Approximate Exchange-correlation Research Articles

A DFT Study of Electronic and Magnetic Properties of Cr2O3 using Spin-Polarized Approach

The study of Cr2O3 magneto-electric material, particularly, the profound understanding of its antiferro-magnetic, is vital for its spintronics applications. In this paper, we present a study on electronic and magnetic properties of Cr2O3 crystal using the first-principles calculations based on the density functional theory. For more accurate results, additional Hubbard (U) parameter has been employed to GGA as well. Our calculated results are homogeneous with available experimental measurements. Results show the effects produced by GGA+U method upon the electronic and magnetic features of the material. We prove that, the spherically symmetric GGA+U approach for exchange correlation approximation portray is a superior depiction of electronic and magnetic properties of Cr2O3.

Approximating the Shifted Hartree-Exchange-Correlation Potential in Direct Energy Kohn-Sham Theory.

Levy and Zahariev [Phys. Rev. Lett. 113 113002 (2014)] have proposed a new approach for performing density functional theory calculations, termed direct energy Kohn-Sham (DEKS) theory. In this approach, the electronic energy equals the sum of orbital energies, obtained from Kohn-Sham-like orbital equations involving a shifted Hartree-exchange-correlation potential, which must be approximated. In the present study, density scaling homogeneity considerations are used to facilitate DEKS calculations on a series of atoms and molecules, leading to three nonlocal approximations to the shifted potential. The first two rely on preliminary Kohn-Sham calculations using a standard generalized gradient approximation (GGA) exchange-correlation functional and the results illustrate the benefit of describing the dominant Hartree component of the shift exactly. A uniform electron gas analysis is used to eliminate the need for these preliminary Kohn-Sham calculations, leading to a potential with an unconventional form that yields encouraging results, providing strong motivation for further research in DEKS theory.

Free Energy Profile of NaCl in Water: First-Principles Molecular Dynamics with SCAN and ωB97X-V Exchange-Correlation Functionals.

Properties of water and aqueous ionic solutions are of great scientific interest because they play a central role in the atmosphere, biological environments, and various industrial processes. Employing two advanced exchange-correlation (XC) approximations, ωB97X-V and SCAN, in first-principles molecular dynamics simulations, we calculate the potential of mean force of NaCl in water as a function of the ion separation distance. Compared to the commonly used GGA-PBE functional, both of these XC functionals perform much better in simulating liquid water at room temperature for obtaining structural properties. The potential of mean force of NaCl in water exhibits two minima corresponding to two distinct types of ion pairing. ωB97X-V predicts that the contact ion pair is energetically more stable than the solvent-separated ion pair. The SCAN functional, however, predicts the opposite stability order, similarly to other XC functionals such as PBE. This is notable especially since classical molecular dynamics simulations with widely used force-field models predict greater stability for the contact ion pair. We also discuss how the electronic structures of water molecules and ions depend on the XC approximations. ωB97X-V and SCAN approximations noticeably improve the description of electron charge on Cl- ion in water while the charge on Na+ ion does not vary appreciably among the three XC functionals.

Interplay between strong correlation and adsorption distances: Co on Cu(001)

Adsorbed transition metal atoms can have partially filled $d$- or $f$-shells due to strong on-site Coulomb interaction. Capturing all effects originating from electron correlation in such strongly correlated systems is a challenge for electronic structure methods. It requires a sufficiently accurate description of the atomistic structure (in particular bond distances and angles), which is usually obtained from Kohn-Sham density functional theory (DFT), which due to the approximate nature of the exchange-correlation functional may provide an unreliable description of strongly correlated systems. To elucidate the consequences of this popular procedure, we apply a combination of DFT with the Anderson impurity model (AIM), as well as DFT+U for a calculation of the potential energy surface along the Co/Cu(001) adsorption coordinate, and compare the results with those obtained from DFT. The adsorption minimum is shifted towards larger distances by applying DFT+AIM, or the much cheaper DFT+U method, compared to the corresponding spin-polarized DFT results, by a magnitude comparable to variations between different approximate exchange-correlation functionals (0.08 to 0.12 Angstrom). This shift originates from an increasing correlation energy at larger adsorption distances, which can be traced back to the Co 3$d_{xy}$ and 3$d_{z2}$ orbitals being more correlated as the adsorption distance is increased.

