Effect of surface species on the alcohol-acid adsorption from FTS wastewater on graphene: A structure-capacity study.

Fischer-Tropsch synthesis (FTS) wastewater retaining low-carbon alcohols and acids are organic pollutants as a limiting factor for FTS industrialization. In this work, the structure-capacity relationships between alcohol-acid adsorption and surface species on graphene were reported, shedding light into their intricate interactions. The graphene oxide (GO) and reduced graphene oxide (rGO) were synthesized via improved Hummers method with flake graphite (G). The physicochemical properties of samples were characterized via SEM, XRD, XPS, FT-IR, and Raman. The alcohol-acid adsorption behaviors and adsorption quantities on G, GO, and rGO were measured via theoretical and experimental method. It was revealed that the presence of COOH, C=O and CO species on graphene occupy the adsorption sites and increase the interactions of water with graphene, which are unfavorable for alcohol-acid adsorption. The equilibrium adsorption quantities of alcohols and acids grow in pace with carbon number. The monolayer adsorption occurs on graphene was verified via model fitting. rGO has the highest FTS modeling wastewater adsorption quantity (110 mg/g) due to the reduction of oxygen species. These novel findings provide a foundation for the alcohol-acid wastewater treatment, as well as the design and development of high-performance carbon-based adsorbent materials.

Web-CONEXS: an inroad to theoretical X-ray absorption spectroscopy.

Accurate analysis of the rich information contained within X-ray spectra usually calls for detailed electronic structure theory simulations. However, density functional theory (DFT), time-dependent DFT and many-body perturbation theory calculations increasingly require the use of advanced codes running on high-performance computing (HPC) facilities. Consequently, many researchers who would like to augment their experimental work with such simulations are hampered by the compounding of nontrivial knowledge requirements, specialist training and significant time investment. To this end, we present Web-CONEXS, an intuitive graphical web application for democratizing electronic structure theory simulations. Web-CONEXS generates and submits simulation workflows for theoretical X-ray absorption and X-ray emission spectroscopy to a remote computing cluster. In the present form, Web-CONEXS interfaces with three software packages: ORCA, FDMNES and Quantum ESPRESSO, and an extensive materials database courtesy of the Materials Project API. These software packages have been selected to model diverse materials and properties. Web-CONEXS has been conceived with the novice user in mind; job submission is limited to a subset of simulation parameters. This ensures that much of the simulation complexity is lifted and preliminary theoretical results are generated faster. Web-CONEXS can be leveraged to support beam time proposals and serve as a platform for preliminary analysis of experimental data.

Quantum Mechanical Cluster Models for Calculations on Enzymatic Reaction Mechanisms: Set-Up and Accuracy.

Enzymes turnover substrates into products with amazing efficiency and selectivity and as such have great potential for use in biotechnology and pharmaceutical applications. However, details of their catalytic cycles and the origins surrounding the regio- and chemoselectivity of enzymatic reaction processes remain unknown, which makes the engineering of enzymes and their use in biotechnology challenging. Computational modelling can assist experimental work in the field and establish the factors that influence the reaction rates and the product distributions. A popular approach in modelling is the use of quantum mechanical cluster models of enzymes that take the first- and second coordination sphere of the enzyme active site into consideration. These QM cluster models are widely applied but often the results are dependent on model choice and selection. Herein, we show that QM cluster models can produce highly accurate results that reproduce experimental product distributions and free energies of activation, regarded that large cluster models with >300 atoms are used. In this tutorial review, we give general guidelines on the set-up and applications of the QM cluster method and discuss its accuracy and reproducibility. Finally, several representative QM cluster model examples on metal-containing enzymes are presented, which highlight the strength of the approach.

Molecular simulation of the slurrying mechanism in microplastic semi-coke water slurry.

