Double Hybrid Research Articles

Realization of half-metal antiferromagnetic (HM-AFM) behaviour in double perovskite Sr2CrReO6 on substitution of Tc at Cr site: Promising material for optoelectronics and thermoelectric applications via DFT framework

• We have studied Sr 2 AReO 6 (A=Cr, Tc) by using both PBEsol-GGA and PBEsol+U. • We report ferrimagnetic half-metal in Sr 2 CrReO 6 while Sr 2 TcReO 6 shows antiferromagnetic half-metal (AFM-HM) behavior. • Among the two materials Sr 2 TcReO 6 is a promising material for spintronic application due to low loss of energy. • Also double perovskite Sr 2 TcReO 6 (STRO) shows high absorption coefficient at UV-Vis range of photon energy. Using the application of the first principle within the Full Potential Linearized Augmented Plane wave (FP-LAPW) method, the electronic, magnetic, optical and thermoelectric properties of double perovskite oxides Sr 2 AReO 6 (A=Cr, Tc)were systematically investigated. We have used the most appropriate functionals like PBEsol-GGA and PBEsol+U. The replacement of Cr atom by Tc atom in Sr 2 CrReO 6 leads to the transition of the magnetic configuration from ferrimagnet to complete antiferromagnet half-metal (AFM-HM) with zero magnetic moments. The mechanisms that govern the ferrimagnetism/antiferromagnetism in the two double perovskites are the Zener double exchange and hybridization p-d, respectively. A careful analysis of the optical and thermoelectric properties in this study leads to the conclusion that the antiferromagnet double perovskite Sr 2 TcReO 6 (STRO)has the power to convert the maximum amount of sunlight in the visible range compared to the ferromagnet compound Sr 2 CrReO 6 (SCRO). Further, we have obtained an optimal figure of merit (ZT∼1) and high electrical conductivity. Finally, the half-metallic antiferromagnetic double perovskiteSTRO is a potential energy material for the spintronic device, photovoltaic solar cells and thermoelectric applications.

The productivity phenomenon of tilapia floating net cages in Jatiluhur Reservoir in line with the Citarum Harum program

The research was conducted to determine the productivity conditions of tilapia cultivation in the field along with the implementation of reducing the number of floating net cages. Production observations of tilapia culture were carried out on net cages owned by fish farmer in the Jatiluhur Reservoir from 2012 to 2019. The first period-P1 (2013-2015) was before the reduction in the number of net cages, the culture used a double net system and hybrid system. The second period-P2 (2016-2019) when the program started, KJA culture was carried out with a self-maintenance system (100% feeding for tilapia). The value of fish harvest weight ranged from 96.39-102.47 g (P1) and 196.84-278.33 g (P2). The range of survival rate is between 56.99–78.79% (P1), and 60.92–80.41% (P2). The feed efficiency value obtained in the P2 period was 75.77–86.34% while for P1 it was not defined because it was not a 100% feed system (independent). The daily weight gain, productivity and multiple values were as follows: 0.58-1.0 g/day, 0.14-0.45 g/m2, and 2.35-4.56x (P1); 1.43–3.00 g/day, 1.92–2.89 kg/m2 and 6.77–10.80x (P2). The monitored water quality parameters were still within a tolerable range for tilapia floating net cage culture.

Synthesis of Sterically Encumbered Thiourea S-Oxides through Direct Thiourea Oxidation.

Thiourea S-oxides can be viewed as formal analogs of the currently unknown diamino-substituted Criegee intermediates (urea O-oxides). However, the preparation of such S-oxides is rather challenging, and the direct oxidation of thioureas typically only leads to formation of desulfurized products. Employing the accurate revDSD-PBEP86-D4 double hybrid density functional, it was found that the peracid mediated oxidation of thiourea S-oxides exhibits a lower reaction barrier than the oxidation of the corresponding thiourea itself in contrast to most other ordinary thioketones. The undesired overoxidation reactivity, which is associated with strong π-donation from the thiourea's nitrogen atoms, can be partially suppressed by introduction of bulky substituents and the utilization of protic solvents. In this regard, we managed to prepare two sterically encumbered thiourea S-oxides in isolated yields of 35-40 %. The S-oxides are stable in the solid state and in alcoholic solutions at room temperature for extended periods of time, but swiftly decompose in aprotic solvents by disproportionation. A dimesityl-substituted thiourea S-oxide complexed with residual mCBA could be characterized by means of X-ray crystallography, confirming the importance of hydrogen bonding in the stabilization of the amino-substituted C=S+ -O- moiety.

