Performance Of Density Functional Theory Research Articles

Performance of density functional theory for calculating the electronic, static, and dynamic nonlinear optical properties of asymmetric (3E,5E)-3,5-dibenzylidene-piperidin-4-one derivatives

Performance of density functional theory for calculating the electronic, static, and dynamic nonlinear optical properties of asymmetric (3E,5E)-3,5-dibenzylidene-piperidin-4-one derivatives

Highly accurate CCSD(T) homolytic Al–H bond dissociation enthalpies – chemical insights and performance of density functional theory

We obtain gas-phase homolytic Al–H bond dissociation enthalpies (BDEs) at the CCSD(T)/CBS level for a set of neutral aluminium hydrides (which we refer to as the AlHBDE dataset). The Al–H BDEs in this dataset differ by as much as 79.2 kJ mol−1, with (H2B)2Al–H having the lowest BDE (288.1 kJ mol−1) and (H2N)2Al–H having the largest (367.3 kJ mol−1). These results show that substitution with at least one –AlH2 or –BH2 substituent exerts by far the greatest effect in modifying the Al–H BDEs compared with the BDE of monomeric H2Al–H (354.3 kJ mol−1). To facilitate quantum chemical investigations of large aluminium hydrides, for which the use of rigorous methods such as W2w may not be computationally feasible, we assess the performance of 53 density functional theory (DFT) functionals. We find that the performance of the DFT methods does not strictly improve along the rungs of Jacob’s Ladder. The best-performing methods from each rung of Jacob’s Ladder are (mean absolute deviations are given in parentheses): the GGA B97-D (6.9), the meta-GGA M06-L (2.3), the global hybrid-GGA SOGGA11-X (3.3), the range-separated hybrid-GGA CAM-B3LYP (2.1), the hybrid-meta-GGA ωB97M-V (2.5) and the double-hybrid methods mPW2-PLYP and B2GP-PLYP (4.1 kJ mol−1).

Improving the transferability of density functional theory predictions through correlation analysis: Structural and energetic properties of NiX alloys (X=C, Si, Ge, and Sn)

This work reports on the performance of density functional theory (DFT) for a series of single and binary systems, aiming for a quantitative description of $\mathrm{Ni}X$ ($X=\mathrm{C}$, Si, Ge, and Sn) alloys. Both semilocal GGA and a meta-GGA density functional, with and without dispersion corrections, are tested. We found in our study that no single functional simultaneously provides an accurate quantitative description of the investigated structural and energetic properties. However, the spread in computed DFT data could be rationalized in terms of the distribution of reduced density gradients and differences in the evolution of the exchange enhancement factors for different functionals. We demonstrate how to construct a regression model based on data from several density functionals that increases the predictivity of semilocal DFT. We foresee that the use of regression models (or extensions of it) can be valuable in the development of more accurate density functionals that in the future could provide a quantitative accuracy for complex multicomponent systems.

Preparation, Antimicrobial Activity and Docking Study of Vanadium Mixed Ligand Complexes Containing 4-Amino-5-hydrazinyl-4H-1,2,4-triazole-3-thiol and Aminophenol Derivatives

The synthesis of mixed-ligand complexes is considered an important strategy for developing new metal complexes of enhanced biological activity. This paper presents the synthesis, characterization, in vitro antimicrobial assessment, and theoretical molecular docking evaluation for synthesized oxidovanadium (V) complexes. The proposed structures of the synthesized compounds were proved using elemental and different spectroscopic analysis. The antimicrobial tests showed moderate activity of the compounds against the Gram-positive bacterial strains and the fungal yeast, whereas no activity was observed against the Gram-negative bacterial strains. The performance of density functional theory (DFT) was conducted to study the interaction mode of the targeted compounds with the biological system. Calculating the quantitative structure-activity relationship (QSPR) was performed depending on optimization geometries, frontier molecular orbitals (FMOs), and chemical reactivities for synthesized compounds. The molecular electrostatic potentials (MEPs) that were plotted link the interaction manner of synthesized compounds with the receptor. The molecular docking evaluation revealed that the examined compounds may possess potential antibacterial activity.