CONTEXT: This study explores the interaction between particles in microplastic semi-coke water slurry at the molecular level using molecular simulation methods, specifically DFT calculations and MD simulations. In addition, the experiment of slurry preparation was carried out to study the viscosity and stability of the slurry. The electrostatic potential analysis shows that the interaction between microplastics and dispersant molecules occurs on atoms with large electronegativity or oxygen-containing functional groups, and the energy gap of frontier molecular orbitals indicated that PVC interacts most easily with the dispersant (0.39 eV), followed by PS (1.08 eV) and PET (3.65 eV). In addition, it is also noted that due to the steric hindrance effect, the adsorption energy was opposite to the DFT calculation results: PET was - 213.338 kcal/mol (NNO) which was highest, followed by PS (- 107.603 kcal/mol, NNO), and PVC (NNO) was lowest which was - 94.808 kcal/mol. And RDF shows similar results, which the probability of water molecules in the PET system was the highest, followed by PS, and finally, PVC. The MD results are consistent with the viscosity and stability characterization results of the slurry which PET has the lowest viscosity of 87.3 mPa·s. Finally, this study provides new ideas for the treatment of microplastics and the improvement of the performance of semi-coke water slurry and reveals the interaction mechanism between microplastics and semi-coke water slurry. METHODS: All calculations were performed using Materials Studio (MS) version 2020 software, BIOVIA Corporation. The DFT calculation was carried out through the DMol3 module. The DFT calculations include electron density, electrostatics, orbitals, and population analysis. In DMol3 module, the GGA-PBE function was selected to consider gradient changes in density in the simulated calculation. The DFT-D correction was selected, and all electrons were calculated by DNP for accurate core potentials and the DNP file was 4.4. MD simulation was performed through the Forcite module. MD simulation mainly focuses on relative concentration distribution analysis, radial distribution function, and adsorption energy calculation. All molecular geometry optimizations are performed in the Forcite module. In the molecular dynamic part, all simulations used PCFF forcefield. The NVT ensemble was adopted and using the Nosé thermostat.

Theoretical Study on the Electrocatalytic CO2 Reduction Mechanism of Single-Atom Co Complexed Carbon-Based (Co-Nχ@C) Catalysts Supported on Carbon Nanotubes.

Electrocatalytic CO2 reduction serves as an effective strategy to tackle energy crises and mitigate greenhouse gas effects. The development of efficient and cost-effective electrocatalysts has been a research hotspot in the field. In this study, we designed four Co-doped single-atom catalysts (Co-Nχ@C) using carbon nanotubes as carriers, these catalysts included tri- and dicoordinated N-doped carbon nanoribbons, as well as tri- and dicoordinated N-doped graphene, respectively denoted as H3(H2)-Co/CNT and 3(2)-Co/CNT. The stable configurations of these Co-Nχ@C catalysts were optimized using the PBE+D3 method. Additionally, we explored the reaction mechanisms of these catalysts for the electrocatalytic reduction of CO2 into four C1 products, including CO, HCOOH, CH3OH and CH4, in detail. Upon comparing the limiting potentials (UL) across the Co-Nχ@C catalysts, the activity sequence for the electrocatalytic reduction of CO2 was H2-Co/CNT > 3-Co/CNT > H3-Co/CNT > 2-Co/CNT. Meanwhile, our investigation of the hydrogen evolution reaction (HER) with four catalysts elucidated the influence of acidic conditions on the electrocatalytic CO2 reduction process. Specifically, controlling the acidity of the solution was crucial when using the H3-Co/CNT and H2-Co/CNT catalysts, while the 3-Co/CNT and 2-Co/CNT catalysts were almost unaffected by the solution's acidity. We hope that our research will provide a theoretical foundation for designing more effective CO2 reduction electrocatalysts.

Superlubric Graphullerene.

Graphullerene (GF), an extended quasi-two-dimensional network of C60 molecules, is proposed as a multicontact platform for constructing superlubric interfaces with layered materials. Such interfaces are predicted to present very small and comparable sliding energy corrugation regardless of the identity of the underlying flat layered material surface. It is shown that, beyond the geometrical effect, covalent interlinking between the C60 molecules results in reduction of the sliding energy barrier. For extended GF supercells, negligible sliding energy barriers are found along all sliding directions considered, even when compared to the case of the robust superlubric graphene/h-BN heterojunction. This suggests that multicontact architectures can be used to design ultrasuperlubric interfaces, where superlubricity may persist under extreme sliding conditions.

Efficient density functional theory directed identification of siderophores with increased selectivity towards indium and germanium.

Siderophores are promising ligands for application in novel recycling and bioremediation technologies, as they can selectively complex a variety of metals. However, with over 250 known siderophores, the selection of suiting complexants in the wet lab is impractical. Thus, this study established a density functional theory (DFT) based approach to efficiently identify siderophores with increased selectivity towards target metals on the example of germanium and indium. Considering 239 structures, chemically similar siderophores were clustered, and their complexation reactions modeled utilizing DFT. The calculations revealed siderophores with, compared to the reference siderophore desferrioxamine B (DFOB), up to 128 % or 48 % higher selectivity for indium or germanium, respectively. Experimental validation of the method was conducted with fimsbactin A and agrobactin, demonstrating up to 40 % more selective indium binding and at least sevenfold better germanium binding than DFOB, respectively. The results generated in this study open the door for the utilization of siderophores in eco-friendly technologies for the recovery of many different critical metals from various industry waters and leachates or bioremediation approaches. This endeavor is greatly facilitated by applying the herein-created database of geometry-optimized siderophore structures as de novo modeling of the molecules can be omitted.

