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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Simulating dirty bosons on a quantum computer

Abstract Quantum computers hold the potential to unlock new discoveries in complex quantum systems by enabling the simulation of physical systems that have heretofore been impossible to implement on classical computers due to intractability. A system of particular interest is that of dirty bosons, whose physics highlights the intriguing interplay of disorder and interactions in quantum systems, playing a central role in describing, for instance, ultracold gases in a random potential, doped quantum magnets, and amorphous superconductors. Here, we demonstrate how quantum computers can be used to elucidate the physics of dirty bosons in one and two dimensions. Specifically, we explore the disorder-induced delocalized-to-localized transition using adiabatic state preparation. In one dimension, the quantum circuits can be compressed to small enough depths for execution on currently available quantum computers. In two dimensions, the compression scheme is no longer applicable, thereby requiring the use of large-scale classical state vector simulations to emulate quantum computer performance. In addition, simulating interacting bosons via emulation of a noisy quantum computer allowed us to study the effect of quantum hardware noise on the physical properties of the simulated system. Our results suggest that scaling laws control how noise modifies observables versus its strength, the circuit depth, and the number of qubits. Moreover, we observe that noise impacts the delocalized and localized phases differently. A better understanding of how noise alters the observed properties of the simulated system is essential for leveraging near-term quantum devices for simulation of dirty bosons, and indeed for condensed matter systems in general.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2022

Glassy quantum nuclear pasta in neutron star crusts

We conduct a comprehensive survey of the shape parameter space of the nuclear pasta phases in neutron star crusts by conducting three-dimensional Hartree-Fock + BCS calculations. Spaghetti, waffles, lasagna, bicontinuous phases and cylindrical holes occupy local minima in the resulting constant-pressure Gibbs energy surfaces, implying multiple geometries coexist at a given depth. Notably, the bicontinuous phase, in which both the neutron gas and nuclear matter extend continuously in all dimensions appears over a large depth range. Our results support the idea that nuclear pasta is a glassy system. At a characteristic temperature, of order 10 8 – 10 9 K, different phases may become frozen into domains whose sizes we estimate to be 1–50 times the lattice spacing and over which the local density and electron fraction can vary. Above this temperature, very little long-range order exists and matter is an amorphous solid. Electron scattering off domain boundaries may contribute to the disorder resistivity of the pasta phases. Annealing of the domains may occur during cooling; repopulating of local minima during crustal heating might lead to temperature-dependent transport properties in the deep crust layers. We identify four regions distinguished by whether pasta is the true ground state, and whether the pasta structure allows delocalization of protons. The whole pasta region can occupy up to 70% of the crust by mass and 25% by thickness, and the layer in which protons are delocalized could occupy 45% of the crust mass and 15% of its thickness.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Magic-Angle Twisted Bilayer Graphene as a Topological Heavy Fermion Problem

Magic-angle (θ=1.05°) twisted bilayer graphene (MATBG) has shown two seemingly contradictory characters: the localization and quantum-dot-like behavior in STM experiments, and delocalization in transport experiments. We construct a model, which naturally captures the two aspects, from the Bistritzer-MacDonald (BM) model in a first principle spirit. A set of local flat-band orbitals (f) centered at the AA-stacking regions are responsible to the localization. A set of extended topological semimetallic conduction bands (c), which are at small energetic separation from the local orbitals, are responsible to the delocalization and transport. The topological flat bands of the BM model appear as a result of the hybridization of f and c electrons. This model then provides a new perspective for the strong correlation physics, which is now described as strongly correlated f electrons coupled to nearly free c electrons—we hence name our model as the topological heavy fermion model. Using this model, we obtain the U(4) and U(4)×U(4) symmetries of Refs. [1–5] as well as the correlated insulator phases and their energies. Simple rules for the ground states and their Chern numbers are derived. Moreover, features such as the large dispersion of the charge ±1 excitations [2,6,7], and the minima of the charge gap at the Γ M point can now, for the first time, be understood both qualitatively and quantitatively in a simple physical picture. Our mapping opens the prospect of using heavy-fermion physics machinery to the superconducting physics of MATBG.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Phonon-Induced Localization of Excitons in Molecular Crystals from First Principles