Elastic and thermodynamic properties of the major clinker phases of Portland cement: Insights from first principles calculations

Portland based cement is one of the most popular materials used in the civil and construction applications. Reliable computational methods to provide an insight into the underlying mechanics of the major phases of this material are of great interest for cement design. The present work investigated the performance of density functional theory (DFT) calculations using the PBE-D2 method to predict the mechanical, thermodynamic properties of four major phases namely Alite C3S, Belite C2S, tricalcium aluminate C3A and tetracalcium aluminoferrite C4AF. The calculated elastic properties were in a good agreement with available experimental data. In addition, a deeper insight into the electron density of state, spin-polarization, atomic charge, as well as free energy and entropy properties were also presented. Further development is necessary to improve the established DFT models for predicting the mechanical properties of the ferrite phase of Portland clinker.

Koopmans-compliant screened exchange potential with correct asymptotic behavior for semiconductors

The performance of density functional theory depends largely on the approximation applied for the exchange functional. We propose here a novel screened exchange potential for semiconductors, with parameters based on the physical properties of the underlying microscopic screening and obeying the requirements for proper asymptotic behavior. We demonstrate that this functional is Koopmans-compliant and reproduces a wide range of band gaps. We also show, that the only tunable parameter of the functional can be kept constant upon changing the cation or the anion isovalently, making the approach suitable for treating alloys.

Quantitative and qualitative performance of density functional theory rationalized by reduced density gradient distributions

We evaluate the qualitative and quantitative accuracy of various flavors of density functionals with and without accounting for dispersion corrections. Our test system is nickel in the form of bulk, surfaces, and nanoparticles for which we compute structural properties, bulk cohesive energies, surface energies, and work functions and compare to experimental data. We find that the inclusion of any dispersion, either by an a posteriori correction or by a self-consistent treatment by explicitly computing the nonlocal correlation contribution to the total energy, has a significant effect on the calculated properties and improves the quantitative comparison to experiments. Besides the quantitative agreement, we also investigate qualitative features by comparing Wulff shapes of metal nanoparticles as obtained using the different density functionals. We find that all tested functionals predict similar Wulff shapes for nickel nanoparticles but still have some small differences. These results show that the relative energies calculated using the semilocal GGA and meta-GGA functionals, with and without dispersion, are quite similar. Our findings can also be generalized to other systems when rationalized in terms of the computed reduced density gradients. We find that the distribution of reduced density gradients in a material is correlated to the steepness of the exchange enhancement factor and propose that this information can be used as a quantitative guide when it comes to picking the most appropriate density functional for specific target systems as well as when it comes to extrapolating DFT data to predict experiments.

Performance of density functional theory and orbital-optimised second-order perturbation theory methods for geometries and singlet–triplet state splittings of aryl-carbenes

Carbenes are challenging molecular species for quantum chemistry because of the energetic proximity of their singlet and triplet spin states and the sensitive dependence of spin-state energetics on the geometry of the carbene site. Here we use an extended set of aryl-carbenes to evaluate the performance of density functional theory (DFT) approximations as well as of wave function based perturbation theory approaches (orbital-optimised perturbation theory methods OO-MP2 and OO-SCS-MP2) against reference coupled cluster calculations with singles, doubles and perturbative triples conducted with the aid of the domain-based local pair natural orbitals approach, DLPNO-CCSD(T). In addition to the expected functional dependence, our results document a remarkable discordance in the performance of DFT methods in the sense that the functionals that yield the best geometries do not coincide with those that provide the best spin-state energetics. Analysis of the results allows us to propose a series of methods that are expected to perform reliably within certain confidence limits for the title systems. Additionally, methodological issues regarding the reference singlet–triplet gaps obtained by the DLPNO-CCSD(T) approach are discussed.