Elucidation of the hydration pattern of trifluoroacetic acid in dilute solutions: FTIR and computational study.

The atmospheric partitioning of trifluoroacetic acid (TFA) in aerosol is a complex function of the size of suspended water droplets and their pH value. The unraveling of the affinity of TFA towards basic but not acidic conditions may be accomplished by providing an insight into the hydration pattern of undissociated TFA. Owing to rather scarce details on very dilute aqueous solutions of trifluoroacetic acid (TFA), we examined CF3COOD and CF3COONa solutions in D2O in the concentration range 0.001-0.1 mol dm-3 using transmission FTIR spectroscopy and computational methods. Besides detecting the signals originated from undissociated species in both CF3COOD (1787 cm-1 and 1766 cm-1 at c0 = 0.1 mol dm-3) and CF3COONa (1807 cm-1 at c0 = 0.1 mol dm-3) D2O solutions, through computational techniques we identified different TFA hydrates that contribute to the complexity of the spectral appearance. The combination of experimental and computational data suggested the concentration dependence of the predominant hydrogen bonding pattern of TFA. The results obtained in this work should help in understanding the partitioning of TFA into micron-size water droplets in the atmosphere in molecular and structural terms, i.e. the eventual stability of a hydrated complex for a particular TFA conformer.

In-Depth Investigation of Role of -BCO2 in the Degradation of Sulfamethazine by Metal-Free Biochar/Persulfate: The Mechanism of Occurrence of Nonradical Process.

The remediation of organic wastewater through advanced oxidation processes (AOPs) based on metal-free biochar/persulfate systems has been extensively researched. In this work, boron-doped alkali lignin biochar (BKC1:3) was utilized to activate peroxymonosulfate (PMS) for the removal of sulfamethazine (SMZ). The porous structure and substantial specific surface area of BKC1:3 facilitated the adsorption and thus degradation of SMZ. The XPS characterization and density functional theory (DFT) calculations demonstrated that -BCO2 was the main active site of BKC1:3, which dominated the occurrence of nonradical pathways. Neither quenching experiments nor EPR characterization revealed the generation of free radical signals. Compared with KC, BKC1:3 possessed more electron-rich regions. The narrow energy gap (ΔEgap = 1.87 eV) of BKC (-BCO2) promoted the electron transfer to the substable complex (BKC@PMS*) on SMZ, driving the electron transfer mechanism. In addition, the adsorption energy of BKC(-BCO2)@PMS was lower (-0.75 eV → -5.12 eV), implying a more spontaneous adsorption process. The O-O (PMS) bond length in BKC(-BCO2)@PMS increased significantly (1.412 Š→ 1.481 Å), which led to the easier decomposition of PMS during adsorption and facilitated the generation of 1O2. More importantly, a combination of Gaussian and LC-MS techniques was hypothesized regarding the attack sites and degradation intermediates of the active species in this system. The synergistic T.E.S.T software and toxicity tests predicted low or even no toxicity of the intermediates. Overall, this study proposed a strategy for the preparation of metal-free biochar, aiming to inspire ideas for the treatment of organic-polluted wastewater through advanced oxidation processes (AOPs).

UoC-10: Exploring the Packings of Chiral Copper(II) Paddle Wheel Based Metal-Organic Cages (MOCs).

The fluorination of the central ring of 1,3,5-benzene-tris-(meta-benzoate) (referred to as BTMB) leads to a twisted tritopic linker which reacts with copper(II) ions to assemble into octahedral (pseudospherical) metal-organic cages (MOCs) with paddle wheel units at their vertices. In this work, the different sphere packings of these MOCs are explored in detail together with their material properties, which closely resemble those of copper-based metal organic frameworks (MOFs). Theoretical investigations of the linkers are carried out to analyze the energetic barrier imposed by the fluorine substituents to form the observed atropisomers.

Unveiling the Obscure Potential of o-carborane Based IFLPs for CO2 Sequestration.

