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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Mild-Temperature Supercritical Water Confined in Hydrophobic Metal–Organic Frameworks

Fluids under extreme confinement show characteristics significantly different from those of their bulk counterpart. This work focuses on water confined within the complex cavities of highly hydrophobic metal–organic frameworks (MOFs) at high pressures. A combination of high-pressure intrusion–extrusion experiments with molecular dynamic simulations and synchrotron data reveals that supercritical transition for MOF-confined water takes place at a much lower temperature than in bulk water, ~250 K below the reference values. This large shifting of the critical temperature (T c ) is attributed to the very large density of confined water vapor in the peculiar geometry and chemistry of the cavities of Cu 2 tebpz (tebpz = 3,3',5,5'-tetraethyl-4,4'-bipyrazolate) hydrophobic MOF. This is the first time the shift of Tc is investigated for water confined within highly hydrophobic nanoporous materials, which explains why such a large reduction of the critical temperature was never reported before, neither experimentally nor computationally.

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

Elevating density functional theory to chemical accuracy for water simulations through a density-corrected many-body formalism

Abstract Density functional theory (DFT) has been extensively used to model the properties of water. Albeit maintaining a good balance between accuracy and efficiency, no density functional has so far achieved the degree of accuracy necessary to correctly predict the properties of water across the entire phase diagram. Here, we present density-corrected SCAN (DC-SCAN) calculations for water which, minimizing density-driven errors, elevate the accuracy of the SCAN functional to that of “gold standard” coupled-cluster theory. Building upon the accuracy of DC-SCAN within a many-body formalism, we introduce a data-driven many-body potential energy function, MB-SCAN(DC), that quantitatively reproduces coupled cluster reference values for interaction, binding, and individual many-body energies of water clusters. Importantly, molecular dynamics simulations carried out with MB-SCAN(DC) also reproduce the properties of liquid water, which thus demonstrates that MB-SCAN(DC) is effectively the first DFT-based model that correctly describes water from the gas to the liquid phase.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Bridging the gap between molecules and materials in quantum chemistry with localized active spaces

The number of materials that “bridge the gap” between single molecules and extended solids, such as metal-organic frameworks and organic semiconductors, has been increasing. Consequently, there is a growing need for modeling approaches that effectively integrate the real-space molecular perspective employed by computational chemists and the reciprocal-space dispersive perspective employed by computational physicists. Here, we propose the localized active space (LAS) approach as a promising method to successfully bridge this gap. The LAS approach extends the active space concept from multiconfigurational methods such as complete active space self-consistent field theory to multiple molecular fragments via a product-form wave function ansatz. Here, we apply this method to solid state phenomena by treating each unit cell as a fragment with different sets of local quantum numbers (e.g., charge and excitation number). State interaction between these LAS states (LASSI) thus provides a comprehensive basis for the study of charge and energy transfer, meeting and surpassing the capabilities of single-reference fragmentation approaches such as constrained density functional theory (cDFT). Most centrally, we show how combining this LASSI approach with multiconfigurational pair-density functional theory (MC-PDFT) provides an elegant and efficient method to compute band structures that capture multiconfigurational character. We apply the LASSI band structure approach to the computation of band gaps in stretched hydrogen chain, polyacetylene, and bulk nickel oxide (NiO), finding good or excellent quantitative agreement with reference values in all cases. Additionally, we use the LAS basis in one-dimensional model systems to demonstrate its ability to treat difficult solid-state phenomena such as exciton transfer and excitation at p-n junctions.

method development↗
DOE OSTI2022

Analysis of solid uranium particulates on cotton swipes with an automated microextraction-ICP-MS system