The effect of steering tail fin on performance on double pillars hybrid vertical axis wind turbine (Sultan Wind Turbine V-4.5)

One of the methods to increase the efficiency of wind turbines is to add directional fins so that the wind turbine faces and is in the same direction as the wind. The use of triangular fins will slightly increase the performance of wind turbines compared to rectangular and trapezoidal shapes. The most crucial factor is that the fin area is not less than 5% of the swept area on the turbine blades. And according to calculations and simulation data, the convex pentagonal shape generates the greatest power. While the tests conducted by P.R. Ebert et al, that a twin wing with a high wing angle shows a greater damping response than a single wing. The aim of this research is to optimize the performance of the Sultan V-4.5 wind turbine by adding guide fins. Simulation methods and design of directional fins were carried out to obtain the most suitable fin shape and size. By using an aspect ratio of 1.4, the distance from the center of gravity to the center axis of the turbine is reduced. Performance tests were carried out using fins with areas of 0.06 m 2 , 0.12 m 2 and 0.22 m 2 . Twin fins are used, with a 30 o angle between them, to reduce the oscillatory forces resulting from wind motion. Fin profiles with maximum force when exposed to wind at angles of 0°, 5°, 10°, 15°, 20°, 25°, and 30° were selected from the available profiles using Computer Fluid Dynamic analysis. To determine the most suitable structure and material for fins, simulate the topology optimization and material selection used. According to his findings, the isosceles and right-angled triangles, which produce forces of 0.91 N and 0.77 N respectively, are the strongest. PVC plates are the materials used. The results of this study indicate that 2 m/s wind speeds frequency, the type 3b fin designs are the best design according to performance tests. The end result, coefficient of power increases and power generates increases respectively 5 and 3.8 times the previous research.

Fabrication of hierarchical Ni nanowires@ NiCo-layered double hydroxide nanosheets core-shell hybrid arrays for high-performance hybrid supercapacitors.

Layered double hydroxides (LDHs) are electrode materials with high specific capacity due to their structure which has a tunable interlayer spacing, however, the disadvantages of their low conductivity and electrochemically limited sites prevent their application in supercapacitors. In this study, we synthesized a high electrochemical performance electrode material with a core-shell structure based on hierarchical nickel nanowires (core) and NiCo LDHs nanosheets (shell). First, hierarchical nickel nanowires, h-Ni NWs, were prepared by the reduction of Ni2+ ions by hydrazine N2H4. Then with the hydrothermal method, the hierarchical nickel nanowires were coated with NiCo LDHs to improve the electrical conductivity of the latter. The electrochemical results showed that the NiCo LDHs@h-Ni NWs electrode had a specific capacity of 1486 C/g at a current density of 1 A/g in 6 M KOH electrolyte with excellent capacity retention (89.7%) after 10,000 charge-discharge cycles at 20 A/g. Due to the synergistic interaction between nickel nanowires and NiCo LDHs which provides excellent conductivity, durability, efficient mesoporous network, and suitable channels for fast ion/electron transfer. In addition, a hybrid supercapacitor (HSC) was fabricated by combining the NiCo LDHs@h-Ni NWs electrode (battery type) with activated carbon (EDLC). The fabricated device provided a high energy density of 72.22 Wh/kg at 800 W/kg, and a maximum power density of 16 kW/kg, the HSC provided an energy density of 50.44 Wh/kg and outstanding cycling stability (88.1% retention after 10,000 cycles).