Расчет стандартных электродных потенциалов электрохимического восстановления ванадиевых соединений: подбор функционала плотности

A systematic benchmark study was performed for the first time to investigate the performance of density functional theory for calculation of reduction potentials of vanadium compounds. Six density functionals of different types were selected for testing: local OLYP and M06L, global hybrid O3LYP and B3LYP, as well as, meta-hybrid functionals TPSSh and M06. Local and hybrid functionals with a relatively high contribution of Hartree-Fock exchange showed unsatisfactory results. In particular, the widely used hybrid functional B3LYP for the transformation VIII→VII occurring in the vanadium redox flow battery yields a negative value of the standard potential instead of a positive one. Among the tested functionals the smallest deviation from the experimental data provides the meta-hybrid functional TPSSh with a 10% contribution of the Hartree-Fock exchange. The computational protocol to calculate redox potentials of vanadium compounds is suggested.

Limits of Coupled-Cluster Calculations for Non-Heme Iron Complexes.

In a large variety of studies, the coupled-cluster method with singles, doubles, and perturbative triples (CCSD(T)) is used as a reference for benchmarking the performance of density functional theory (DFT) functionals. In the case of open-shell species, this theory can be applied in different forms depending on the restricted or unrestricted treatment of spin. In this study, we show that these different approaches can produce results which deviate by ∼5 kcal/mol for different species on the potential energy surfaces. This was demonstrated for a simple model of the C-H activation carried out by non-heme iron enzymes. Assessing the limits of CCSD(T) prior to its use as a general benchmark tool is warranted. This was done using higher-order coupled-cluster calculations as well as multiconfigurational second-order perturbation theory (CASPT2), since iron-oxo species present some multireference character. Furthermore, we tested two different implementations of the local coupled-cluster method and compared them to the CCSD(T) results, showing that even though these novel approaches are promising, without further developments they appear not to be suitable for describing two-state reactivity of the system investigated in the current study. Additionally, we implemented and assessed the performance of the hotspot approach for the local unrestricted CCSD(T) scheme which aims at reducing the pair error for systems containing transition metals.

Computational DFT study on nickel symmetric bis(thiosemicarbazone) complexes: Electronic absorption and redox potentials

This work deals with the performance of density functional theory (DFT) for evaluating one-electron reduction potentials and UV–Vis spectra of nickel complexes containing symmetric bis(thiosemicarbazones). Nine DFT calculation methods in combination with the polarisable continuum solvation model (PCM) were applied to calculate one-electron redox potentials (Ecalc) of nickel complexes. The best predicted results were gained by B3PW91/6-311++G(2df,2p)//B3LYP/6-31+G(d) level of theory in DMF. The results revealed that the most important effective thermodynamic factor is the solvation factor. Although the contribution of the electron attachment (EA) energy is more than ΔΔsolvG° and ΔΔεgeom for NiL1, NiL2, NiL3, and NiL4, ΔΔsolvG° and ΔΔεgeom play important roles in redox potentials. The calculated reduction potentials reproduce the tendency in experimental data. The derived error was in the region of −0.342 to −0.051 V. Reduction potentials have correlation with the energy of the frontier molecular orbitals LUMO/HOMO. According to the Natural Population Analysis (NPA), the geometries of nickel complexes remain distorted square planar, after reduction.

Hydrogen Activation by Silica-Supported Metal Ion Catalysts: Catalytic Properties of Metals and Performance of DFT Functionals.

