by the NHC side groups. These findings pave the way towards a tailor-made organic functionalization of silicon surfaces and, thanks to the high modularity of NHCs, new electronic and optoelectronic applications. Although monolayers of N-heterocyclic carbenes (NHCs) readily form on metals, surface reactivity usually hinders their self-assembly on semiconductors. Now, it has been shown that thermally stable, well-ordered monolayers of NHCs can be formed on silicon surfaces. A large reduction in work function is observed and steric effects enable sufficient diffusivity of the NHCs.

Polarons influence decisively the performance of lithium niobate for optical applications. In this work, the formation of (defect) bound polarons in lithium niobate is studied by ab initio molecular dynamics. The calculations show a broad scatter of polaron formation times. Rising temperature increases the share of trajectories with long formation times, which leads to an overall increase of the average formation time with temperature. However, even at elevated temperatures, the average formation time does not exceed the value of 100 femtoseconds, i.e., a value close to the time measured for free, i.e., self-trapped polarons. Analyzing individual trajectories, it is found that the time required for the structural relaxation of the polarons depends sensitively on the excitation of the lithium niobate high-frequency phonon modes and their phase relation.

A constrained density functional theory/classical trajectory surface hopping study of the photochemical dissociation of oxirane (CH2)2O is presented. The calculations confirm the Gomer–Noyes mechanism for the initial reaction and agree largely with experimental photolysis data including reaction yields. The calculated yields, however, depend both on temperature and its modeling. The timescales of the various reaction steps are well below 100 fs, similar to previous time-dependent density functional calculations. At variance with those, however, the present calculations obey Kasha’s rule, i.e., the photoreaction is initiated in the energetically lowest excited state.

We present an X- and Q-band continuous wave (CW) and pulse electron paramagnetic resonance (EPR) study of a manganese doped [NH4][Zn(HCOO)3] hybrid framework, which exhibits a ferroelectric structural phase transition at 190 K. The CW EPR spectra obtained at different temperatures exhibit clear changes at the phase transition temperature. This suggests a successful substitution of the Zn2+ ions by the paramagnetic Mn2+ centers, which is further confirmed by the pulse EPR and 1H ENDOR experiments. Spectral simulations of the CW EPR spectra are used to obtain the temperature dependence of the Mn2+ zero-field splitting, which indicates a gradual deformation of the MnO6 octahedra indicating a continuous character of the transition. The determined data allow us to extract the critical exponent of the order parameter (β = 0.12), which suggests a quasi two-dimensional ordering in [NH4][Zn(HCOO)3]. The experimental EPR results are supported by the density functional theory calculations of the zero-field splitting parameters. Relaxation time measurements of the Mn2+ centers indicate that the longitudinal relaxation is mainly driven by the optical phonons, which correspond to the vibrations of the metal–oxygen octahedra. The temperature behavior of the transverse relaxation indicates a dynamic process in the ordered ferroelectric phase.