Here, an automated microextraction method coupled to an inductively coupled plasma – mass spectrometer (ICP-MS) was developed for the direct analysis of solid uranium particulates on the surface of cotton swipes. The microextraction probe extracts particulates from the sample surface, in a flowing solvent, and directs the removed analyte to an ICP-MS for isotopic determination. The automated system utilizes a mechanical XY stage that is software controlled with the capability of saving and returning to specific locations and a camera focused to the swipe surface for optimal viewing of the extracted locations (i.e., material present). Here, particulates (n = 135) were extracted and measured by ICP-MS, including 35 depleted uranyl nitrate hexahydrate (UN) (used for mass bias corrections), 50 uranyl fluoride (UO 2 F 2 ), and 50 uranyl acetate (UAc) particulates. Blank extractions were performed on the cotton swipes between triplicate sample analyses. Between each swipe extraction, the probe was sent between two wells containing 10% and 5% HNO 3 to clean the probe head and to eliminate any analyte carryover between particulates. The measured 235 U/ 238 U and 234 U/ 238 U isotope ratios for the UO 2 F 2 particulates were 0.00725(8) and 0.000054(4), a percent relative difference (% RD) of –0.041% and –1.7% from the reference isotope ratios determined in-lab through multi-collector ICP-MS analysis of dissolved aliquots of the U material. The UAc samples had a measured 235 U/ 238 U isotope ratio of 0.00206(7), a –0.96% relative difference from the reference value of 0.00208(1). The 234 U/ 238 U and 236 U/ 238 U isotope ratios were 0.000008(1) and 0.000031(4), –5.1% RD and –4.3% RD, respectively. The automated sample stage enabled seamless and rapid particle analysis, leading to a significant increase in throughput versus what was previously possible. Additionally, the saved location capability reduced user sampling error as sampling locations were easily stored and recalled. Analysis of U particles on the swipe surface – including blanks, mass bias, and triplicate extractions – was completed in less than an hour without any sample preparation necessary.

47 OTHER INSTRUMENTATION↗
DOE OSTI2024

Normative Ranges for Oculomotor and Reaction Time Tests in U.S. Military Service Members and Veterans

AbstractBackground Oculomotor and reaction time tests are frequently used assessments of vestibular symptoms, traumatic brain injury (TBI), or other neurological disorders in both clinical and research contexts. When interpreting these tests it is important to have a reference interval (RI) as a comparison for what constitutes a typical/expected response; however, the current body of research has only limited information regarding normative ranges calculated according to established standards or for a military-specific sample.Purpose The purpose of the present study was to describe RIs for oculomotor and reaction time tests in a cohort of service members and veterans (SMVs) for use as comparators by clinicians and scientists.Research Design Descriptive.Study Sample Participants were prospectively enrolled in the Defense and Veterans Brain Injury Center-Traumatic Brain Injury Center of Excellence 15-year Longitudinal Traumatic Brain Injury Study. Only SMVs without a history of TBI or blast exposure were included in the RI calculations.Data Collection and Analysis The test paradigms included in this analysis were: smooth pursuit, prosaccades, antisaccades, saccades and reaction time, predictive saccades, optokinetic nystagmus, auditory reaction time, and visual reaction time. Nonparametric methods, based on the U.S. Food and Drug Administration's recognized consensus standards, were used to calculate 95% RIs. A comparison between the calculated RIs and those available from previously published research is provided.Results Summary statistics and RIs were calculated for 47 outcome parameters from 13 oculomotor and reaction time tests. Sample sizes and age ranges varied across outcome parameters depending on the availability of reference values for RI calculations. The sample sizes used to calculate RIs ranged from 51 to 69. The age of SMVs included in each RI ranged from 19 to 61 years with mean ages ranging from 37 to 39 years. Similarities/differences between the RIs in the present study and those in previously published research are highly dependent on the outcome parameter; however, in general, the RIs in the present study tended to be somewhat wider.Conclusion The RIs provided in this paper can serve as comparisons for clinicians and scientists who are utilizing these oculomotor and reaction time testing paradigms in similar cohorts of patients or research participants.

Audiology & Speech-Language Pathology↗
DOE OSTI2019

Characterization and Engineering Properties of Dry and Ponded Class-F Fly Ash

Characterization studies conducted on Class-F fly-ash specimens gathered from different producers in the southeastern United States confirm general trends reported for fly ash worldwide. Further tests and detailed analyses explain the spread in specific gravity (interparticle porosity cenospheres), highlight the tendency to segregation and layering, and show marked ferromagnetism. Furthermore, data show that early diagenetic cementation—within days after wetting—hinders densification and produces a fabric that is prone to collapse. New procedures are particularly developed to diagnose and characterize early diagenesis, including (1) pH measurements as an indicator of diagenetic potential, (2) test protocols to assess early diagenesis using oedometer tests and shear-wave velocity, and (3) procedures to determine realizable unit weights as reference values for the analyses of contractive or dilative tendencies and instability. In the absence of early diagenetic cementation, dilative fly-ash behavior is expected in the upper ≈20 m under monotonic shear loading. Flow instability may follow the failure of the containment structure if the ponded ash is saturated and has experienced hindered densification.