The spatial extent of excitons in molecular systems underpins their photophysics and utility for optoelectronic applications. Phonons are reported to lead to both exciton localization and delocalization. However, a microscopic understanding of phonon-induced (de)localization is lacking, in particular, how localized states form, the role of specific vibrations, and the relative importance of quantum and thermal nuclear fluctuations. Here, we present a first-principles study of these phenomena in solid pentacene, a prototypical molecular crystal, capturing the formation of bound excitons, exciton-phonon coupling to all orders, and phonon anharmonicity, using density functional theory, the ab initio GW-Bethe-Salpeter equation approach, finite-difference, and path integral techniques. In this study, we find that for pentacene zero-point nuclear motion causes uniformly strong localization, with thermal motion providing additional localization only for Wannier-Mott-like excitons. Anharmonic effects drive temperature-dependent localization, and, while such effects prevent the emergence of highly delocalized excitons, we explore the conditions under which these might be realized

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Organic Macromolecular materials for Efficient Transport Properties in Light-Energy Conversion Applications. Final Report

We are grateful for the Department of Energy for support of this research related to the improvement of power conversion efficiency of organic photovoltaic architectures over the years. As we noted at the beginning and now, the fundamental photophysical pathways that connect the absorption of light to the production of charge carriers remain elusive in spite of continuing experimental and theoretical efforts. Our investigations were directed toward gaining information about the mechanism of this ultrafast, long-range charge separation in photovoltaic systems with non-fullerene acceptors. This problem is still of high importance for the organic photovoltaics because solving this problem will allow us to minimize the contribution of the geminate recombination and trapping the charges in bound charge transfer states. Extremely low charge separation driving energy specific to non-fullerene acceptor systems reduces the energy loss in organic photovoltaic cells making them competitive with inorganic and perovskite photovoltaic systems. A major accomplishment of this study was to detail the long-range ballistic charge separation in donor-non-fullerene acceptor photovoltaic systems. We have successfully probed the spatial structure of ultrafast long-range (~40nm) ballistic charge separation in donor-non-fullerene acceptor photovoltaic system. We performed a systematic investigation of the delocalized states in their connection to the efficient long-range charge separation using the pulse pair interferometric near-field microscopy method. This method possesses unique capability of detecting coherent effects with spatial resolution of few tens of nanometers. These measurements allowed us the determination of delocalized excitations locally in a thin film photovoltaic system and to be connected to the long-range charge separation and the power conversion efficiency. We also investigated long-lived coupled triplet pairs in a singlet fission process for the possibility of concerted extraction of two electrons from triplet entangled states. New experimental and theoretical approaches of the concerted double electron extraction were carried out. The impact of this work is the development of important structure-property relationships to the design criteria of more efficient organic photovoltaic cells in accordance with the BES mission.

14 SOLAR ENERGY↗
DOE OSTI2023

Biomimetic Light Harvesting Complexes Based on Self-Assembled Dye-DNA Nanostructures (Final Technical Report)

A fundamental limitation in the development of artificial molecular light harvesting structures is that generally if one places pigment molecules close enough to achieve very high energy transfer efficiency and absorbance cross section, the dyes interact in such a way that self-quenching occurs. This limits both the optical cross section and the overall efficiency of light capture in such systems. Nature overcomes this problem and achieves efficient energy transfer without self-quenching by controlling the environment, vibration characteristics, orientation and dynamics of the pigments involved in light harvesting. Natural light harvesting systems have evolved highly intricate chromophore architectures of protein-bound organic molecules that absorb and funnel solar energy with high efficiency and fast transfer rates using elegant excitonic circuitries. Nature achieves this precise control over the properties of pigment complexes by using specific proteins as templates to guide the formation of very well-defined pigment aggregates, groups of pigment molecules that are in close enough contact to undergo excitonic interactions resulting in new electronic properties that were not present in the monomer. In synthetic systems, pigment aggregates are well known, and J-aggregates and H-aggregates have been long studied for their unique properties. In Nature, the chlorosomes of green bacteria form what appear to be classical J-aggregates and the light harvesting complexes of purple nonsulfur bacteria form ring structures that have many of the properties of J-aggregates such as a red-shifted absorbance spectrum and excited states that are delocalized over multiple pigment molecules. These photosynthetic systems leverage the spectral and enhanced transport properties of J-like aggregates to achieve fast exciton transport within the antenna and thus high light-harvesting efficiency. The close interaction of the pigments results in substantial electronic coupling that lifts the degeneracy of excitonic states and therefore modifies the absorption and emission spectra of the monomer. In the case of J-aggregation, lower energy excitonic states acquire significant oscillator strength, resulting in a characteristic bathochromic shift of the absorption and fluorescence and often superradiant delocalized exciton states.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2021