Sequestering carbon dioxide (CO2) from the atmosphere is necessary to achieve a sustainable environment. The emergence of frustrated Lewis pairs (FLPs) has opened a new dimension in the development of organocatalysts for CO2 sequestration. To date, various FLPs have been developed for CO2 sequestration, yet the quest for robust FLPs continues. Based on the intriguing electronic effects of the carborane polyhedral, o-carboranes can be projected as a versatile bridging unit for intramolecular FLPs (IFLPs). In the present work, o-carborane based IFLPs AlP, BP, AlN and BN have been proposed for the activation of CO2 molecule. The density functional theory (DFT) based calculations and thorough orbital analysis have been carried out to extensively study the electronic structure of the o-carborane unit. The proposed IFLPs were systematically compared with their corresponding phenyl bridged analogues to assess the effect of o-carborane bridging unit on the reactivity of the acidic and basic sites. The results show that the o-carborane supported IFLPs are more reactive towards CO2 than the phenyl bridged IFLPs. Also, placing the basic site on the B atom at the 4th position of the o-carborane bridge rather than the C atom at the 2nd position results in more reactive IFLPs.

Quantum-Confined Lifshitz Transition on Weyl Semimetal Td-MoTe2.

Adsorption of alkali atoms onto material surfaces is widely utilized for controlling electronic properties and is particularly effective for two-dimensional materials. While tuning the chemical potential and band gap and creating quantum-confined states are well established for alkali adsorption on semiconductors, the effects on semimetallic systems remain largely elusive. Here, utilizing angle-resolved photoemission spectroscopy measurements and density functional theory calculations, we disclose the creation of two-dimensional electron gas and the quantum-confined Lifshitz transition at the surface of a Weyl semimetal Td-MoTe2 by potassium adsorption. Electrons from potassium adatoms are shown to be transferred mainly to the lowest unoccupied band within the gapped part of the Brillouin zone, which, in turn, induces strong surface band bending and quantum confinement in the topmost layer. The quantum-confined topmost layer evolves from a semimetal to a strong metal with a Lifshitz transition departing substantially from the bulk band. The present finding and its underlying mechanism can be exploited for the creation of electronic heterojunctions in van der Waals semimetals.

Taming the 1,5-sigmatropic shift across protonated spirocyclic 4H-pyrazoles.

The condensation of 1,3-diketones with hydrazine to access 4H-pyrazoles is a well-established synthetic route that travels through a 4H-pyrazol-1-ium intermediate. In the route to a 3,5-diphenyl-4H-pyrazole containing a cyclobutane spirocycle, density functional theory calculations predict and experiments show that the protonated intermediate undergoes a rapid 1,5-sigmatropic shift to form a tetrahydrocyclopenta[c]pyrazole. Replacing the 3,5-diphenyl groups with 2-furanyl groups decreases the calculated rate of the 1,5-sigmatropic shift by 6.2 × 105-fold and enables the isolation of new spirocyclic 4H-pyrazoles for click chemistry.

Ca n neutral clusters: a two-step G 0 W 0 and DFT benchmark.

Electronic and structural properties of calcium clusters with a varying size range of 2-20 atoms are studied using a two-step scheme within the GW and density functional theory (DFT) with generalized gradient approximation (GGA). The GGA overestimates the binding energies, optimized geometries, electron affinities, and ionization potentials reported in the benchmark. The ground-state structure geometry and binding energy were obtained from the DFT for the ground-state structure of each cluster. The binding energy of the neutral clusters of the calcium series follows an increasing trend, except for a few stable even and odd clusters. The electronic properties of the calcium cluster were studied with an all-electron FHI-aims code. In the G 0 W 0 calculation, the magic cluster Ca10 has relatively high ionization potential and low electron affinity. The obtained ionization potentials from the G 0 W 0 @PBE calculation showed that the larger cluster has less variation, whereas the electron affinities of the series have an increasing trend. The ionization potentials from the G 0 W 0 benchmark for the calcium cluster series have not yet been described in the literature.

Modification of metals and ligands in two-dimensional conjugated metal-organic frameworks for CO2 electroreduction: A combined density functional theory and machine learning study.