36 MATERIALS SCIENCE↗
DOE OSTI2017

A low-cost approach to electronic excitation energies based on the driven similarity renormalization group

Here, we propose an economical state-specific approach to evaluate electronic excitation energies based on the driven similarity renormalization group truncated to second order (DSRG-PT2). Starting from a closed-shell Hartree–Fock wave function, a model space is constructed that includes all single or single and double excitations within a given set of active orbitals. The resulting VCIS-DSRG-PT2 and VCISD-DSRG-PT2 methods are introduced and benchmarked on a set of 28 organic molecules [M. Schreiber et al. , J. Chem. Phys. 128, 134110 (2008)]. Taking CC3 results as reference values, mean absolute deviations of 0.32 and 0.22 eV are observed for VCIS-DSRG-PT2 and VCISD-DSRG-PT2 excitation energies, respectively. Overall, VCIS-DSRG-PT2 yields results with accuracy comparable to those from time-dependent density functional theory using the B3LYP functional, while VCISD-DSRG-PT2 gives excitation energies comparable to those from equation-of-motion coupled cluster with singles and doubles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Reflectance determination of optical spectral emissivity of metal surfaces at ambient conditions

Optical pyrometry requires knowledge of both spectral radiance and spectral emissivity to accurately measure temperature. No reliable compendium of spectral emissivity data currently exists for common metals in the optical and near-infrared spectral regions where pyrometry is typically performed. In this paper, we measure the spectral reflectivity of numerous common metals, with known surface finishes, between 400 and 1100 nm. The measurements are carried out under ambient conditions, near 300 K at an atmospheric pressure of ~0.78 bar. We then calculate the emissivity as a function of the wavelength for each sample. We define and use the illumination and collection geometries most practical for applying these measurements to radiometric thermometry. We also examine the effect of surface finish upon the relative spectral emissivity of a given material and find qualitative guidelines for predicting the increase in emissivity with increasing surface roughness. Finally, these measurements can both improve the accuracy and precision of optical pyrometry and provide the necessary reference value for converting emerging diagnostic measurements of relative spectral emissivity under extreme dynamic conditions into absolute dynamic spectral emissivity.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Thermal conductivity of MoS 2 monolayers from molecular dynamics simulations

Quantification of lattice thermal conductivity of two-dimensional semiconductors like MoS 2 is necessary for the design of electronic and thermoelectric devices, but direct experimental measurements on free-standing samples is challenging. Molecular dynamics simulations, with appropriate corrections, can provide a reference value for thermal conductivity for these material systems. Here, we construct a new empirical forcefield of the Stillinger-Weber form, parameterized to phonon dispersion relations, lattice constants and elastic moduli and we use it to compute a material-intrinsic thermal conductivity of 38.1 W/m-K at room temperature and estimate a maximum thermal conductivity of 85.4 W/m-K at T = 200 K. We also identify that phonon scattering by the large isotopic mass distribution of Mo and S contributes a significant correction (>45%) to the thermal conductivity at low temperatures.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Enhancing the applicability of multicomponent time-dependent density functional theory

The multicomponent extension of time-dependent density functional theory (TDDFT) within the nuclear-electronic orbital (NEO) framework enables the calculation of both electronic and vibrational excitations simultaneously. In this NEO-TDDFT approach, all electrons and select nuclei, typically protons, are treated quantum mechanically on the same level. Herein, the dependence of the proton vibrational excitation energies on the nuclear and electronic basis sets is examined. Protonic basis sets that include f basis functions in conjunction with substantial electronic basis sets for the quantum hydrogen are found to produce accurate proton vibrational excitation energies that are mostly within ~30 cm -1 of reference values for the molecules studied. The NEO-TDDFT approach is shown to be effective for open-shell as well as closed-shell systems. Additionally, an approach for computing and visualizing the nuclear transition densities associated with the proton vibrational excitations is implemented. These nuclear transition densities are important for characterizing the proton vibrational excitations and determining the spatial orientations of the corresponding vibrational modes. These capabilities are essential for a variety of applications, including the incorporation of anharmonic effects into molecular vibrational frequency calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Explicitly correlated coupled cluster method for accurate treatment of open-shell molecules with hundreds of atoms