Fracture Network Localization Preceding Catastrophic Failure in Triaxial Compression Experiments on Rocks

We quantify the spatial distribution of fracture networks throughout six in situ X-ray tomography triaxial compression experiments on crystalline rocks at confining stresses of 5–35 MPa in order to quantify how fracture development controls the final macroscopic failure of the rock, a process analogous to those that control geohazards such as earthquakes and landslides. Tracking the proportion of the cumulative volume of fractures with volumes >90th percentile to the total fracture volume, ∑ v 90 / v t o t indicates that the fracture networks tend to increase in localization toward these largest fractures for up to 80% of the applied differential stress. The evolution of this metric also matches the evolution of the Gini coefficient, which measures the deviation of a population from uniformity. These results are consistent with observations of localizing low magnitude seismicity before large earthquakes in southern California. In both this analysis and the present work, phases of delocalization interrupt the general increase in localization preceding catastrophic failure, indicating that delocalization does not necessarily indicate a reduction of seismic hazard. However, the proportion of the maximum fracture volume to the total fracture volume does not increase monotonically. Experiments with higher confining stress tend to experience greater localization. To further quantify localization, we compare the geometry of the largest fractures, with volumes >90th percentile, to the best fit plane through these fractures immediately preceding failure. The r 2 scores and the mean distance of the fractures to the plane indicate greater localization in monzonite than in granite. The smaller mean mineral diameter and lower confining stress in the granite experiments may contribute to this result. Tracking these various metrics of localization reveals a close association between macroscopic yielding and the acceleration of fracture network localization. Near yielding, ∑ v 90 / v t o t and the Gini coefficient increase while the mean distance to the final failure plane decreases. Macroscopic yielding thus occurs when the rate of fracture network localization increases.

58 GEOSCIENCES↗
NASA NTRS1990

A technique for determining Urbach edge, midgap states and electric field in a-Si:H and a-(Si,Ge):H devices

A technique for measuring the Urbach energy of valence band tail states and midgap defect densities in a-Si:H and a-(Si,Ge):H devices is described. The Urbach energy is determined by measuring the quantum efficiency (QE) of delocalized holes in the devices, whereas the midgap state density (DOS) is estimated by measuring the QE of localized holes. The distinction between delocalized and localized holes is obtained from the behavior of the QE upon the application of reverse bias to the device. The QE of holes localized in midgap states increases significantly upon the application of reverse bias because of Frenkel-Poole tunneling, whereas the QE of holes in tail states does not show such an increase. It is shown that upon light soaking the Urbach edge does not change, but the midgap DOS does increase significantly. A primary consequence of the increase in DOS is a decrease in electric field in the low-field middle i region of the p-i-n cell. The decrease in electric field is experimentally estimated by fitting the increase in the reverse bias QE to Frenkel-Poole tunneling.

Dalal, Vikram L.↗
NASA NTRS1994

The Fraternal Twins of Quartet O4(+)