Atomic structures of graphene-like nanomaterials including SiC and BP

Honeycomb sheet, graphene like, structure has been interested and the planar structures of silicon carbide (h-SiC), boron phosphide (h-BP) and mixed of both materials h-(SiC)1-x(BP)x were investigated with x values of 0.00, 0.25, 0.50, 0.75 and 1.00. The 2 atoms per unit cell of hexagonal and 4, 8 and 16 atoms per unit cell of orthorhombic configurations were used in atomic structure calculation with 1.5 nm space distance between layers of graphene like structure. The calculation is set for 500 eV energy cutoff, using local density approximation (LDA) exchange-correlation functional, 200 Ry mesh cutoff. The lattice constant was varied to evaluate the stable atomic structures together with the average bond length. Then, the band structures including energy band gap, used to determine electronic property, was calculated to guide the utilization of novel electronic device for new millennium.

Exchange-correlation approximations for reduced-density-matrix-functional theory at finite temperature: Capturing magnetic phase transitions in the homogeneous electron gas

We derive an intrinsically temperature-dependent approximation to the correlation grand potential for many-electron systems in thermodynamical equilibrium in the context of finite-temperature reduced-density-matrix-functional theory (FT-RDMFT). We demonstrate its accuracy by calculating the magnetic phase diagram of the homogeneous electron gas. We compare it to known limits from highly accurate quantum Monte Carlo calculations as well as to phase diagrams obtained within existing exchange-correlation approximations from density functional theory and zero-temperature RDMFT.

Charge localization and ordering in A2Mn8O16 hollandite group oxides: Impact of density functional theory approaches

The phases of ${A}_{2}{\mathrm{Mn}}_{8}{\mathrm{O}}_{16}$ hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples ($A$ = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn $3d$ electrons are more explicitly considered with the DFT + $U$ approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-$U$ and a high-$U$ approach. In the low-$U$ case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-$U$ case, the electrons donated by A result in formation of local ${\mathrm{Mn}}^{3+}$ centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Finally, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + $U$ gives the best overall agreement with results from the hybrid functional.

Deorbitalization strategies for meta-generalized-gradient-approximation exchange-correlation functionals

We explore the simplification of widely used meta-generalized-gradient approximation (mGGA) exchange-correlation functionals to the Laplacian level of refinement by use of approximate kinetic energy density functionals (KEDFs). Such deorbitalization is motivated by the prospect of reducing computational cost while recovering a strictly Kohn-Sham local potential framework (rather than the usual generalized Kohn-Sham treatment of mGGAs). A KEDF that has been rather successful in solid simulations proves to be inadequate for deorbitalization but we produce other forms which, with parametrization to Kohn-Sham results (not experimental data) on a small training set, yield rather good results on standard molecular test sets when used to deorbitalize the meta-GGA made very simple, TPSS, and SCAN functionals. We also study the difference between high-fidelity and best-performing deorbitalizations and discuss possible implications for use in ab initio molecular dynamics simulations of complicated condensed phase systems.

Coupled electron-ion Monte Carlo simulation of hydrogen molecular crystals.

We performed simulations for solid molecular hydrogen at high pressures (250 GPa ≤ P ≤ 500 GPa) along two isotherms at T = 200 K (phase III) and at T = 414 K (phase IV). At T = 200 K, we considered likely candidates for phase III, the C2c and Cmca12 structures, while at T = 414 K in phase IV, we studied the Pc48 structure. We employed both Coupled Electron-Ion Monte Carlo (CEIMC) and Path Integral Molecular Dynamics (PIMD). The latter is based on Density Functional Theory (DFT) with the van der Waals approximation (vdW-DF). The comparison between the two methods allows us to address the question of the accuracy of the exchange-correlation approximation of DFT for thermal and quantum protons without recurring to perturbation theories. In general, we find that atomic and molecular fluctuations in PIMD are larger than in CEIMC which suggests that the potential energy surface from vdW-DF is less structured than the one from quantum Monte Carlo. We find qualitatively different behaviors for systems prepared in the C2c structure for increasing pressure. Within PIMD, the C2c structure is dynamically partially stable for P ≤ 250 GPa only: it retains the symmetry of the molecular centers but not the molecular orientation; at intermediate pressures, it develops layered structures like Pbcn or Ibam and transforms to the metallic Cmca-4 structure at P ≥ 450 GPa. Instead, within CEIMC, the C2c structure is found to be dynamically stable at least up to 450 GPa; at increasing pressure, the molecular bond length increases and the nuclear correlation decreases. For the other two structures, the two methods are in qualitative agreement although quantitative differences remain. We discuss various structural properties and the electrical conductivity. We find that these structures become conducting around 350 GPa but the metallic Drude-like behavior is reached only at around 500 GPa, consistent with recent experimental claims.