We present a near-linear scaling formulation of the explicitly correlated coupled-cluster singles and doubles with the perturbative triples method [CCSD(T)F12¯] for high-spin states of open-shell species. The approach is based on the conventional open-shell CCSD formalism [M. Saitow et al., J. Chem. Phys. 146, 164105 (2017)] utilizing the domain local pair-natural orbitals (DLPNO) framework. The use of spin-independent set of pair-natural orbitals ensures exact agreement with the closed-shell formalism reported previously, with only marginally impact on the cost (e.g., the open-shell formalism is only 1.5 times slower than the closed-shell counterpart for the C160H322 n-alkane, with the measured size complexity of ≈1.2). Evaluation of coupled-cluster energies near the complete-basis-set (CBS) limit for open-shell systems with more than 550 atoms and 5000 basis functions is feasible on a single multi-core computer in less than 3 days. The aug-cc-pVTZ DLPNO-CCSD(T)F12¯ contribution to the heat of formation for the 50 largest molecules among the 348 core combustion species benchmark set [J. Klippenstein et al., J. Phys. Chem. A 121, 6580–6602 (2017)] had root-mean-square deviation (RMSD) from the extrapolated CBS CCSD(T) reference values of 0.3 kcal/mol. For a more challenging set of 50 reactions involving small closed- and open-shell molecules [G. Knizia et al., J. Chem. Phys. 130, 054104 (2009)], the aug-cc-pVQ(+d)Z DLPNO-CCSD(T)F12¯ yielded a RMSD of ∼0.4 kcal/mol with respect to the CBS CCSD(T) estimate.

Kumar, Ashutosh (ORCID:0000000175896030)↗
DOE OSTI2021

Density-related properties from self-interaction corrected density functional theory calculations

The Perdew–Zunger self-interaction correction (PZ-SIC) removes unphysical electron self-interaction from calculations employing standard density functional approximations. Doing so improves many computed properties, bringing them into better agreement with experimental observations or with results from high-level quantum chemistry calculations. However, while PZ-SIC generally corrects in the right direction relative to the corresponding reference values, in many cases, it over-corrects. For this reason, scaled-down versions of PZ-SIC have been proposed and investigated. These approaches have mostly employed exterior scaling in which SIC correction terms are scaled in the same way at every point in space. Recently, a new local, or interior, scaling SIC method was proposed on non-empirical grounds to restore a property of the exact, but unknown, density functional that is broken in PZ-SIC. Here, the scaling at each point depends on the character of the charge density at that point. However, the local scaling can be done in various ways while still restoring the behavior of the exact functional. In this work, we compare and contrast the performance of various interior scaling approaches for addressing over-corrections of calculated molecular dipole moments and atomic polarizabilities and properties that reflect the nature of the electronic charge density.

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

Fermi–Löwdin orbital self-interaction correction of adsorption energies on transition metal ions

Density functional theory (DFT)-based descriptions of the adsorption of small molecules on transition metal ions are prone to self-interaction errors. Here, we show that such errors lead to a large over-estimation of adsorption energies of small molecules on Cu + , Zn + , Zn 2+ , and Mn + in local spin density approximation (LSDA) and Perdew, Burke, Ernzerhof (PBE) generalized gradient approximation calculations compared to reference values computed using the coupled-cluster with single, doubles, and perturbative triple excitations method. These errors are significantly reduced by removing self-interaction using the Perdew–Zunger self-interaction correction (PZ-SIC) in the Fermi–Löwdin Orbital (FLO) SIC framework. In the case of FLO-PBE, typical errors are reduced to less than 0.1 eV. Furthermore, analysis of the results using DFT energies evaluated on self-interaction-corrected densities [DFT(@FLO)] indicates that the density-driven contributions to the FLO-DFT adsorption energy corrections are roughly the same size in DFT = LSDA and PBE, but the total corrections due to removing self-interaction are larger in LSDA.