Optically addressable spin-triplet defects in silicon carbide, such as divacancies and negatively charged nitrogen vacancy $({\mathrm{NV}}^{\ensuremath{-}})$ allow to develop modern quantum technologies operating in the near-infrared range based on the well-developed semiconductor material. Here, by means of both high-frequency (94 GHz) pulsed electron paramagnetic resonance (EPR) and electron-nuclear double Rresonance (ENDOR) techniques the ground state properties of the negatively charged ${\mathrm{NV}}^{\ensuremath{-}}$ defect in $4H$-SiC were studied. We experimentally determined the ordering of the ground state spin sublevels and established the sign of the zero-field splitting to be positive as predicted by theory. Analysis of nuclear magnetic resonance transitions in ENDOR spectra allowed to determine the sign, symmetry, and absolute values of the hyperfine interaction of the ${\mathrm{NV}}^{\ensuremath{-}}$ defect electron spin with $^{14}\mathrm{N}$ nuclear spin as ${\mathit{A}}_{\ensuremath{\parallel}}=\ensuremath{-}1.142\phantom{\rule{4pt}{0ex}}\mathrm{MHz}$ and ${\mathit{A}}_{\ensuremath{\perp}}=\ensuremath{-}1.184\phantom{\rule{4pt}{0ex}}\mathrm{MHz}$. The absolute value of the nuclear quadrupole interaction constant reflecting an interaction between the $^{14}\mathrm{N}$ nuclear electric quadrupole moment with the electric field gradient was determined to be $|{\mathit{C}}_{q}|=2.44\phantom{\rule{4pt}{0ex}}\mathrm{MHz}$. This large value is compatible with a threefold coordinated $^{14}\mathrm{N}$ nucleus with uniaxial symmetry and proves conclusively the existence of a nearestneighbor ${\mathrm{N}}_{\mathrm{C}}{\mathrm{V}}_{\mathrm{Si}}$ pair in the material. For this ${\mathrm{NV}}^{\ensuremath{-}}$ defect, an ensemble (Hahn-echo) coherence time of ${\mathit{T}}_{\text{2}}=49\phantom{\rule{4pt}{0ex}}\ensuremath{\mu}\mathrm{s}$ was measured, a value which is in the range previously reported for silicon vacancy spin ensembles and slightly longer than ${\mathit{T}}_{\text{2}}=40\phantom{\rule{4pt}{0ex}}\ensuremath{\mu}\mathrm{s}$ measured here on the divacancy spin ensemble.

Density-functional theory within a Berry-phase formulation of the dynamical polarization is used to determine the second-order susceptibility $\chi^{(2)}$ of lithium niobate (LiNbO$_3$). Defect trapped polarons and bipolarons are found to strongly enhance the nonlinear susceptibility of the material, in particular if localized at Nb$_\mathrm{V}$-V$_{\mathrm{Li}}$ defect pairs. This is essentially a consequence of the polaronic excitation resulting in relaxation-induced gap states. The occupation of these levels leads to strongly enhanced $\chi^{(2)}$ coefficients and allows for the spatial and transient modification of the second-harmonic generation of macroscopic samples., Comment: 5 pages, 6 figures

The stacking of different two-dimensional (2D) materials provides a promising approach to realize new states of quantum matter. In this combined scanning tunneling microscopy (STM) and density functional theory (DFT) study we show that the structure in weakly bound, purely van der Waals (vdW) interacting systems is strongly influenced by screening and relaxation. We studied in detail the physisorption of lead phthalocyanine (PbPc) molecules on epitaxial monolayer graphene on SiC(0001) as well as on highly ordered pyrolytic graphite (HOPG), resembling truly 2D and anisotropic, semi-infinite three-dimensional (3D) supports. Our analysis demonstrates that the different deformation ability of the vdW coupled systems, i.e., their actual thickness and buckling, triggers the molecular morphology and exhibits a proximity coupled band structure. It thus provides important implications for future 2D design concepts.

The $\mathrm{Si}(111)\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3}R{30}^{\ensuremath{\circ}}\text{\ensuremath{-}}\mathrm{B}\phantom{\rule{0.28em}{0ex}}[\mathrm{Si}(111)\text{\ensuremath{-}}\mathrm{B}]$ surface has evolved into a particularly interesting surface in the context of on-surface molecular self-assembly. Photoemission spectroscopy is a powerful tool to understand the interaction between the surface and the adsorbates. Previous studies of $\mathrm{Si}(111)\text{\ensuremath{-}}\mathrm{B}$ contain many inconsistencies with regard to the Si $2p$ core level and valence-band dispersion. Here we employ synchrotron-based core-level and angle-resolved photoemission spectroscopy measurements in combination with density functional theory (DFT) calculations to address these issues. DFT calculations of the Si $2p$ core-level spectra accurately identify contributions from one bulk and five surface components, which allows us to obtain a comprehensive understanding of the spectra recorded at different photon energies. As an archetypal example, this refined decomposition is employed to understand the changes in Si $2p$ spectra upon the adsorption of cobalt phthalocyanine molecules. Regarding the valence-band dispersion of the clean $\mathrm{Si}(111)\text{\ensuremath{-}}\mathrm{B}$ surface, our comprehensive DFT and photoemission investigations are able to reconcile the inconsistencies appearing in previous studies and reveal several yet unreported surface states. Furthermore, we are able to theoretically and experimentally resolve the distribution of these surface states in constant energy plots.