Testing of Exchange-Correlation Functionals of DFT for a Reliable Description of the Electron Density Distribution in Organic Molecules

Researchers carrying out calculations using the DFT method face the problem of the correct choice of the exchange-correlation functional to describe the quantities they are interested in. This article deals with benchmark calculations aimed at testing various exchange-correlation functionals in terms of a reliable description of the electron density distribution in molecules. For this purpose, 30 functionals representing all rungs of Jacob's Ladder are selected and then the values of some QTAIM-based parameters are compared with their reference equivalents obtained at the CCSD/aug-cc-pVTZ level of theory. The presented results show that the DFT method undoubtedly has the greatest problems with a reliable description of the electron density distribution in multiple strongly polar bonds, such as C=O, and bonds associated with large electron charge delocalization. The performance of the tested functionals turned out to be unsystematic. Nevertheless, in terms of a reliable general description of QTAIM-based parameters, the M11, SVWN, BHHLYP, M06-HF, and, to a slightly lesser extent, also BLYP, B3LYP, and X3LYP functionals turned out to be the worst. It is alarming to find the most popular B3LYP functional in this group. On the other hand, in the case of the electron density at the bond critical point, being the most important QTAIM-based parameter, the M06-HF functional is especially discouraged due to the very poor description of the C=O bond. On the contrary, the VSXC, M06-L, SOGGA11-X, M06-2X, MN12-SX, and, to a slightly lesser extent, also TPSS, TPSSh, and B1B95 perform well in this respect. Particularly noteworthy is the overwhelming performance of double hybrids in terms of reliable values of bond delocalization indices. The results show that there is no clear improvement in the reliability of describing the electron density distribution with climbing Jacob's Ladder, as top-ranked double hybrids are also, in some cases, able to produce poor values compared to CCSD.

Spin-State Splittings in 3d Transition-Metal Complexes Revisited: Benchmarking Approximate Methods for Adiabatic Spin-State Energy Differences in Fe(II) Complexes.

The CASPT2+δMRCI composite approach reported in a companion paper has been extended and used to provide high-quality reference data for a series of adiabatic spin gaps (defined as ΔE = Equintet - Esinglet) of [FeIIL6]2+ complexes (L = CNH, CO, NCH, NH3, H2O), either at nonrelativistic level or including scalar relativistic effects. These highly accurate data have been used to evaluate the performance of various more approximate methods. Coupled-cluster theory with singles, doubles, and perturbative triples, CCSD(T), is found to agree well with the new reference data for Werner-type complexes but exhibits larger underestimates by up to 70 kJ/mol for the π-acceptor ligands, due to appreciable static correlation in the low-spin states of these systems. Widely used domain-based local CCSD(T) calculations, DLPNO-CCSD(T), are shown to depend very sensitively on the cutoff values used to construct the localized domains, and standard values are not sufficient. A large number of density functional approximations have been evaluated against the new reference data. The B2PLYP double hybrid gives the smallest deviations, but several functionals from different rungs of the usual ladder hierarchy give mean absolute deviations below 20 kJ/mol. This includes the B97-D semilocal functional, the PBE0* global hybrid with 15% exact-exchange admixture, as well as the local hybrids LH07s-SVWN and LH07t-SVWN. Several further functionals achieve mean absolute errors below 30 kJ/mol (M06L-D4, SSB-D, B97-1-D4, LC-ωPBE-D4, LH12ct-SsirPW92-D4, LH12ct-SsifPW92-D4, LH14t-calPBE-D4, LHJ-HFcal-D4, and several further double hybrids) and thereby also still overall outperform CCSD(T) or uncorrected CASPT2. While exact-exchange admixture is a crucial factor in favoring high-spin states, the present evaluations confirm that other aspects can be important as well. A number of the better-performing functionals underestimate the spin gaps for the π-acceptor ligands but overestimate them for L = NH3, H2O. In contrast to a previous suggestion, non-self-consistent density functional theory (DFT) computations on top of Hartree-Fock orbitals are not a promising path to produce accurate spin gaps in such complexes.