Single-site heterogeneous catalysts (SSHC) have received increasing attention due to their well-defined active sites and potentially high specific activity. Detailed computational studies were carried out on a set of potential SSHC's, i.e., silica-supported metal ions, to investigate the reactivity of these catalysts with H2 as well as to evaluate the performance of density functional theory (DFT) methods in conjunction with triple-ζ quality basis sets (i.e., cc-pVTZ) on reaction energetics. The ions considered include 4d and 5d metals as well as several post-transition metal ions. A representative cluster model of silica is used to calculate reaction free energies of the metal hydride formation that results from the heterolytic cleavage of H2 on the M-O bond. The hydride formation free energy is previously shown to be strongly correlated with the catalytic activity of such catalysts for alkene hydrogenation. ONIOM calculations (CCSD(T)//MP2) are used to assess the accuracy and reliability of the MP2 results and it is found that MP2 is a suitable level of theory for gauging the performance of DFT functionals. The performance of various DFT functionals is assessed relative to MP2 results and it is found that the wB97xd and PBE0 functionals have the lowest standard deviation (STD) value while the MN12SX and PBE functionals have the lowest mean absolute deviation (MAD) values. The B3LYP functional is shown to have similar MAD and STD values as the top performing functionals. Potential active SSHC's for exergonic hydrogen activation predicted in this study include mostly late and post transition metal ions, i.e., Au3+, Pd2+, Pt4+, Pd4+, Ir4+, Hg2+, Rh3+, Pb4+, Tl3+, In3+, Ir3+, Os4+, Cd2+, Ru2+, and Ga3+. This study provides important guidance to future computational studies of such catalyst systems.

Iron(II) and Iron(III) Spin Crossover: Toward an Optimal Density Functional.

Spin crossover (SCO) plays a major role in biochemistry, catalysis, materials, and emerging technologies such as molecular electronics and sensors, and thus accurate prediction and design of SCO systems is of high priority. However, the main tool for this purpose, density functional theory (DFT), is very sensitive to applied methodology. The most abundant SCO systems are Fe(II) and Fe(III) systems. Even with average good agreement, a functional may be significantly more accurate for Fe(II) or Fe(III) systems, preventing balanced study of SCO candidates of both types. The present work investigates DFT's performance for well-known Fe(II) and Fe(III) SCO complexes, using various design types and customized versions of GGA, hybrid, meta-GGA, meta-hybrid, double-hybrid, and long-range-corrected hybrid functionals. We explore the limits of DFT performance and identify proficient Fe(II)-Fe(III)-balanced functionals. We identify and quantify remarkable differences in the DFT description of Fe(II) and Fe(III) systems. Most functionals become more accurate once Hartree-Fock exchange is adjusted to 10-17%, regardless of the type of functionals involved. However, this typically introduces a clear Fe(II)-Fe(III) bias. The most accurate functionals measured by mean absolute errors <10 kJ/mol are CAMB3LYP-17, B3LYP*, and B97-15 with 15-17% Hartree-Fock exchange, closely followed by CAMB3LYP and CAMB3LYP-15, OPBE, rPBE-10, and B3P86-15. While GGA functionals display a small Fe(II)-Fe(III) bias, they are generally inaccurate, except the O exchange functional. Hybrid functionals (including B2PLYP double hybrids and meta hybrids) tend to favor HS too much in Fe(II) vs Fe(III), which is important in many studies where the oxidation state of iron can vary, e.g. rational SCO design and studies of catalytic processes involving iron. The only functional with a combined bias <5 kJ/mol and a decent MAE (15 kJ/mol) is our customized PBE0-12 functional. Alternatively one has to sacrifice Fe(II)-Fe(III) balance to use the best functionals for each group separately. We also investigated the precision (measured as the standard deviation of errors) and show that the target accuracy for iron SCO is 10 kJ/mol for accuracy and 5 kJ/mol for precision, and DFT is probably not going to break this limit in the near future. Importantly, all four types of functional behavior (accurate/precise, accurate/imprecise, inaccurate/precise, inaccurate/imprecise) are observed. More generally, our work illustrates the importance not only of overall accuracy but also of balanced accuracy for systems likely to occur in context.