The Si(111) ? 3 × 3R30o-B [Si(111)-B] surface has evolved into a particularly interesting surface in the ? context of on-surface molecular self-assembly. Photoemission spectroscopy is a powerful tool to understand the interaction between the surface and the adsorbates. Previous studies of Si(111)-B contain many inconsistencies with regard to the Si 2p core level and valence-band dispersion. Here we employ synchrotron-based core-level and angle-resolved photoemission spectroscopy measurements in combination with density functional theory (DFT) calculations to address these issues. DFT calculations of the Si 2p core-level spectra accurately identify contributions from one bulk and five surface components, which allows us to obtain a comprehensive understand- ing of the spectra recorded at different photon energies. As an archetypal example, this refined decomposition is employed to understand the changes in Si 2p spectra upon the adsorption of cobalt phthalocyanine molecules. Regarding the valence-band dispersion of the clean Si(111)-B surface, our comprehensive DFT and photoemis- sion investigations are able to reconcile the inconsistencies appearing in previous studies and reveal several yet unreported surface states. Furthermore, we are able to theoretically and experimentally resolve the distribution of these surface states in constant energy plots.

The magnetic signatures of ${\mathrm{Ti}}^{3+}$ centers in potassium titanyl phosphate (KTP) are studied within density-functional theory (DFT). The hyperfine tensor elements are very sensitive to the structural surrounding; the paramagnetic hyperfine splittings are used to evaluate the defect models. For each of the four experimentally observed electron paramagnetic resonance (EPR) spectra, we identify a defect model that reproduces the paramagnetic signature. All of them are electron donors, whereby one specific Ti atom can be identified, whose formal oxidation number is lowered from $4+$ in the ideal crystal to $3+$. The related charge redistribution leads to a strong polarization of the corresponding ${\mathrm{Ti}}^{3+}$ center. However, in three cases a second Ti atom, connected to the first by a mutual polarized O atom, is polarized too. Positively charged O vacancies at the lattice site O(10) are unique in leading to the formation of the only ${\mathrm{Ti}}^{3+}$ center that is stable at room temperature. This defect induces a defect state within the band gap, which may be excited during second harmonic generation (SHG) applications and thus is a plausible candidate to explain the so-called gray tracking, i.e., photochromic damage.

The attachment of homoleptic Ru bis-terpy complexes on graphene oxide significantly improved the photocatalytic activity of the complexes. These straightforward complexes were applied as photocatalysts in a Heck reaction. Due to covalent functionalization on graphene oxide, which functions as an electron reservoir, excellent yields were obtained. DFT investigations of the charge redistribution revealed efficient hole transfer from the excited Ru unit towards the graphene oxide.

Polarons in dielectric crystals play a crucial role for applications in integrated electronics and optoelectronics. In this work, we use density-functional theory and Green's function methods to explore the microscopic structure and spectroscopic signatures of electron polarons in lithium niobate (LiNbO3). Total-energy calculations and the comparison of calculated electron paramagnetic resonance data with available measurements reveal the formation of bound polarons at Nb_Li antisite defects with a quasi-Jahn-Teller distorted, tilted configuration. The defect-formation energies further indicate that (bi)polarons may form not only at Nb_Li antisites but also at structures where the antisite Nb atom moves into a neighboring empty oxygen octahedron. Based on these structure models, and on the calculated charge-transition levels and potential-energy barriers, we propose two mechanisms for the optical and thermal splitting of bipolarons, which provide a natural explanation for the reported two-path recombination of bipolarons. Optical-response calculations based on the Bethe-Salpeter equation, in combination with available experimental data and new measurements of the optical absorption spectrum, further corroborate the geometries proposed here for free and defect-bound (bi)polarons.