Automation methodologies and large-scale validation for GW : Towards high-throughput GW calculations

The search for new materials, based on computational screening, relies on methods that accurately predict, in an automatic manner, total energy, atomic-scale geometries, and other fundamental characteristics of materials. Many technologically important material properties directly stem from the electronic structure of a material, but the usual workhorse for total energies, namely density-functional theory, is plagued by fundamental shortcomings and errors from approximate exchange-correlation functionals in its prediction of the electronic structure. At variance, the $GW$ method is currently the state-of-the-art {\em ab initio} approach for accurate electronic structure. It is mostly used to perturbatively correct density-functional theory results, but is however computationally demanding and also requires expert knowledge to give accurate results. Accordingly, it is not presently used in high-throughput screening: fully automatized algorithms for setting up the calculations and determining convergence are lacking. In this work we develop such a method and, as a first application, use it to validate the accuracy of $G_0W_0$ using the PBE starting point, and the Godby-Needs plasmon pole model ($G_0W_0^\textrm{GN}$@PBE), on a set of about 80 solids. The results of the automatic convergence study utilized provides valuable insights. Indeed, we find correlations between computational parameters that can be used to further improve the automatization of $GW$ calculations. Moreover, we find that $G_0W_0^\textrm{GN}$@PBE shows a correlation between the PBE and the $G_0W_0^\textrm{GN}$@PBE gaps that is much stronger than that between $GW$ and experimental gaps. However, the $G_0W_0^\textrm{GN}$@PBE gaps still describe the experimental gaps more accurately than a linear model based on the PBE gaps.

Examining real-time time-dependent density functional theory nonequilibrium simulations for the calculation of electronic stopping power

In ion irradiation processes, electronic stopping power describes the energy transfer rate from the irradiating ion to the target material's electrons. Due to the scarcity and significant uncertainties in experimental electronic stopping power data for materials beyond simple solids, there has been growing interest in the use of first-principles theory for calculating electronic stopping power. In recent years, advances in high-performance computing have opened the door to fully first-principles nonequilibrium simulations based on real-time time-dependent density functional theory (RT-TDDFT). While it has been demonstrated that the RT-TDDFT approach is capable of predicting electronic stopping power for a wide range of condensed matter systems, there has yet to be an exhaustive examination of the physical and numerical approximations involved and their effects on the calculated stopping power. We discuss the results of such a study for crystalline silicon with protons as irradiating ions. We examine the influences of key approximations in RT-TDDFT nonequilibrium simulations on the calculated electronic stopping power, including approximations related to basis sets, finite size effects, exchange-correlation approximation, pseudopotentials, and more. Finally, we propose a simple and efficient correction scheme to account for the contribution from core-electron excitations to the stopping power, as it was found to be significant for large proton velocities.

Crystal and Electronic Structures of MgCo2-XMnxO4 As Cathode Material for Magnesium Secondary Battery Using First Principle Calculation and Quantum Beam