Eleven stationary geometries of quartet O4(+) have been studied by ab initio methods. The geometries were optimized at the Complete Active Space Self-Consistent Field (CASSCF) level of theory and the energies were calculated by the multiconfigurational second order pertubation method (CASPT2), using Double-Zeta Plus polarization (DZP), Triple-Zeta Plus Double Polarization (TZ2P), average Atomic Natural Orbital (ANO) (5s4p2d) and average ANO (6s5p3d2f) basis sets. The rectangular and trans-planar structures are found to be the most stable, with an energy barrier to conversion between the two at the threshold of dissociation. Both have a delocalized hole and are stable relative to separated 02 and 02(+)by 11.0 and 11.5 kcal/mol for the rectangular and the 2 trans-planar structure, respectively, compared with the experimentally deduced energy in the range of 9.2 to 10.8 kcal/mol. The adiabatic ionization potentials of 04 and 02 are computed to be 11.67 and 12.21 eV, while experimental values are 11.66 and 12.07 eV, respectively. The vibrational frequencies have been computed for all degrees of freedom at the CASSCF level of theory. Symmetry breaking is found to be a particular problem in the computation of the antisymmetric stretch frequency for the delocalized structures at the CASSCF level of theory. Attempts to rectify these problems using the restricted active space self-consistent field (RASSCF) method leads to additional difficulties, but further analysis yields insight into the symmetry breaking and problems with earlier calculations. Finally, a nonorthogonal configuration interaction (CI) calculation based on the interaction of localized CASSCF wave functions using the Complete Active Space State Interation (CASSI) method leads to a balanced treatment of the antisymmetric stretch which is free from symmetry breaking. The study explains the four most prominent absorption frequencies observed in the partially unassigned IR spectrum of O4(+) isolated in solid neon as the antisymmetric OO stretch, and the combination band of the symmetric and antisymmetric 00 stretch of both the rectangular and trans-planar structures.

Lindh, Roland↗
NASA NTRS2018

Mechanism of Quantum Speedup in Novel Population Transfer Protocol for Binary Optimization Problems

We consider a novel quantum population transfer protocol to solve binary optimization problems that exploits quantum many-body dynamics in the delocalized regime. Hard optimization problems are characterized by energy landscape with a large number of local minima separated by large Hamming distances which scale with the problem size. This landscape gives rise to an interesting computational primitive: given an initial bit-string, we are to produce other bit-strings within certain narrow range of energies around the initial state. We consider a specific model we call "impurity band": a system of n qubits in a transverse field, where a number of bitstrings $M<<2^n$ selected at random are assigned random energies distributed in a narrow window of width $W<<1$ around the mean energy $-n$. We demonstrate the existence of the many-body delocalized regime in this model when the spectrum of the model splits into many-body minibands, and a typical eigenstate wave function is a superposition of peaks centered at a large number of local minima. The typical width of the minibands in energy determines the efficiency of the population transfer protocol. We demonstrate theoretically that the population transfer protocol achieves Grover type speedup in the unstructured impurity band model.

Kechedzhi, Kostyantyn↗
DOE OSTI2024

Regulating the Electron Distribution of Metal-Oxygen for Enhanced Oxygen Stability in Li-rich Layered Cathodes

Li-rich Mn-based layered oxides (LLO) hold great promise as cathode materials for lithium-ion batteries (LIBs) due to their unique oxygen redox (OR) chemistry, which enables additional capacity. However, the LLOs face challenges related to the instability of their OR process due to the weak transition metal (TM)-oxygen bond, leading to oxygen loss and irreversible phase transition that results in severe capacity and voltage decay. Herein, a synergistic electronic regulation strategy of surface and interior structures to enhance oxygen stability is proposed. In the interior of the materials, the local electrons around TM and O atoms may be delocalized by surrounding Mo atoms, facilitating the formation of stronger TM—O bonds at high voltages. Besides, on the surface, the highly reactive O atoms with lone pairs of electrons are passivated by additional TM atoms, which provides a more stable TM—O framework. Hence, this strategy stabilizes the oxygen and hinders TM migration, which enhances the reversibility in structural evolution, leading to increased capacity and voltage retention. This work presents an efficient approach to enhance the performance of LLOs through surface-to-interior electronic structure modulation, while also contributing to a deeper understanding of their redox reaction.

25 ENERGY STORAGE↗
DOE OSTI2022

Thermodynamic modeling of aqueous polyelectrolyte solutions with mixed-valent counterions

Thermodynamic modeling of aqueous polyelectrolyte solutions with salts is of significant interest for many industrial applications. Here this study applies the polyelectrolyte Nonrandom Two-liquid activity coefficient model to aqueous polyelectrolyte solutions with mixed-valent counterions. A modified Delocalized Binding Theory was proposed to determine the polyion condensation fractions of the mixed counterions. This modified theory accounts for the electrostatic binding of the counterions on the polyion, the dissociation entropy of the counterions, and the electrostatic interactions between the uncondensed ionic species. Given the polyion condensation fractions, the critical value of Manning’s parameter ξ and the amounts of uncondensed polyions and counterions can be calculated along with the activity coefficients of mobile ions. The model successfully correlates experimental data for various aqueous polyelectrolyte systems with mixed-valent counterions.