Combining electron paramagnetic resonance (EPR) spectroscopy and first-principles density functional theory calculations we have identified the carbon monovacancy center and a second carbon vacancy-related defect, the carbon vacancy--carbon antisite defect in $3C$-SiC. In close analogy to the vacancy in silicon, the carbon vacancy in $3C$-SiC with its four potentially equivalent silicon dangling bonds shows a strong Jahn-Teller effect, confirming previously predicted negative-$U$ properties. High-temperature annealing (above 700 \ifmmode^\circ\else\textdegree\fi{}C) of electron or proton irradiated samples anneals out the primary silicon monovacancies and generates a new defect, which we assign to the carbon vacancy--carbon antisite complex. As predicted by theory, this defect is the result of a structural instability of the silicon vacancy in the positive charge state, which transforms at high temperatures according to ${V}_{\mathrm{Si}}{\mathrm{C}}_{4}\ensuremath{\rightarrow}{V}_{\mathrm{C}}{\mathrm{C}}_{\mathrm{Si}}{\mathrm{C}}_{3}$. Both defects are deep donors and thus not suitable for achieving semi-insulating properties.

The spin-orbit coupling in solid state spin qubits allows for the lifting of spin degeneracy in the absence of an external magnetic field. The paper presents a theoretical framework to address this zero-field splitting in extended periodic systems, unravels its microscopic origin, and showcases its implications for coherent electrical control.

Density-functional theory is used to explore the Si(553)-Au surface dynamics. Our study (i) reveals a complex two-stage order-disorder phase transition where with rising temperature first the $\ifmmode\times\else\texttimes\fi{}3$ order along the Si step edges and, subsequently, the $\ifmmode\times\else\texttimes\fi{}2$ order of the Au chains is lost, (ii) identifies the transient modification of the electron chemical potential during soft Au chain vibrations as instrumental for disorder at the step edge, and (iii) shows that the transition leads to a self-doping of the Si dangling-bond wire at the step edge. The calculations are corroborated by Raman measurements of surface phonon modes and explain previous electron diffraction, scanning tunneling microscopy, and surface transport data.

The rapid and reliable detection of lethal agents such as sarin is of increasing importance. Here, density-functional theory (DFT) is used to compare the interaction of sarin with single-metal-centered phthalocyanine (MPc) and MPc layer structures to a benign model system, i.e., the adsorption of dimethyl methylphosphonate (DMMP). The calculations show that sarin and DMMP behave nearly identical to the various MPcs studied. Among NiPc, CuPc, CoPc, and zinc phthalocyanine (ZnPc), we find the interaction of both sarin and DMMP to be the strongest with ZnPc, both in terms of interaction energy and adsorption-induced work function changes. ZnPc is thus proposed as a promising sensor for sarin detection. Using X-ray photoelectron spectroscopy, the theoretically predicted charge transfer from DMMP to ZnPc is confirmed and identified as a key component in the sensing mechanism.

Inorganic organic interfaces are important for enhancing the power conversion efficiency of silicon based solar cells through singlet exciton fission SF . We elucidated the structure of the first monolayers of tetracene Tc , a SF molecule, on hydrogen passivated Si 111 [H Si 111 ] and hydrogenated amorphous Si a Si H by combining near edge X ray absorption fine structure NEXAFS and X ray photoelectron spectroscopy XPS experiments with density functional theory DFT calculations. For samples grown at or below substrate temperatures of 265 K, the resulting ultrathin Tc films are dominated by almost upright standing molecules. The molecular arrangement is very similar to the Tc bulk phase, with only slightly higher average angle between the conjugated molecular plane normal and the surface normal alpha around 77 . Judging from carbon K edge X ray absorption spectra, the orientation of the Tc molecules are almost identical when grown on H Si 111 and a Si H substrates as well as for sub mono to several monolayer coverages. Annealing to room temperature, however, changes the film structure towards a smaller alpha of about 63 . A detailed DFT assisted analysis suggests that this structural transition is correlated with a lower packing density and requires a well chosen amount of thermal energy. Therefore, we attribute the resulting structure to a distinct monolayer configuration that features less inclined, but still well ordered molecules. The larger overlap with the substrate wavefunctions makes this arrangement attractive for an optimized interfacial electron transfer in SF assisted silicon solar cells

The impact of condensed-phase and finite-temperature effects on the theoretical X-ray absorption spectra of transition metal complexes is assessed. The former are included in terms of the all-electron Gaussian and augmented plane-wave approach, whereas the latter are taken into account by extensive ensemble averaging along second-generation Car-Parrinello ab initio molecular dynamics trajectories. We find that employing the periodic boundary conditions and including finite-temperature effects systematically improves the agreement between our simulated X-ray absorption spectra and experimental measurements. © 2018 Wiley Periodicals, Inc.