Introduction Recent years have witnessed growing hopes that lithium-ion secondary batteries will find applications in large-scale devices, creating demand for further increases in energy density and output density. Magnesium ion is divalent ion and has the nearly ionic radius as lithium ion. Then, magnesium secondary battery expects as a next generation battery material due to high energy density than that of lithium ion. MgCo2O4, one of magnesium ion cathode material, is synthesized and examined the battery characteristic property1). Although, the other oxide cathode materials are admitted to investigate the suitable structure with diffusion pathway of Mg ion. The purpose of the present study was to evaluate the electrochemical property, to analysis the crystal and electronic structures for a magnesium cathode material, spinel system of MgCo2-xMnxO4, using the first principle calculation and quantum beam. Experimental and first principle calculation The spinel type of MgCo2-xMnxO4 samples were synthesized by reverse co-precipitation method1). The obtained sample of metallic components was determined using ICP and of charge and discharge test (a two-electrode flat cell (HS cell) : 3.5 - 0V vs. Mg/Mg2+, three electrode cell : 0.345 ~ -1.155V vs. Ag/Ag+, electrolyte : 0.5M-Mg(N(SO2CF3)2)2/CH3CN or Triglyme) was performed. Rietveld analysis is performed by synchrotron X-ray diffraction (BL19B2, Spring-8) and neutron diffraction (iMATERIA, J-PARC) data. The determination of valence of Co and Mn atom is analyzed using synchrotron X-ray absorption spectroscopy (BL01B1, Spring-8). The structural relaxation calculation was performed by generalized gradient approximation (GGA-PBE) exchange-correlation potential used with a plane-wave cutoff energy of 500 eV, and a (1×1×1) k-point mesh was sampled, corresponding to the inverses of the lattice constants on Vienna Ab-initioSimulation Package (VASP) code. The convergence criterion for structural optimization was that the energy difference per iteration be less than or equal to 0.02 eV/Å. Initial structure that is a 1×1×1 cell was created and structural relaxation was performed on various initial structural models to determine the energetically optimal structure. Initial structure models were constructed to ensure reproduction of the occupancies determined by an average structure analysis from Rietveld analysis using synchrotron X-ray diffraction. Results and discussion From the measurement of XRD pattern of MgCo2-xMnxO4, all of diffraction peak could be assigned to space group Fd3(-)m. The calculated stable structure of MgCo2O4 and MgCo1.5Mn0.5O4 which space group is Fd3(-)m and cell size is a 1×1×1 cell are shown in figure 1 a) and b), respectively. From Figure 1 a), Mg atoms exist only 8a site and Co atoms exist only 16d site in stable structure of MgCo2O4. It is found that the cation mixing is not occurred and the diffraction pathway of Mg is formed in MgCo2O4. From figure 1 b), Mg atoms posit only 8a site and Co and Mn atoms posit only 16d site in Mn replaced material, MgCo1.5Mn0.5O4. Also, from the result of Rietveld analysis using synchrotron X-ray diffraction, the occupancy of 16d site of Mn atom become large with increasing the amount of Mn. The result of first principle calculation is in agreement with Rietveld analysis using synchrotron X-ray diffraction. In the calculated stable structure of MgCo1.5Mn0.5O4, the diffraction pathway of Mg and Mn atoms layer are formed. Next, the distortion parameter of M-O6 (M=Co, Mn) and Mg-O4 polyhedral are calculated in stable structure of MgCo2O4 and MgCo1.5Mn0.5O4. From the charge and discharge profile using three electrode cell, it is formed that the first discharge capacity of MgCo1.5Mn0.5O4 is lower than MgCo2O4 at 60oC. On the other hands, the cycle performance of MgCo1.5Mn0.5O4 is improved than MgCo2O4. The averaged bond length of Mg-O for MgCo1.5Mn0.5O4 is little shorter than that of MgCo2O4. Therefore, the interaction between Mg and O atom in MgCo1.5Mn0.5O4 may be slightly stronger than MgCo2O4, and Mg ion is difficult to detach and insert in crystal. Accordingly, the first discharge capacity of MgCo1.5Mn0.5O4 is lower. On the other hands, the distortion parameter of Mg-O4 and Co-O4 polyhedral in MgCo1.5Mn0.5O4 becomes larger than that in MgCo2O4. In other words, the strength of Mg-O bond and Co-O bond are localized by the influence of Mn. With increasing the charge and discharge cycle, Mg ion might be easy to detach and insert from weakly interaction between Mg and O. In this presentation, the bond valence sum, the electron density, the structural stability with Mg detachment and insertion and the analysis of electronic structure will be discussed. Acknowledgement This work was supported in part by ALCA-SPRING, Japan. We are deeply grateful for the cooperation. 1) S. Yagi et al., Jpn. J. Appl. Phys., 52, 025501 (2013). Figure 1

Site preference, structural and magnetic properties of La3Co29−xNixSi4B10 predicted by first-principles calculations