Synthesis of layered double hydroxide-based hybrid electrode for efficient removal of phosphate ions in capacitive deionization.

The removal of phosphate ions by capacitive deionization has become one of the most frontier research topics in the water treatment field in recent years. In this work, hybrid electrodes composed of nickel-iron layered double hydroxide (NiFe-LDH) - anchored on activated carbon fiber (ACF)-were synthesized by a hydrothermal method and subsequently applied in capacitive deionization to remove phosphate ions. The adsorption performance of the two hybrid electrodes on phosphate ions was compared by capacitive deionization experiments. The experiment was carried out for 3 hours to reach equilibrium, and the optimum adsorption of 33.48 mg/g was obtained using NiFe-LDH/ACF-2 hybrid electrode at room temperature (25 °C) and pH = 6.0. The results showed that increasing the loading capacity of NiFe-LDH on ACF might enhance the adsorption capacity of phosphate ions. Furthermore, the calculation of adsorption kinetics and adsorption isotherms elucidated that the adsorption capacity increased with the increasing of applied voltage. Meanwhile, the experimental data were fitted well with pseudo-first-order kinetics and Langmuir isotherms. Notably, it was observed that the pH first increased, then decreased during the adsorption due to the electrolysis of water, while the form of phosphate ions was transformed, with low pH favoring the adsorption of phosphate ions.

Importance and necessity double hybrids in the sericulture industry

Importance and necessity double hybrids in the sericulture industry

Comparison of construction methods of the Pingtang Bridge in China and the Millau Viaduct in France

The cable-stayed bridge is a kind of bridge deck system under pressure and a support system under tension. The Pingtang Bridge is 2135m long, with the main bridge being 249.5m + 550m + 550m + 249.5m three-tower, double cable-faced steel and hybrid combination girder cable-stayed bridge. Its highest cable-stayed tower is 320m, making it the third highest bridge structure in the world. The Millau Viaduct is 2460 m long, with two end spans of 204 m each and six central spans of 342 m each. Its tallest tower is 343 m, making it the second tallest bridge structure in the world. The two bridges suffer from similar climatic and geological factors, but the construction methods differ significantly. This paper summarizes the similarities between the construction methods of the two bridges and compares their differences. Results show that the construction methods of the Milo Viaduct are very creative, challenging and technically difficult, and the construction methods of the Pingtang Bridge are operational and imitative.

Evaluation of nutritional indices and conversion efficiency in multivoltine, cross-breeds and popular bivoltine double hybrid of mulberry silkworm Bombyx mori

In sericulture, the nutritional ability of mulberry varieties and conversional traits of silkworm breeds have an important role in the improvement of silk yield. The present study aims to evaluate silk conversion efficiency in a few breeds and hybrids. The silkworm Bombyx mori breeds and hybrids viz., MVI, PMxCSR2, MV1xS8 and FC1xFC2 were assessed during the fifth instar, with PM as control during the years 2019 and 2020. The study focused on the nutritional indices and conversion traits of silkworms by feeding V1 mulberry leaves, reared under the same environmental conditions. Significant variations were observed among silkworm breeds and hybrids. The test breed and hybrids were found superior to the control PM, which recorded an ingestion of 2.33g and a conversion ability of 8.65%. The bivoltine double hybrid FC1xFC2 showed high food ingestion (3.25g) and conversion (18.18%), followed by the cross breed MV1xS8 with moderate ingestion (3.17g) and conversion (16.63%). The values for ingesta and conversion in PMxCSR2 were 3.43 g and 8.92%, respectively. Further, in respect of Efficiency Conversion of Ingesta (ECI) of shell, the highest conversion of shell is shown by FC1xFC2 (13.56%) followed by MV1xS8 (10.14%), MV1 (9.73%) and PMxCSR2 (9.36%), having a percentage difference of 63.27%, 36.08%, 32.11% and 28.30% respectively over PM. The silk conversion efficiency of bivoltine double hybrid FC1xFC2 was found to be profoundly high, followed by multivoltine cross-breeds and pure line (PM) tested.