Whereas intrinsic defects in silicon carbide (SiC) have been widely considered for qubit applications, transition metals in this material have not yet been recognized as alternative systems. We have investigated the magneto-optical properties of the ${\mathrm{V}}^{3+}$ center in $4H\text{-SiC}$ by electron paramagnetic resonance (EPR) and photo-EPR spectroscopy in view of their possible application in quantum technology. We show that they fulfill all the requirements for such applications: a high-spin $S=1$ ground state, optically induced ground-state spin polarization of more than 70%, long spin-lattice relaxation times of the order of a second, as well as associated zero-phonon photoluminescence emission lines in the range of 1.8 \ensuremath{\mu}m. Further, the zero-field splitting parameter $D$ is temperature dependent and increases between $T=4\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ and $T=292\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ linearly with a rate of 440 kHz/K, allowing potential nanoscale temperature sensing. These properties make the vanadium acceptor an extremely promising candidate for qubit applications with optical properties in the telecommunication optical range.

We demonstrate here that theory-assisted near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy enables the site-sensitive monitoring of on-surface chemical reactions, thus, providing information not accessible by other techniques. As a prototype example, we have used free-base 5,10,15-tris(pentafluorophenyl)corroles (3H-TpFPC) adsorbed on Ag(111) and present a detailed investigation of the angle-dependent NEXAFS of this molecular species as well as of their thermally induced derivatives. For this, we have recorded experimental C and N K-edge NEXAFS spectra and interpret them based on XAS cross-section calculations by using a continuous fraction approach and core-hole including multiprojector PAW pseudopotentials within DFT. We have characterized the as-deposited low temperature (200 K) phase and unraveled the subsequent changes induced by dehydrogenation (at 330 K) and ring-closure reactions (at 430 K). By exemplarily obtaining profound insight into the on-surface chemistry of free-base corrolic species adsorbed on a noble metal this work highlights how angle-dependent XAS combined with accurate theoretical modeling can serve for the investigation of on-surface reactions, whereby even highly similar molecular structures, such as tautomers and isomers, can be distinguished.

The hexanuclear thioguanidine mixed-valent copper complex cation [Cu6 (NGuaS)6 ]+2 (NGuaS = o-SC6 H4 NC(NMe2 )2 ) and its oxidized/reduced states are theoretically analyzed by means of density functional theory (DFT) (TPSSh + D3BJ/def2-TZV (p)). A detailed bonding analysis using overlap populations is performed. We find that a delocalized Cu-based ring orbital serves as an acceptor for donated S p electrons. The formed fully delocalized orbitals give rise to a confined electron cloud within the Cu6 S6 cage which becomes larger on reduction. The resulting strong electrostatic repulsion might prevent the fully reduced state. Experimental UV/Vis spectra are explained using time-dependent density functional theory (TD-DFT) and analyzed with a natural transition orbital analysis. The spectra are dominated by MLCTs within the Cu6 S6 core over a wide range but LMCTs are also found. The experimental redshift of the reduced low energy absorption band can be explained by the clustering of the frontier orbitals. © 2017 Wiley Periodicals, Inc.

Radical cyclization is among the most powerful and versatile reactions for constructing mono- and polycyclic systems, but has, to date, remained unexplored in the context of on-surface synthesis. We report the controlled on-surface synthesis of stable corrole radicals on Ag(111) via site-specific dehydrogenation of a pyrrole N-H bond in the 5,10,15-tris(pentafluoro-phenyl)-corrole triggered by annealing at 330 K under ultrahigh-vacuum conditions. We reveal a thermally induced regioselective cyclization reaction mediated by a radical cascade and resolve the reaction mechanism of the pertaining cyclodefluorination reaction at the single-molecule level. Via intramolecularly resolved probing of the radical-related Kondo signature, we achieve real space visualization of the distribution of the unpaired electron density over specific sites within the corrole radical. Annealing to 550 K initiates intermolecular coupling reactions, producing an extended π-conjugated corrole system.