Electrochemical carbon dioxide reduction reaction (CO2RR) is a promising technology to establish an artificial carbon cycle. Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) with high electrical conductivity have great potential as catalysts. Herein, we designed a range of 2D c-MOFs with different transition metal atoms and organic ligands, TMNxO4-x-HDQ (TM = Cr∼Cu, Mo, Ru∼Ag, W∼Au; x  = 0, 2, 4; HDQ = hexadipyrazinoquinoxaline), and systematically studied their catalytic performance using density functional theory (DFT). Calculation results indicated that all of TMNxO4-x-HDQ structures possess good thermodynamic and electrochemical stability. Notably, among the examined 37 MOFs, 6 catalysts outperformed the Cu(211) surface in terms of catalytic activity and product selectivity. Specifically, NiN4-HDQ emerged as an exceptional electrocatalyst for CO production in CO2RR, yielding a remarkable low limiting potential (UL) of -0.04 V. CuN4-HDQ, NiN2O2-HDQ, and PtN2O2-HDQ also exhibited high activity for HCOOH production, with UL values of -0.27, -0.29, and -0.27 V, respectively, while MnN4-HDQ, and NiO4-HDQ mainly produced CH4 with UL values of -0.58 and -0.24 V, respectively. Furthermore, these 6 catalysts efficiently suppressed the competitive hydrogen evolution reaction. Machine learning (ML) analysis revealed that the key intrinsic factors influencing CO2RR performance of these 2D c-MOFs include electron affinity (EA), electronegativity (χ), the first ionization energy (Ie), p-band center of the coordinated N/O atom (εp), the radius of metal atom (r), and d-band center (εd). Our findings may provide valuable insights for the exploration of highly active and selective CO2RR electrocatalysts.

Enhanced Electrocatalytic Performance of the FePt/PPy-C Composite toward Methanol Oxidation.

A novel FePt/PPy-C composite nanomaterial has been designed and investigated as a methanol oxidation reaction (MOR) electrocatalyst. The FePt nanoparticles with an average diameter of about 3 nm have been prepared by the co-reduction method and then loaded onto the PPy-C composite support. The electrocatalytic performance is affected by the composition of the FePt nanoparticles. The experimental results indicated that the Fe1.5Pt1/PPy-C catalyst exhibited excellent catalytic activity and stability for MOR, with mass activity and specific activity of 1.76 A mgPt-1 and 2.71 mA cm-2, respectively, which are 5.18 and 4.60 times higher than that of the commercial Pt/C catalyst. Density functional theory (DFT) has been employed to simulate the electrical structures of catalyst supports, and the mechanism of the methanol oxidation process has been further analyzed. The heterojunctions of the PPy-C interface could accelerate the electron migration from the electrocatalytic center to the electrodes. The possibility of methanol oxidation has been improved effectively, which can be confirmed by the d-band center and CO adsorption energy on FePt nanoparticles in the DFT calculation results.

In-situ growth of a covalent organic framework-based matrix-compatible microextraction coating for sensitive extraction of multiple pesticides.

The potential pesticide hazard to non-target organisms is a global concern. It is critical to develop the sensitive detection methods of multiple pesticides in various complex matrices. Here, benzene-1,3,5-tricarbaldehyde (BTCA) and 1,3,5-Tri (4-aminophenyl) benzene (TAPB) were employed as precursors for the in-situ growth of COFTAPB-BTCA on the surface of amino-functionalized stainless steel wire (SS) via a solvothermal method. The successful COFTAPB-BTCA bonded fiber exhibited significant enrichment capability of pyrethroids insecticides (PYs), organophosphorus (OPPs), and organochlorine (OCPs), with enrichment factors (EFs) ranging from 1133-7762, 1319-7291, and 734.1-2882, respectively. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations indicated that various interactions contributed to its high enrichment capacity. Automated detection of PYs, OPPs, and OCPs in water, foods, and biological samples was realized by coupling this fiber with gas chromatography-mass spectrometry (GC-MS). The detection limits were as low as 0.0370-0.657 ng/L, 0.0128-0.400 ng/L, and 0.0329-0.202 ng/L for PYs, OPPs, and OCPs, respectively. In addition, the environmental risks of these samples were assessed based on the above data. This work not only provided a straightforward technique for sensitive monitoring of pesticides in complex matrices but also presented a novel approach for the in-situ controlled growth of versatile adsorbents with broad-spectrum properties.

Performance of coal slime-based silicon fertilizer in simulating lead-contaminated soil: Heavy metal solidification and multi-nutrient release characteristics.