RNA double strand hybridization measured at the single molecule level

RNA double strand hybridization is a hallmark for gene expression regulation. In this function, single stranded regulatory RNA forms Watson-Crick base pairs with complementary messenger RNA. In the presented work the dissociation constants of complementary equally sized RNA single strands were measured at the single molecule level applying fluorescence correlation spectroscopy (FCS). Dissociation constants of 3.2 nM, 1.4 nM and 1.0 nM were determined for 26 bp, 41 bp and 54 bp dsRNA, respectively. The translational diffusion coefficients of RNA, measured at infinite dilution, could be accurately predicted applying the model D = 4.58 × 10−10 N−0.39 m2s−1.

Molecular Recognition of FDA-Approved Small Molecule Protein Kinase Drugs in Protein Kinases.

Protein kinases are key enzymes that catalyze the covalent phosphorylation of substrates via the transfer of the γ-phosphate of ATP, playing a crucial role in cellular proliferation, differentiation, and various cell regulatory processes. Due to their pivotal cellular role, the aberrant function of kinases has been associated with cancers and many other diseases. Consequently, competitive inhibition of the ATP binding site of protein kinases has emerged as an effective means of curing these diseases. Decades of intense development of protein kinase inhibitors (PKIs) resulted in 71 FDA-approved PKI drugs that target dozens of protein kinases for the treatment of various diseases. How do FDA-approved protein kinase inhibitor PKI drugs compete with ATP in their own binding pocket? This is the central question we attempt to address in this work. Based on modes of non-bonded interactions and their calculated interaction strengths by means of the advanced double hybrid DFT method B2PLYP, the molecular recognition of PKI drugs in the ATP-binding pockets was systematically analyzed. It was found that (1) all the FDA-approved PKI drugs studied here form one or more hydrogen bond(s) with the backbone amide N, O atoms in the hinge region of the ATP binding site, mimicking the adenine base; (2) all the FDA-approved PKI drugs feature two or more aromatic rings. The latter reach far and deep into the hydrophobic regions I and II, forming multiple CH-π interactions with aliphatic residues L(3), V(11), A(15), V(36), G(51), L(77) and π-π stacking interactions with aromatic residues F(47) and F(82), but ATP itself does not utilize these regions extensively; (3) all FDA-approved PKI drugs studied here have one thing in common, i.e., they frequently formed non-bonded interactions with a total of 12 residues L(3),V(11), A(15), K(17), E(24),V(36),T(45), F(47), G(51), L(77), D(81) and F(82) in the ATP binding. Many of those 12 commonly involved residues are highly conserved residues with important structural and catalytic functional roles. K(17) and E(24) are the two highly conserved residues crucial for the catalytic function of kinases. D(81) and F(82) belong to the DFG motif; T(45) was dubbed the gate keeper residue. F(47) is located on the hinge region and G(51) sits on the linker that connects the hinge to the αD-helix. It is this targeting of highly conserved residues in protein kinases that led to promiscuous PKI drugs that lack selectivity. Although the formation of hydrogen bond(s) with the backbone of the hinge gives PKI drugs the added binding affinity and the much-needed directionality, selectivity is sacrificed. That is why so many FDA-approved PKI drugs are known to have multiple targets. Moreover, off-target-mediated toxicity caused by a lack of selectivity was one of the major challenges facing the PKI drug discovery community. This work suggests a road map for future PKI drug design, i.e., targeting non-conserved residues in the ATP binding pocket to gain better selectivity so as to avoid off-target-mediated toxicity.