Corrole compounds attract increasing interest due to their potential to stabilize high-valent metal states. X-ray spectroscopy is a powerful tool for the investigation and development of functional interfaces. For corrolic species, however, the required reference data are missing. Here, we employ a multitechnique X-ray investigation of thin films of the prototypical free-base 5,10,15-tris(pentafluorophenyl)corrole (3H-TpFPC) grown on the Ag(111) surface under ultrahigh vacuum conditions. Ultrapure corrole multilayer samples are prepared and characterized by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. In parallel, the X-ray fingerprints are simulated using the continued-fraction approach within density functional theory (DFT) for extended, (quasi-)periodic molecular structures. An excellent agreement between experimental and theoretical spectra enables a thorough interpretation of the detailed spectral features and proves an accurate descripti...

Atomlike defect levels in silicon carbide (SiC) polytypes have been proposed and proven to be an excellent platform for various quantum technology applications. Single-photon emitters, coherent control at room temperature, and temperature and magnetic field sensing at the nanoscale have already been demonstrated for the case of vacancy and divacancy defects in SiC and more recently proposed for negatively charged NV centers. NV centers, which allow a better control of their generation, offer in addition a further shift of the spectral range in the near infrared, i.e., in the $O$- and $S$-band telecom range. We demonstrate here that the association of high resolution optical spectroscopy and electron paramagnetic resonance spectroscopy combined with first-principles calculations allow the identification of the microscopic structure of the six distinct NV centers in $6H\ensuremath{-}\mathrm{SiC}$ and the assignment of their associated zero-phonon photoluminescence lines. Time resolved photo-EPR measurements at $T=4\phantom{\rule{0.16em}{0ex}}\mathrm{K}$ show that NV centers in $6H\ensuremath{-}\mathrm{SiC}$ present spin lattice relaxation times of several seconds. These excellent qubit properties should enable their application and implementation in quantum information devices.

An accurate description of the two-electron density, crucial for magnetic coupling in spin systems, provides in general a major challenge for density functional theory calculations. It affects, e.g., the calculated zero-field splitting (ZFS) energies of spin qubits in semiconductors that frequently deviate significantly from experiment. In the present work (i) we propose an efficient and robust strategy to correct for spin contamination in both extended periodic and finite-size systems, (ii) verify its accuracy using model high-spin molecules, and finally (iii) apply the methodology to calculate accurate ZFS of spin qubits (NV$^-$ centers, divacancies) in diamond and silicon carbide. The approach is shown to reduce the dependence on the used exchange-correlation functional to a minimum.

The atomic geometry and energetics of oxygen and potassium vacancies in potassium titanyl phosphate (KTP) as well as their electronic and optical properties are studied within density-functional theory in dependence of their charge state. Oxygen vacancies formed between Ti and P are characterized by a negative-U behavior. Their neutral charge state is favored for Fermi levels near the conduction band and gives rise to a defect level in the band gap, which leads to an additional optical absorption peak. In contrast, the two-fold positive charge state, stable for low and intermediate values of the Fermi level, modifies the KTP optical response only slightly. Oxygen vacancies formed between two Ti atoms are two-fold positively charged, while potassium vacancies are negatively charged irrespective of the Fermi level position. In both these cases, the KTP optical response is essentially not affected.