Performance of Density Functional Theory for Predicting Methane-to-Methanol Conversion by a Tri-Copper Complex

Efficient, low-temperature, and catalytic methane-to-methanol conversion (MMC) is of great interest, as methanol can be used as a liquid fuel and is a value-adding intermediate in the petrochemical industry. MMC can be achieved through direct C–H activation or via oxidation in strongly acidic media using noble metal catalysts. However, these processes are expensive and generally have low selectivity for methanol. In contrast, copper-exchanged zeolites can facilitate methane oxidation stoichiometrically under mild conditions with high selectivities for methanol. Approaches for achieving catalytic MMC on copper-exchanged zeolites have recently been developed. A better understanding of this process is required in order to facilitate the design of more efficient catalysts. In this work, we benchmark the performance of density functional theory (DFT) for modeling the MMC pathway by a tri-copper complex, [Cu3O3(H2O)6]2+. This complex is reminiscent of [Cu3O3]2+ proposed as the active-site motif in the zeolite m...

Assessing the performance of the Tran–Blaha modified Becke–Johnson exchange potential for optical constants of semiconductors in the ultraviolet–visible light region

We report on the performance of density functional theory (DFT) with the Tran–Blaha modified Becke–Johnson exchange potential and the random phase approximation dielectric function for optical constants of semiconductors in the ultraviolet–visible (UV-Vis) light region. We calculate optical bandgaps Eg, refractive indices n, and extinction coefficients k of 70 semiconductors listed in the Handbook of Optical Constants of Solids [(Academic Press, 1985), Vol. 1; (Academic Press, 1991), Vol. 2; and (Academic Press, 1998), Vol. 3] and compare the results with experimental values. The results show that the calculated bandgaps and optical constants agree well with the experimental values to within 0.440 eV for Eg, 0.246–0.299 for n, and 0.207–0.598 for k in root mean squared error (RMSE). The small values of the RMSEs indicate that the optical constants of semiconductors in the UV-Vis region can be quantitatively predicted even by a low-cost DFT calculation of this type.

The performance of density functional theory for the description of ground and excited state properties of inorganic and organometallic uranium compounds

Molecular uranium complexes are the most widely studied in actinide chemistry, and make a significant and growing contribution to inorganic and organometallic chemistry. However, reliable computational procedures to accurately describe the properties of such systems are not yet available. In this contribution, 18 experimentally characterized molecular uranium compounds, in oxidation states ranging from III to VI and with a variety of ligand environments, are studied computationally using density functional theory. The computed geometries and vibrational frequencies are compared with X-ray crystallographic, and infra-red and Raman spectroscopic data to establish which computational approach yields the closest agreement with experiment. NMR parameters and UV–vis spectra are studied for three and five closed-shell U(VI) compounds respectively. Overall, the most robust methodology for obtaining accurate geometries is the PBE functional with Grimme's D3 dispersion corrections. For IR spectra, different approaches yield almost identical results, which makes the PBE functional with Grimme's D3 dispersion corrections the best choice. However, for Raman spectra the dependence on functional is more pronounced and no clear recommendation can be made. Similarly, for 1H and 13C NMR chemical shifts, no unequivocal recommendation emerges as to the best choice of density functional, although for spin-spin couplings, the LC-ωPBE functional with solvent corrections is the best approach. No form of time-dependent density functional theory can be recommended for the simulation of the electronic absorption spectra of uranyl (VI) compounds; the orbitals involved in the transitions are not calculated correctly, and the energies are also typically unreliable. Two main approaches are adopted for the description of relativistic effects on the uranium centres: either a relativistic pseudopotential and associated valence basis set, or an all-electron basis set with the ZORA Hamiltonian. The former provides equal, if not better, agreement with experiment vs all-electron basis set calculations, for all properties investigated.

Bias-Free Chemically Diverse Test Sets from Machine Learning.