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

An optimally tuned range-separated hybrid starting point for ab initio GW plus Bethe–Salpeter equation calculations of molecules

The ab initio GW plus Bethe–Salpeter equation (GW-BSE, where G is the one particle Green's function and W is the screened Coulomb interaction) approach has emerged as a leading method for predicting excitations in both solids and molecules with a predictive power contingent upon several factors. Among these factors are the (1) generalized Kohn–Sham eigensystem used to construct the GW self-energy and to solve the BSE and (2) the efficacy and suitability of the Tamm–Dancoff approximation. Here, we present a detailed benchmark study of low-lying singlet excitations from a generalized Kohn–Sham (gKS) starting point based on an optimally tuned range-separated hybrid (OTRSH) functional. We show that the use of this gKS starting point with one-shot G0W0 and G0W0-BSE leads to the lowest mean absolute errors (MAEs) and mean signed errors (MSEs), with respect to high-accuracy reference values, demonstrated in the literature thus far for the ionization potentials of the GW100 benchmark set and for low-lying neutral excitations of Thiel’s set molecules in the gas phase, without the need for self-consistency. The MSEs and MAEs of one-shot G0W0-BSE@OTRSH excitation energies are comparable to or lower than those obtained with other functional starting points after self-consistency. Additionally, we compare these results with linear-response time-dependent density functional theory (TDDFT) calculations and find GW-BSE to be superior to TDDFT when calculations are based on the same exchange-correlation functional. This work demonstrates tuned range-separated hybrids used in combination with GW and GW-BSE can greatly suppress starting point dependence for molecules, leading to accuracy similar to that for higher-order wavefunction-based theories for molecules without the need for costlier iterations to self-consistency.

McKeon, Caroline A. (ORCID:0000000217373503)↗
DOE OSTI2023

An in-silico NMR laboratory for nuclear magnetic shieldings computed via finite fields: Exploring nucleus-specific renormalizations of MP2 and MP3

Here we developed and implemented a method-independent, fully numerical, finite difference approach to calculating nuclear magnetic resonance shieldings, using gauge-including atomic orbitals. The resulting capability can be used to explore non-standard methods, given only the energy as a function of finite-applied magnetic fields and nuclear spins. For example, standard second-order Møller-Plesset theory (MP2) has well-known efficacy for 1H and 13C shieldings and known limitations for other nuclei such as 15N and 17O. It is, therefore, interesting to seek methods that offer good accuracy for 15N and 17O shieldings without greatly increased compute costs, as well as exploring whether such methods can further improve 1H and 13C shieldings. Using a small molecule test set of 28 species, we assessed two alternatives: κ regularized MP2 (κ-MP2), which provides energy-dependent damping of large amplitudes, and MP2.X, which includes a variable fraction, X, of third-order correlation (MP3). The aug-cc-pVTZ basis was used, and coupled cluster with singles and doubles and perturbative triples [CCSD(T)] results were taken as reference values. Our κ-MP2 results reveal significant improvements over MP2 for 13C and 15N, with the optimal κ value being element-specific. κ-MP2 with κ = 2 offers a 30% rms error reduction over MP2. For 15N, κ-MP2 with κ = 1.1 provides a 90% error reduction vs MP2 and a 60% error reduction vs CCSD. On the other hand, MP2.X with a scaling factor of 0.6 outperformed CCSD for all heavy nuclei. These results can be understood as providing renormalization of doubles amplitudes to partially account for neglected triple and higher substitutions and offer promising opportunities for future applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Self-interaction error overbinds water clusters but cancels in structural energy differences

Here, we gauge the importance of self-interaction errors in density functional approximations (DFAs) for the case of water clusters. To this end, we used the Fermi–Löwdin orbital self-interaction correction method (FLOSIC) to calculate the binding energy of clusters of up to eight water molecules. Three representative DFAs of the local, generalized gradient, and metageneralized gradient families [i.e., local density approximation (LDA), Perdew–Burke–Ernzerhof (PBE), and strongly constrained and appropriately normed (SCAN)] were used. We find that the overbinding of the water clusters in these approximations is not a density-driven error. We show that, while removing self-interaction error does not alter the energetic ordering of the different water isomers with respect to the uncorrected DFAs, the resulting binding energies are corrected toward accurate reference values from higher-level calculations. In particular, self-interaction–corrected SCAN not only retains the correct energetic ordering for water hexamers but also reduces the mean error in the hexamer binding energies to less than 14 meV/ H 2 O from about 42 meV/ H 2 O for SCAN. By decomposing the total binding energy into many-body components, we find that large errors in the two-body interaction in SCAN are significantly reduced by self-interaction corrections. Higher-order many-body errors are small in both SCAN and self-interaction–corrected SCAN. These findings suggest that orbital-by-orbital removal of self-interaction combined with a proper DFA can lead to improved descriptions of water complexes.