Nanodiamond (ND) hosting nitrogen-vacancy (NV) centers is a promising platform for quantum sensing applications. Sensitivity of the applications using NV centers in NDs is often limited due to presence of paramagnetic impurity contents near the ND surface. Here, we investigate near-surface paramagnetic impurities in NDs. Using high-frequency (HF) electron paramagnetic resonance spectroscopy, the near-surface paramagnetic impurity within the shell of NDs is probed and its g-value is determined to be 2.0028(3). Furthermore, HF electron-electron double resonance-detected nuclear magnetic resonance spectroscopy and a first principle calculation show that a possible structure of the near-surface impurity is the negatively charged vacancy V-. The identification of the near-surface impurity by the present investigation provides a promising pathway to improve the NV properties in NDs and the NV-based sensing techniques., Comment: 21 pages, 6 figures

Spin-spin zero-field splitting (ZFS) is a sensitive spectroscopic signature accessable by electron paramagnetic resonance. It is the key fingerprint used for the identification of high-spin defect centers in semiconducting host materials and for the characterization of their electronic structure. In recent years, much progress has been made in developing an efficient first-principles methodology for ZFS calculations that help in the interpretation of experimental data. Here we address the negatively charged nitrogen-vacancy center (NV\(^-\)) in diamond. It is used as a test system to explore the accuracy and efficiency of spin-spin zero-field splitting calculations on massively parallel computing systems.

Density functional theory (DFT) and time-dependent DFT calculations are presented for the dicopper thiolate complex Cu2 (NGuaS)2 Cl2 [NGuaS=2-(1,1,3,3-tetramethylguanidino) benzenethiolate] with a special focus on the bonding mechanism of the Cu2 S2 Cl2 core and the spectroscopic response. This complex is relevant for the understanding of dicopper redox centers, for example, the CuA center. Its UV/Vis absorption is theoretically studied and found to be similar to other structural CuA models. The spectrum can be roughly divided in the known regions of metal d-d absorptions and metal to ligand charge transfer regions. Nevertheless the chloride ions play an important role as electron donors, with the thiolate groups as electron acceptors. The bonding mechanism is dissected by means of charge decomposition analysis which reveals the large covalency of the Cu2 S2 diamond core mediated between Cu dz2 and S-S π and π* orbitals forming Cu-S σ bonds. Measured resonant Raman spectra are shown for 360- and 720-nm excitation wavelength and interpreted using the calculated vibrational eigenmodes and frequencies. The calculations help to rationalize the varying resonant behavior at different optical excitations. Especially the phenylene rings are only resonant for 720 nm. © 2016 Wiley Periodicals, Inc.

Density functional theory (DFT) calculations with localized as well as plane-wave basis functions are performed for the recently reported dicopper thiolate species Cu2 (NGuaS)2 Cl2 [NGuaS = 2-(1,1,3,3-tetramethylguanidino) benzenethiolate, C11 H16 N3 S] and its bromo derivative [Neuba et al., Angew. Chem. Int. Ed. 2012, 51, 1714.]. For both hybrid and semilocal functionals, the neutral complexes are found to have broken symmetry (BS) character, with electron paramagnetic resonance silent, antiferromagnetically coupled [Cu(2+) …Cu(2+) ] site in which the coupling is driven by super exchange interaction within the Cu2 S2 diamond core. The accurate theoretical description of the geometric structure, however, provides a major challenge for DFT: (i) the multideterminant character of the ground state wave function has to be covered by the BS approach. It requires (ii) metageneralized gradient approximations, that is hybrid functionals with an explicit dependence on the kinetic energy of the individual orbitals: In combination with a dispersion correction, the metafunctional TPSSh results in a CuCu distance close to the experimentally observed value of 2.7 Å. For the negative charge state of the complex, a mixed-valent [Cu(1.5+) …Cu(1.5+) ] electronic structure with a smaller CuCu distance of 2.6 Å is predicted, similar to the value of the CuA site of cytochrome c oxidase.

The interplay between Mn ions and corrole ligands gives rise to complex scenarios regarding the metal centers' electronic properties expressing a range of high oxidation states and spin configurations. The resulting potential of Mn-corroles for applications such as catalysts or fuel cells has recently been demonstrated. However, despite being crucial for their functionality, the electronic structure of Mn-corroles is often hardly accessible with traditional techniques and thus is still under debate, especially under interfacial conditions. Here, we unravel the electronic ground state of the prototypical Mn-5,10,15-tris(pentafluorophenyl)corrole complex through X-ray spectroscopic investigations of ultrapure thin films and quantum chemical analysis. The theory-based interpretation of Mn photoemission and absorption fine structure spectra (3s and 2p and L2,3-edge, respectively) evidence a Mn(III) oxidation state with an S = 2 high-spin configuration. By referencing density functional theory calculations with the experiments, we lay the basis for extending our approach to the characterization of complex interfaces.