Adopting the first-principles calculations based on the density functional theory (DFT) with the generalized gradient approximation (GGA) exchange-correlation functional, which are organized in a high-throughput workflow, the structural properties, site preference and magnetic properties of compounds La3Co29−xNixSi4B10 in tetragonal crystal system are studied. To cross check our results, the calculated lattice parameters of the undoped La3Co29Si4B10 and the mean magnetic moment of its Co atoms are in consistence with existing experimental results. The interatomic distances and local environments of each Co (Ni) site are investigated. The calculated results show that Ni atoms prefer to substitute the Co atoms on the 8i3 site, based on the cohesive energy analysis. Furthermore, the total magnetic moment and electronic density of states of La3Co29−xNixSi4B10 are calculated with varying number of Co substituted by Ni. In addition, the charge density distribution of La3Co29−xNixSi4B10 indicates that an ionic bond are formed between Co/Ni and B.

Ab initio study of the lattice thermal conductivity of Cu2O using the generalized gradient approximation and hybrid density functional methods

Lattice thermal conductivity of Cu$_2$O was studied using ab initio density functional methods. The performance of generalized gradient approximation, GGA-PBE, and PBE0 exchange-correlation functionals was compared for various electronic and phonon-related properties. 3d transition metal oxides such as Cu$_2$O are known to be a challenging case for pure GGA functionals and in comparison to GGA-PBE the PBE0 hybrid functional clearly improves the description of both electronic and phonon-related properties. The most striking difference is found in the lattice thermal conductivity, where GGA underestimates it as much as 40% in comparison to experiment, while the difference between the experiment and the PBE0 hybrid functional is only a few percent.

Why are GGAs so accurate for reaction kinetics on surfaces? Systematic comparison of hybrid vs. nonhybrid DFT for representative reactions.

"Jacob's Ladder" of approximate exchange-correlation (XC) functionals in Kohn-Sham density functional theory are widely accepted to have systematic errors in reaction barriers. The first-rung local spin-density approximation (LDA) typically predicts barriers below generalized gradient approximations, which in turn predict barriers below experiment and below fourth-rung hybrid functionals incorporating a fraction of exact exchange. We show that several reactions from previous literature reports, as well as new simulations of carbon-carbon coupling in the Fischer-Tropsch process, do not follow this conventional picture. We introduce the AB9 test set of nine abnormal reaction barriers, in which density gradient corrections and exact exchange admixture tend to lower rather than to raise predicted barriers. Comparisons of normal and abnormal reactions rationalize this phenomenon in terms of how density gradient and exact-exchange corrections stabilize transition states relative to reaction intermediates. Multireference diagnostics confirm that this behavior is not merely a consequence of multireference character. Benchmarks of the AB9 set, using the best available ab initio reference values, highlight the role of symmetry breaking and show surprisingly good performance from both the LDA and "Rung 3.5" functionals. This motivates benchmarks of the AB9 set in future XC functional development.

Plane-wave pseudopotential implementation and performance of SCAN meta-GGA exchange-correlation functional for extended systems

We present the implementation and performance of the strongly constrained and appropriately normed, SCAN, meta-GGA exchange-correlation (XC) approximation in the planewave-pseudopotential (PW-PP) formalism using the Troullier-Martins pseudopotential scheme. We studied its performance by applying the PW-PP implementation to several practical applications of interest in condensed matter sciences: (a) crystalline silicon and germanium, (b) martensitic phase transition energetics of phosphorene, and (c) a single water molecule physisorption on a graphene sheet. Given the much-improved accuracy over the GGA functionals and its relatively low computational cost compared to hybrid XC functionals, the SCAN functional is highly promising for various practical applications of density functional theory calculations for condensed matter systems. At same time, the SCAN meta-GGA functional appears to require more careful attention to numerical details. The meta-GGA functional shows more significant dependence on the fast Fourier transform grid, which is used for evaluating the XC potential in real space in the PW-PP formalism, than other more conventional GGA functionals do. Additionally, using pseudopotentials that are generated at a different/lower level of XC approximation could introduce noticeable errors in calculating some properties such as phase transition energetics.

Dispersion-Corrected Spin-Component-Scaled Double-Hybrid Density Functional Theory: Implementation and Performance for Non-covalent Interactions.