Current benchmarking methods in quantum chemistry rely on databases that are built using a chemist's intuition. It is not fully understood how diverse or representative these databases truly are. Multivariate statistical techniques like archetypal analysis and K-means clustering have previously been used to summarize large sets of nanoparticles however molecules are more diverse and not as easily characterized by descriptors. In this work, we compare three sets of descriptors based on the one-, two-, and three-dimensional structure of a molecule. Using data from the NIST Computational Chemistry Comparison and Benchmark Database and machine learning techniques, we demonstrate the functional relationship between these structural descriptors and the electronic energy of molecules. Archetypes and prototypes found with topological or Coulomb matrix descriptors can be used to identify smaller, statistically significant test sets that better capture the diversity of chemical space. We apply this same method to find a diverse subset of organic molecules to demonstrate how the methods can easily be reapplied to individual research projects. Finally, we use our bias-free test sets to assess the performance of density functional theory and quantum Monte Carlo methods.

Benchmark coupled-cluster g-tensor calculations with full inclusion of the two-particle spin-orbit contributions.

We present a parallel implementation to compute electron spin resonance g-tensors at the coupled-cluster singles and doubles (CCSD) level which employs the ACES III domain-specific software tools for scalable parallel programming, i.e., the super instruction architecture language and processor (SIAL and SIP), respectively. A unique feature of the present implementation is the exact (not approximated) inclusion of the five one- and two-particle contributions to the g-tensor [i.e., the mass correction, one- and two-particle paramagnetic spin-orbit, and one- and two-particle diamagnetic spin-orbit terms]. Like in a previous implementation with effective one-electron operators [J. Gauss et al., J. Phys. Chem. A 113, 11541-11549 (2009)], our implementation utilizes analytic CC second derivatives and, therefore, classifies as a true CC linear-response treatment. Therefore, our implementation can unambiguously appraise the accuracy of less costly effective one-particle schemes and provide a rationale for their widespread use. We have considered a large selection of radicals used previously for benchmarking purposes including those studied in earlier work and conclude that at the CCSD level, the effective one-particle scheme satisfactorily captures the two-particle effects less costly than the rigorous two-particle scheme. With respect to the performance of density functional theory (DFT), we note that results obtained with the B3LYP functional exhibit the best agreement with our CCSD results. However, in general, the CCSD results agree better with the experimental data than the best DFT/B3LYP results, although in most cases within the rather large experimental error bars.

Towards Reliable Modeling of Challengingf Electrons Bearing Materials: Experience from Modeling of Nuclear Materials

ABSTRACTBecause of steady increase in the availability of computing power, ab initio methods of computational materials science become everyday investigation tools in various research fields. This popularity of the first-principle-based atomistic modeling is in large part due to the performance of density functional theory (DFT), which could be used for simulations of chemically and structurally complex materials, including minerals, fluids and melts. However, because of intrinsic approximations, DFT is not always able to deliver reliable predictions. This is especially pronounced for f-elements bearing materials such as nuclear materials considered in nuclear waste management. Properties such as reaction enthalpies or electronic state are often badly predicted. In this contribution we discuss our experience with different computational methods, including the parameter free DFT+U method, in which the Hubbard U parameter is derived ab initio, for prediction of various properties of f electrons bearing materials. We show significant improvement obtained for structural and thermochemical parameters of various lanthanide-bearing ceramic materials and actinide-bearing molecular and solid compounds when the f electrons correlations are explicitly accounted for. Last, but not least, we demonstrate that complementary experimental and atomistic modeling studies result in superior and more complete characterization of challenging materials considered in nuclear waste management.

Performance of Density Functional Theory and Relativistic Effective Core Potential for Ru-Based Organometallic Complexes.

Herein a performance assessment of density functionals used for calculating the structural and energetic parameters of bi- and trimetallic Ru-containing organometallic complexes has been performed. The performance of four popular relativistic effective core potentials (RECPs) has also been assessed. On the basis of the calculated results, the MN12-SX (range-separated hybrid functional) demonstrates good performance for calculating the molecular structures, while MN12-L (local functional) performs well for calculating the energetics, including that of the Ru-Ru bond breaking process. The choice of appropriate density functional is a crucial factor for calculating the energetics. The LANL08 demonstrates the lowest performance of the RECPs for calculating the molecular structures, especially the Ru-Ru bond length.