Density-functional theory is used to probe the spin structure of the Si(553)-Au surface. A diamagnetic $s{p}^{2}+p$ rehybridized structure, where the dangling bonds are either filled with two spin-paired electrons or are empty, is more favorable and in better agreement with experiment than the generally accepted spin-chain model. The shallow potential energy surface of Si(553)-Au, together with the ordered array of empty dangling bonds, suggests this surface as susceptible for spin polarization by doping, however.

The impact of condensed-phase and finite-temperature effects on the theoretical X-ray absorption spectra of transition metal complexes is assessed. The former are included in terms of the all-electron Gaussian and augmented plane-wave approach, whereas the latter are taken into account by extensive ensemble averaging along second-generation Car-Parrinello ab initio molecular dynamics trajectories. We find that employing the periodic boundary conditions and including finite-temperature effects systematically improves the agreement between our simulated X-ray absorption spectra and experimental measurements. © 2018 Wiley Periodicals, Inc.

For high-spin centers, one of the key spectroscopic fingerprints is the zero-field splitting (ZFS) addressable by electron paramagnetic resonance. In this paper, an implementation of the spin-spin contribution to the ZFS tensor within the projector augmented-wave (PAW) formalism is reported. We use a single-determinant approach proposed by M. J. Rayson and P. R. Briddon [Phys. Rev. B 77, 035119 (2008)], and complete it by adding a PAW reconstruction term which has not been taken into account before. We benchmark the PAW approach against a well-established all-electron method for a series of diatomic radicals and defects in diamond and cubic silicon carbide. While for some of the defect centers the PAW reconstruction is found to be almost negligible, in agreement with the common assumption, we show that in general it significantly improves the calculated ZFS towards the all-electron results.

𝛽-Ga2O3 has recently received attention as an ultra-wide-band-gap material, promising as transparent conductor and for high-power device applications. In this talk, we review some recent computational work on the electronic band structure and it defects. The electronic band structure was calculated using the quasiparticle self-consistent GW method including a correction of the screened Coulomb interaction W for electron-hole interaction and lattice-polarization effect. The selection rules of the optical transition help understand the anisotropy of the optical absorption.1 Among the point defects, which have already been discussed in various papers,2 we here focus on the two types of Ga–vacancies, which can occur on both the tetrahedral and octahedral Ga site. Electron paramagnetic resonance (EPR) related to the Ga-vacancy has been reported.3,4 Here we present first-principles calculations of the g-factor and hyperfine structure, which allow us to identify the EPR spectrum observed after high energy particle irradiation, with the tetrahedral Ga vacancy in the 2- charge state. Modification of the EPR spectrum under low temperature photoexcitation are explained by the following model. The EPR spectrum of the tetrahedral Ga vacancy shows superhyperfine interaction with two Ga atoms which are nearest neighbors to the oxygen on which the defect localizes in the q=2- charge state. The g-tensor has its largest deviation from the free-electron value for the crystallographic b-direction in which the defect Ga-O-Ga complex is oriented. According to Ref. 2, the tetrahedral Ga vacancy has its 2-/3- transition level closer to the conduction band minimum than the octahedral one. Upon illumination, this defect may become inactivated while the octahedral one is activated. The latter has a different orientation of its main largest g-tensor component but similar superhyperfine splitting with two Ga atoms. These computational findings explain the corresponding experimental observations. 1 Amol Ratnaparkhe and Walter R. L. Lambrecht, Appl. Phys. Lett. 110, 132103 (2017) 2 Peter Deak, Quoc Duy Ho, Florian Seemann, Balint Aradi, Michael Lorke, and Thomas Frauenheim, Phys. Rev. B 95, 075208 (2017) and references therein. 3 B. E. Kananen , L. E. Halliburton , K. T. Stevens , G. K. Foundos , and N. C. Giles, Appl. Phys. Lett. 110, 202104 (2017) 4 H.Jurgen von Bardeleben, unpublished