High-ash coal slime-based silica fertilizer (CSF) has the potential to provide mineral nutrients and passivate lead (Pb) in the soil to ensure the sustainable development of the coal industry and agriculture. This study investigated the performance and passivation mechanism of CSF, which contains potassium tobermorite and potassium silicate as the main components for soil improvement. Leaching experiments showed that low-crystalline muscovite was the only crystalline phase for CSF etching and that the silicon (Si), calcium (Ca), and potassium (K) in CSF had significant citric solubility. Soil cultivation and planting trials confirmed the ability of CSF to neutralize soil acidity, increase available soil Si and K, improve exchangeable Ca content, reduce the bioefficacy of Pb (exchangeable Pb by 19-75 % and carbonate-bound Pb by 6-18 %), and increase residual state Pb content. Compared to untreated Pb-contaminated soil, the 0.4 % CSF treatment reduced Pb in Chinese cabbage (Brassica rapa) by 25 % and increased plant biomass, Ca, and K by 37 %, 36 %, and 4 %, respectively. At the same time, soil pH increased by 0.58, and residual state Pb increased by 5 %. In CSF-treated soils, lead silicate is the dominant form of Pb present in the residual state. First-principle calculations showed that Pb3Si2O7 (cohesion energy -1.98 eV) formed by the passivation of Pb by CSF had greater stability in the soil compared to lead carbonate (PbCO3) (cohesion energy -1.38 eV) and lead sulfate (PbSO4) (cohesion energy -1.41 eV). This work shows the promising application of coal slime mineral fertilizers prepared using hydrothermal methods for soil improvement.

Reactive adsorption and catalytic oxidation of gaseous hydrogen sulfide using a prototype air purifier built with bismuth-doped titanium dioxide.

A prototype air purifier (AP) module has been constructed using bismuth-doped titanium dioxide (Bix-P25: x(%) as Bi/Ti molar ratios of 1.1, 2.1, 3.3, 5.3, and 8.7). The reactive adsorption property of Bix-P25 materials is evaluated against H2S gas at a recirculation rate of 160 L min-1 in a 17 L closed chamber. The AP (Bi5.3-P25) exhibits superior performance against 10 ppm H2S in dry air under dark conditions (i.e., without light irradiation), with a removal efficiency (XH2S)= 99% in 5 mins, reaction kinetic rate (r (at X = 10%))= 7.3 mmol h-1g-1, and partition coefficient= 0.18 mol kg-1 Pa-1. As such, its superiority is evident over the reference AP (P25) filter with XH2S < 10%. The clean air delivery rate (CADR) of AP (Bi5.3-P25) increases noticeably from 9.9 to 17.8 L min-1 with increasing relative humidity (RH) from 0 to 80%, respectively. In contrast, the CADR decreases from 9.9 to 5.8 L min-1 as the H2S increases from 10 to 20 ppm. According to density functional theory (DFT), the presence of H2O vapor enhances the hydroxylation of Bix-P25 surface to promote H2S mineralization through the formation of TiS3 (i.e., thermodynamic reaction of S atom with the catalytic surface). Complete removal of H2S on the Bi5.3-P25 surface is also confirmed consistently through gas chromatography-mass spectrometry (GC-MS), in-situ diffuse reflection infrared spectroscopy (in-situ DRIFTS), and elemental analysis (EA). This work represents the first utilization of Bix-P25 materials fabricated on an AP platform toward the desulfurization of H2S at room temperature (RT). The practical utility of Bix-P25 is overall validated by its eminent role in reactive adsorption and catalytic oxidation (RACO) of H2S from the air.

Extended benchmark set for lattice parameters of inorganic solids.

The development of novel methods in solid-state quantum chemistry necessitates reliable reference data sets for their assessment. The most fundamental solid-state property of interest is the crystal structure, quantified by the lattice parameters. In the last decade, several studies were conducted to assess theoretical approaches based on the agreement of calculated lattice parameters with respect to experiment as a measure. However, most of these studies used a limited number of reference systems with high symmetry. The present work offers a more comprehensive reference benchmark denoted as Sol337LC, which consists of 337 inorganic compounds with 553 symmetry-inequivalent lattice parameters, representing every element of the periodic table for atomic numbers between 1 and 86, except noble gases, the radioactive elements and lanthanoids. The reference values were taken from earlier benchmarks and from measurements at very low temperature or extrapolation to 0 K. The experimental low-temperature lattice parameters were then corrected for zero-point energy effects via the quasi-harmonic approximation for direct comparison with quantum-chemical optimized structures. A selection of standard density functional approximations was assessed for their deviations from the experimental reference data. The calculations were performed with the crystal orbital program CRYSTAL23, applying optimized atom-centered basis sets of triple-zeta plus polarization quality. The SCAN functional family and the global hybrid functional PW1PW, augmented with the D3 dispersion correction, were found to provide closest agreement with the Sol337LC reference data.