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

Tuning counterion chemistry to reduce carrier localization in doped semiconducting carbon nanotube networks

Understanding and controlling the impact that electrostatic interactions have on the transport of injected charge carriers is important for the utilization of pi-conjugated semiconductors in opto-electronic applications. Here, we explore the impact of dopant chemical and electronic structure on the doping efficacy and charge carrier transport in semiconducting single-walled carbon nanotube (s-SWCNT) networks using molecular charge-transfer dopants based on functionalized icosahedral dodecaborane (DDB) clusters. Calculations indicate that localization of electron density on the DDB core reduces the coulombic interactions that contribute to hole localization in the s-SWCNTs, thereby improving charge carrier transport. The enhanced delocalization produces an increase in the electrical conductivity and thermopower at lower charge carrier densities, yielding enhanced thermoelectric transport and a thermoelectric power factor that surpasses the previous best in class for enriched s-SWCNT thin-film networks. This strategy can be applied broadly across pi-conjugated semiconductors to tune and enhance performance in a variety of energy harvesting devices.

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

Electronic structure of mononuclear Cu-based molecule from density-functional theory with self-interaction correction

In this paper, we investigate the electronic structure of a planar mononuclear Cu-based molecule [Cu(C 6 H 4 S 2 ) 2 ] z in two oxidation states ( z = –2, –1) using density-functional theory (DFT) with Fermi–Löwdin orbital (FLO) self-interaction correction (SIC). The dianionic Cu-based molecule was proposed to be a promising qubit candidate. Self-interaction error within approximate DFT functionals renders severe delocalization of electron and spin densities arising from 3 d orbitals. The FLO-SIC method relies on optimization of Fermi–Löwdin orbital descriptors (FODs) with which localized occupied orbitals are constructed to create SIC potentials. Starting with many initial sets of FODs, we employ a frozen-density loop algorithm within the FLO-SIC method to study the Cu-based molecule. We find that the electronic structure of the molecule remains unchanged despite somewhat different final FOD configurations. In the dianionic state (spin S = 1/2), FLO-SIC spin density originates from the Cu d and S p orbitals with an approximate ratio of 2:1, in quantitative agreement with multireference calculations, while in the case of SIC-free DFT, the orbital ratio is reversed. Overall, FLO-SIC lowers the energies of the occupied orbitals and, in particular, the 3 d orbitals unhybridized with the ligands significantly, which substantially increases the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) compared to SIC-free DFT results. The FLO-SIC HOMO–LUMO gap of the dianionic state is larger than that of the monoanionic state, which is consistent with experiment. Our results suggest a positive outlook of the FLO-SIC method in the description of magnetic exchange coupling within 3 d -element-based systems.

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

Manipulating meso-scale solvent structure from Pd nanoparticle deposits in deep eutectic solvents

Deep Eutectic Solvents (DESs) are complex solutions that present unique challenges compared to traditional electrolytes. Unlike most electrolytes and ionic liquids, DESs have delicate hydrogen bond networks that are responsible for their highly sensitive compositional dependence on the melting point. Prior work has demonstrated unique nanoscale structure both experimentally and theoretically that brings both challenges and opportunities to their adoption in traditional electrochemical processes. In this study, we use in-situ sample-rotated ultra-small angle X-ray scattering to resolve the near-interface solvent structure after electrodepositing Pd nanoparticles onto a glassy carbon electrode in choline chloride:urea and choline chloride:ethylene glycol DESs. Our results indicate that solvent structure can be observed on the meso-scale in the choline chloride:urea and choline chloride:ethylene glycol systems. Importantly, this extended solvent structure peaks at -0.5 V (vs. Ag/AgCl) and decreases slightly with higher overpotentials during Pd electrodeposition. Experimentally, the nature of this structure is more pronounced in the ethylene glycol system, as evidenced by both the X-ray scattering as well as the electrochemical impedance spectroscopy (EIS). Here, molecular dynamics simulations and dipolar orientation analysis reveal that chloride delocalization near the Pd interface and long-range interactions between the choline and each hydrogen bond donor are very different and qualitatively consistent with the experimental data. These results show how the long-range solvent-deposit interactions can be tuned by changing the hydrogen bond donor in the DES and the applied potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Density functional theory of water with the machine-learned DM21 functional