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

Validation of Light Water Reactor Ex-Core Calculations with VERA

The Consortium for Advanced Simulation of Light Water Reactors (CASL) Virtual Environment for Reactor Applications (VERA) is a reactor simulation software. It offers unique capabilities by combining high-fidelity in-core radiation transport with temperature feedback by using MPACT (a deterministic neutron transport code) and COBRA-TF (a thermal-hydraulic code) with follow-on, fixed-source transport calculations using the Shift Monte Carlo code to calculate ex-core quantities of interest. In these coupled calculations, MPACT provides Shift with the fission source for follow-on ex-core calculations. These ex-core simulations can be set up to calculate detector responses, as well as the flux and fluence in ex-core regions of interest, such as the reactor pressure vessel, nozzle, and irradiated capsules. A Watts Bar Nuclear Plant Unit 1 (WBN1) ex-core model was developed, as described in this paper, and this model was used to perform coupon calculations. The results for the coupon flux calculations show close agreement with the reference values for cycle 1 produced by the two-dimensional Discrete Ordinates Transport (DORT) code and presented in a BWXT Services Inc. report. However, differences in the results (10%) seen in cycles 2 and 3 and the reasons for these differences are discussed in this paper. The VERA WBN1 model was also used to perform a vessel fluence calculation for cycle 1. Additionally, a collaboration between CASL and Duke Energy led to the first code-to-code validation of VERA for reactor ex-core applications that used a model for the Shearon Harris reactor. Results from this collaboration show excellent agreement between VERA and the Monte Carlo N-Particle Transport Code for the detector response calculations. The work performed under this collaboration is also detailed in this paper.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

Density functionals combined with van der Waals corrections for graphene adsorbed on layered materials

Standard density functionals like Perdew-Burke-Ernzerhof (PBE) or Strongly Constrained and Appropriately Normed (SCAN) need a correction to account for long-range van der Waals (vdW) interaction. The damped Zaremba-Kohn model (dZK) starts from a formula for the vdW interaction of a distant atom with a solid surface, both with known dielectric properties, damps this formula at short range, and then treats an adsorbed molecule or atomic layer as a collection of renormalized atoms. Here, we extend this model to graphene adsorbed on semiconducting layered materials [bulk graphite and hBN, and multilayer transition metal dichalcogenides (TMD)] by including the C 4 asymptotic term and multiple electrostatic image effects due to the two surfaces of the substrate slabs in the vdW calculations. The resulting SCAN-vdW-dZK and PBE-vdW-dZK give approximately the same results for the systems considered here, in agreement with available reference values. The predicted binding energies are roughly 25% lower than those from SCAN+rVV10 (revised Vydrov and Van Voorhis 2010), and ~15% lower than those from PBE+rVV10. Since SCAN+rVV10 usually overbinds, the predicted binding energies by SCAN-vdW-dZK and PBE-vdW-dZK are expected to be closer to the true values. The predicted equilibrium binding distances from SCAN-vdW-dZK and PBE-vdW-dZK are slightly larger (~ 0.1 Å) than those from SCAN+rVV10, and close to those from SCAN. The binding energy depends upon the number of substrate layers more strongly in vdW-dZK than in rVV10. The C 4 -term contributions can be 40% of the total vdW interactions, and the C 5 term contributes about 10%. The effects of images and the back surfaces of slabs can contribute about 4–10%. The vdW interaction energy power laws from the vdW-dZK model for graphene adsorbed on multilayer MoS 2 show slowly varying decay to the pairwise exponent –4 with increasing separation $\textit{D}$, very similar to those obtained from the random-phase approximation and renormalization group approaches by Ambrosetti et al. Both the PBE-vdW-dZK and SCAN-vdW-dZK give a greater increase in interlayer binding energy when the TMD substrate changes from monolayer to four-layer for the graphene/TMD adsorption systems. This is consistent with the relevant electron-energy-loss spectroscopy experimental results showing increased dielectric response from the substrate with increasing substrate layer number.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