A flexible and high energy density -hydrous RuO2 and keratin-derived renewable carbon composite-based asymmetric supercapacitor in redox-mediated electrolytes

The present study exploits a chemical-free, low-cost, simple, scalable, and facile synthesis technique using an in-situ methodology to prepare composite electrodes. The as-synthesized composite is utilized as a hybrid electrode for supercapacitor application. The hydrous RuO2 and keratin fiber-derived carbon (ROKF-2) show excellent specific capacitance of 3542 F g−1 at 2 A g−1. However, true analysis reveals that the actual capacitance is 2556 F g−1. It focuses on delivering the actual performance of the hybrid device by eliminating the use of conventional equations. In symmetric assembly, the excellent device capacitance of 121 F g−1 at 1 A g-1 is achieved while maintaining its coulombic efficiency above 90% throughout the applied current. The double hybridization assembly shows the broadening of working potential with an outstanding energy density of 226 Wh kg−1 at 1000 W Kg−1. Upon introducing redox additives, the performance increases, suggesting their effective contribution to the charge storage process. In the presence of K3Fe(CN)6, the device delivers a remarkable rate capability of 50% till 5 A g−1, whereas, in the KI environment, the device efficiency gets enhanced ∼45%. The wire-shaped flexible device shows a specific capacitance of 142 mF cm−1 at a scan rate of 10 mV s−1 with an energy density of 0.03 mWh cm−1 at 33 W cm−1. The process approaches a chemical-free process for the composite synthesis, which can be utilized in various hybridization modes. The study eliminates the traditional equations to minimize the overestimated electrochemical performance. The prepared composites pave a new path in hybrid energy storage systems.

Zaltoprofen-layered double hydroxide hybrids to enhance zaltoprofen solubility and dissolution rate

The zaltoprofen-LDH hybrid was successfully synthesized by coprecipitation method, and its dissolution profile and solubility in different fluids, that simulate the gastro-intestinal environment, were investigated. The zaltoprofen-LDH hybrid stoichiometry was determined by EDS and TGA, and the Zn0.70Al0.30(OH)2Z0.30·0.76H2O chemical formula was obtained, which well compares to the Zn/Al molar ratio of the pristine LDH (nitrate-LDH hybrid: Zn0.73Al0.27(OH)2(NO3)0.27·0.44H2O), synthesized to prepare the zaltoprofen-LDH physical mixture for the dissolution tests. The XRPD results confirmed the successful insertion of the zaltoprofen in the interlayer space of the LDH structure: the 003 reflection, detected at d-value of 8.7 Å in the pristine LDH, was observed at d-value of 21.8 Å, and the drug occupied a gallery of about 17 Å. Based on the zaltoprofen size (9.9 × 4.9 Å), a drug arrangement in which the molecules form a monolayer of partially superimposed drug anions into the brucite-like layer is suggested. The DSC peak due to the melting process of the pure zaltoprofen was not observed in the zaltoprofen-LDH hybrid, thus indicating the loss of the long-range structural order in the active principle. FT-IR spectroscopy confirmed that the zaltoprofen entered the host structure in the anionic form (COO−). Deep insights in the drug-LDH interaction were obtained by 13C and 27Al solid state NMR: the zaltoprofen molecules strongly interacted with the LDH layers involving the COO- and the OH moieties respectively, while the packing of the drug molecules in the layers was comparable to the conformation of the pure zaltoprofen crystals. The zaltoprofen anion insertion caused local structural changes within the host crystal structure. The solubility and dissolution tests, performed on the synthesized hybrid and compared to the pure zaltoprofen and zaltoprofen-LDH physical mixture, demonstrated enhanced solubility and dissolution rate of the drug in the hybrid system.

Study of ferromagnetism and thermoelectric behaviour of thiospinels MgFe2(S/Se)4 for spintronics and energy harvesting

Magnesium-based spinel chalcogenides are remarkable materials for spintronic and energy harvesting applications. Therefore, the electronic, ferromagnetism, and thermoelectric characteristics of MgFe2(S/Se)4 spinels are addressed comprehensively by modified Becke Johnson potential (TB-mBJ). The stability of cubic phase has been illustrated by formation energy and energy released during optimization. The Curie temperature and spin polarization have been calculated by Heisenberg model and density of states at Fermi level. Ferromagnetism has been studied by exchange energies, double exchange mechanism, exchange constants, and hybridization process. The reduction of magnetic moment of Fe and its shifting on nonmagnetic (Mg, S/Se) sites shows the ferromagnetism is due to the exchange of electrons spin rather than the clustering effect of internal magnetic of Fe atoms in the structure. Moreover, thermoelectric analysis of studied spinels has been illustrated by electrical and thermal conductivities, Seebeck coefficient (S), and power factor.