The delicate interplay between functional-driven and density-driven errors in density functional theory (DFT) has hindered traditional density functional approximations (DFAs) from providing an accurate description of water for over 30 years. Recently, the deep-learned DeepMind 21 (DM21) functional has been shown to overcome the limitations of traditional DFAs as it is free of delocalization error. To determine if DM21 can enable a molecular-level description of the physical properties of aqueous systems within Kohn–Sham DFT, we assess the accuracy of the DM21 functional for neutral, protonated, and deprotonated water clusters. Furthermore, we find that the ability of DM21 to accurately predict the energetics of aqueous clusters varies significantly with cluster size. Additionally, we introduce the many-body MB-DM21 potential derived from DM21 data within the many-body expansion of the energy and use it in simulations of liquid water as a function of temperature at ambient pressure. We find that size-dependent functional-driven errors identified in the analysis of the energetics of small clusters calculated with the DM21 functional result in the MB-DM21 potential systematically overestimating the hydrogen-bond strength and, consequently, predicting a more ice-like local structure of water at room temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Polariton enhanced free charge carrier generation in donor–acceptor cavity systems by a second-hybridization mechanism

Cavity quantum electrodynamics has been studied as a potential approach to modify free charge carrier generation in donor–acceptor heterojunctions because of the delocalization and controllable energy level properties of hybridized light–matter states known as polaritons. However, in many experimental systems, cavity coupling decreases charge separation. In this work, we theoretically study the quantum dynamics of a coherent and dissipative donor–acceptor cavity system, to investigate the dynamical mechanism and further discover the conditions under which polaritons may enhance free charge carrier generation. We use open quantum system methods based on single-pulse pumping to find that polaritons have the potential to connect excitonic states and charge separated states, further enhancing free charge generation on an ultrafast timescale of several hundred femtoseconds. The mechanism involves polaritons with optimal energy levels that allow the exciton to overcome the high Coulomb barrier induced by electron–hole attraction. Moreover, we propose that a second-hybridization between a polariton state and dark states with similar energy enables the formation of the hybrid charge separated states that are optically active. These two mechanisms lead to a maximum of 50% enhancement of free charge carrier generation on a short timescale. However, our simulation reveals that on the longer timescale of picoseconds, internal conversion and cavity loss dominate and suppress free charge carrier generation, reproducing the experimental results. Thus, our work shows that polaritons can affect the charge separation mechanism and promote free charge carrier generation efficiency, but predominantly on a short timescale after photoexcitation.

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

Spin-state gaps and self-interaction-corrected density functional approximations: Octahedral Fe(II) complexes as case study

Accurate prediction of a spin-state energy difference is crucial for understanding the spin crossover phenomena and is very challenging for density functional approximations, especially for local and semi-local approximations due to delocalization errors. Here, we investigate the effect of the self-interaction error removal from the local spin density approximation (LSDA) and Perdew–Burke–Ernzerhof generalized gradient approximation on the spin-state gaps of Fe(II) complexes with various ligands using recently developed locally scaled self-interaction correction (LSIC) by Zope et al. [J. Chem. Phys. 151, 214108 (2019)]. The LSIC method is exact for one-electron density, recovers the uniform electron gas limit of the underlying functional, and approaches the well-known Perdew–Zunger self-interaction correction (PZSIC) as a particular case when the scaling factor is set to unity. Our results, when compared with reference diffusion Monte Carlo results, show that the PZSIC method significantly overestimates spin-state gaps favoring low spin states for all ligands and does not improve upon density functional approximations. The perturbative LSIC-LSDA using PZSIC densities significantly improves the gaps with a mean absolute error of 0.51 eV but slightly overcorrects for the stronger CO ligands. Finally, the quasi-self-consistent LSIC-LSDA, such as coupled-cluster single double and perturbative triple [CCSD(T)], gives a correct sign of spin-state gaps for all ligands with a mean absolute error of 0.56 eV, comparable to that of CCSD(T) (0.49 eV).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