The implementation of 300 combinations of generalized gradient approximation/local density approximation exchange-correlation dispersion-corrected spin-component-scaled double-hybrid (DSD) density functional theory (DFT) methods has been carried out and the performance assessed against several DFT and post-Hartree-Fock methods, enabling further advancements toward the long-standing challenge of accurate prediction of interaction energies and associated properties. The resulting framework is flexible and has been further extended to include the resolution of identity (RI) approximation for solving the critical four-center two-electron repulsion integrals in the basis of the Kohn-Sham orbitals for cost effectiveness. To evaluate the performance of this set of new cost-effective methods, denoted as RI-DSD-DFTs, seven validation data sets were designed to cover a broad range of non-covalent interactions with characteristic stabilizing contributions. Inclusion of the perturbative treatment of correlation effects is shown to significantly improve the description of weak interactions. The set of DSD-DFTs provide interaction energies with root-mean-square deviations and mean absolute errors within 0.5 kcal/mol. The cost-effective RI-DSD-DFT counterparts deviate by less than 0.18 kcal/mol on average with only 2% of the computational cost.

An assessment of low-lying excitation energies and triplet instabilities of organic molecules with an ab initio Bethe-Salpeter equation approach and the Tamm-Dancoff approximation.

The accurate prediction of singlet and triplet excitation energies is an area of intense research of significant fundamental interest and critical for many applications. Most calculations of singlet and triplet energies use time-dependent density functional theory (TDDFT) in conjunction with an approximate exchange-correlation functional. In this work, we examine and critically assess an alternative method for predicting low-lying neutral excitations with similar computational cost, the ab initio Bethe-Salpeter equation (BSE) approach, and compare results against high-accuracy wavefunction-based methods. We consider singlet and triplet excitations of 27 prototypical organic molecules, including members of Thiel's set, the acene series, and several aromatic hydrocarbons exhibiting charge-transfer-like excitations. Analogous to its impact in TDDFT, we find that the Tamm-Dancoff approximation (TDA) overcomes triplet instabilities in the BSE approach, improving both triplet and singlet energetics relative to higher level theories. Finally, we find that BSE-TDA calculations built on effective DFT starting points, such as those utilizing optimally tuned range-separated hybrid functionals, can yield accurate singlet and triplet excitation energies for gas-phase organic molecules.

Is the Accuracy of Density Functional Theory for Atomization Energies and Densities in Bonding Regions Correlated?

The development of approximate exchange-correlation functionals is critical for modern density functional theory. A recent analysis of atomic systems suggested that some modern functionals are straying from the path toward the exact functional because electron densities are becoming less accurate while energies are becoming more accurate since the year 2000. To investigate this trend for more chemically relevant systems, the electron densities in the bonding regions and the atomization energies are analyzed for a series of diatomic molecules with 90 different functionals. For hybrid generalized gradient approximation functionals developed since the year 2000, the errors in densities and atomization energies are decoupled; the accuracy of the energies remains relatively consistent while the accuracy of the densities varies significantly. Such decoupling is not observed for generalized gradient and meta-generalized gradient approximation functionals. Analysis of electron densities in bonding regions is found to be important for the evaluation of functionals for chemical systems.

Examining the Effect of Exchange-Correlation Approximations in First-Principles Dynamics Simulation of Interfacial Charge Transfer.

We examine the extent to which the exchange-correlation (XC) approximation influences modeling interfacial charge transfer using fewest-switches surface hopping (FSSH) simulations within the single-particle description. A heterogeneous interface between a lithium ion and an extended boron-nitride sheet was considered here, being an extreme case in which wave function localization and energy level alignments are highly sensitive to the XC approximation. The PBE0 hybrid XC approximation yields nonadiabatic couplings (NACs) that are significantly smaller than the values obtained from the PBE-GGA approximation by an order of magnitude for localized electronic states. This difference between the two XC functionals for the calculated NACs was found to derive mainly from the wave function characteristics rather than from the lattice movement although first-principles molecular dynamics trajectories, along which NACs are obtained, differ noticeably between the two XC functionals. Using the NACs and single-particle energy level alignments at different levels of theory, FSSH simulations were performed to model the electron transfer dynamics at the interface. The electron transfer time scale was found to vary as much as, but not more than, 1 order of magnitude. The time scale was found to be quite sensitive to both NACs and energy level alignments. While the order of magnitude consistency for the charge transfer rate is encouraging even for this rather extreme model of heterojunction interface, continued advancement in electronic structure methods is required for quantitatively accurate determination of the transfer rate.