Designing and implementing a location-based model to identify areas suitable for multi-renewable energy development for supplying electricity to agricultural wells

The purpose of this study is to design and implement a spatial model to identify optimal areas for energy sources (solar power plant (SPS), wind turbine generator (WTG), Distributed Gas Turbine-Generators (DGTG), and direct connection to power distribution system (PDS) to supply electricity to agricultural wells using a combination of data-driven methods and geographic information system (GIS). This study used 13 spatial criteria to identify suitable areas for SPS, 11 for WTG, 11 for DGTG, and 3 for PDS. A combination of data-driven decision-making (DDDM) and GIS was used for data analysis. The results of the present study showed that in the pilot study area, solar energy has a higher potential than other energies. Also, the results of the sensitivity analysis showed that changing the weight of the criteria has no significant effect on the model outputs and clearly proves the stability of the proposed model. The hybrid power plant scenarios showed that had the highest number of pixels suitable for development were associated with double and triple hybrid power solutions generator, respectively. These were hybrid SPS and DGTG and hybrid SPS, PDS, and DGTG systems.

Evaluation of Various Double Haploid Maize Hybrids Under Water Deficit Condition

Evaluation of Various Double Haploid Maize Hybrids Under Water Deficit Condition

Reduced-Scaling Double Hybrid Density Functional Theory with Rapid Basis Set Convergence through Localized Pair Natural Orbital F12.

Following earlier work [Mehta, N.; Martin, J. M. L. J. Chem. Theory Comput.2022, 10.1021/acs.jctc.2c00426] that showed how the slow basis set convergence of the double hybrid density functional theory can be obviated by the use of F12 explicit correlation in the GLPT2 step (second order Görling-Levy perturbation theory), we demonstrate here for the very large and chemically diverse GMTKN55 benchmark suite that the CPU time scaling of this step can be reduced (asymptotically linearized) using the localized pair natural orbital (PNO-L) approximation at negligible cost in accuracy.

Probing the Reactions of Thiourea (CH4N2S) with Metals (X = Au, Hf, Hg, Ir, Os, W, Pt, and Re) Anchored on Fullerene Surfaces (C59X).

Upon various investigations conducted in search for a nanosensor material with the best sensing performance, the need to explore these materials cannot be overemphasized as materials associated with best sensing attributes are of vast interest to researchers. Hence, there is a need to investigate the adsorption performances of various metal-doped fullerene surfaces: C59Au, C59Hf, C59Hg, C59Ir, C59Os, C59Pt, C59Re, and C59W on thiourea [SC(NH2)2] molecule using first-principles density functional theory computation. Comparative adsorption study has been carried out on various adsorption models of four functionals, M06-2X, M062X-D3, PBE0-D3, and ωB97XD, and two double-hybrid (DH) functionals, DSDPBEP86 and PBE0DH, as reference at Gen/def2svp/LanL2DZ. The visual study of weak interactions such as quantum theory of atoms in molecule analysis and noncovalent interaction analysis has been invoked to ascertain these results, and hence we arrived at a conclusive scientific report. In all cases, the weak adsorption observed is best described as physisorption phenomena, and CH4N2S@C59Pt complex exhibits better sensing attributes than its studied counterparts in the interactions between thiourea molecule and transition metal-doped fullerene surfaces. Also, in the comparative adsorption study, DH density functionals show better performance in estimating the adsorption energies due to their reduced mean absolute deviation (MAD) and root-mean-square deviation (RMSD) values of (MAD = 1.0305, RMSD = 1.6277) and (MAD = 0.9965, RMSD = 1.6101) in DSDPBEP86 and PBE0DH, respectively.