Accurate Potential Energy Surfaces Using Atom-Centered Potentials and Minimal High-Level Data.

We demonstrate that a Δ-density functional theory (Δ-DFT) approach based on atom-centered potentials (ACPs) represents a computationally inexpensive and accurate method for representing potential energy surfaces (PESs) for the HONO and HFCO molecules and vibrational frequencies derived therefrom. Using as few as 100 CCSD(T)-F12a reference energies, ACPs developed for use with B3LYP/def2-TZVPP are shown to produce PESs for HONO and HFCO with mean absolute errors of 27.7 and 5.8 cm-1, respectively. Application of the multiconfigurational time-dependent Hartree (MCTDH) method with ACP-corrected B3LYP/def2-TZVPP PESs produces vibrational frequencies for cis- and trans-HONO with mean absolute percent errors (MAPEs) of 0.8 and 1.1, compared to 0.8 obtained for the two isomers with CCSD(T)-F12a/cc-pVTZ-F12/MCTDH. For HFCO, the vibrational frequencies obtained using the present (Δ-DFT)/MCTDH approach give a MAPE of 0.1, which is the error obtained with CCSD(T)-F12a/cc-pVTZ-F12/MCTDH. The ACP approach is therefore successful in representing a PES calculated at a high level of theory (CCSD(T)-F12a) and a promising method for the development of a general protocol for the representation of accurate molecular PESs and the calculation of molecular properties from them.

Electrochemical PINOylation of Methylarenes: Improving the Scope and Utility of Benzylic Oxidation through Mediated Electrolysis.

A mediated electrosynthetic method has been developed for selective benzylic oxidation of methylarenes. Phthalimide-N-oxyl (PINO) radical generated by proton-coupled electrochemical oxidation of N-hydroxypthalimide serves as a hydrogen atom-transfer (HAT) mediator and as a radical trap for the benzylic radicals generated in situ. This mediated electrolysis method operates at much lower anode potentials relative to direct electrolysis methods for benzylic oxidation initiated by single-electron transfer (SET). A direct comparison of SET and mediated-HAT electrolysis methods with a common set of substrates shows that the HAT reaction exhibits a significantly improved substrate scope and functional group compatibility. The PINOylated products are readily converted into the corresponding benzylic alcohol or benzaldehyde derivative under photochemical conditions, and the synthetic utility of this method is highlighted by the late-stage functionalization of the non-steroidal anti-inflammatory drug celecoxib.

Bimodal Evans-Polanyi Relationships in Hydrogen Atom Transfer from C(sp3)-H Bonds to the Cumyloxyl Radical. A Combined Time-Resolved Kinetic and Computational Study.

The applicability of the Evans-Polanyi (EP) relationship to HAT reactions from C(sp3)-H bonds to the cumyloxyl radical (CumO•) has been investigated. A consistent set of rate constants, kH, for HAT from the C-H bonds of 56 substrates to CumO•, spanning a range of more than 4 orders of magnitude, has been measured under identical experimental conditions. A corresponding set of consistent gas-phase C-H bond dissociation enthalpies (BDEs) spanning 27 kcal mol-1 has been calculated using the (RO)CBS-QB3 method. The log kH' vs C-H BDE plot shows two distinct EP relationships, one for substrates bearing benzylic and allylic C-H bonds (unsaturated group) and the other one, with a steeper slope, for saturated hydrocarbons, alcohols, ethers, diols, amines, and carbamates (saturated group), in line with the bimodal behavior observed previously in theoretical studies of reactions promoted by other HAT reagents. The parallel use of BDFEs instead of BDEs allows the transformation of this correlation into a linear free energy relationship, analyzed within the framework of the Marcus theory. The ΔG⧧HAT vs ΔG°HAT plot shows again distinct behaviors for the two groups. A good fit to the Marcus equation is observed only for the saturated group, with λ = 58 kcal mol-1, indicating that with the unsaturated group λ must increase with increasing driving force. Taken together these results provide a qualitative connection between Bernasconi's principle of nonperfect synchronization and Marcus theory and suggest that the observed bimodal behavior is a general feature in the reactions of oxygen-based HAT reagents with C(sp3)-H donors.

Computational Study of Hydrogen Bond Interactions in Water Cluster-Organic Molecule Complexes.

We analyzed the interactions present in complexes that acetone, azomethane, dimethylamine, dimethyl ether, methyl acetate, and oxirane form with 39 different (H2O)n clusters (n = 1-10). A random generation of configurations and a subsequent screening procedure were employed to sample representative interactions. Using quantum chemical computations, we calculated the associated binding energies, which range from -0.19 to -10.76 kcal/mol at the DLPNO-CCSD(T)/CBS level. It was found that the binding energies can be understood in terms of various factors, including the water cluster size, the nature of the organic molecule, and the type of hydrogen bond donor. We find that the most stable complexes often arise from a combination of a strong hydrogen bond plus a secondary interaction between the organic molecule and the water cluster.

Reply to the 'Comment on "Extent of conjugation in diazonium-derived layers in molecular junction devices determined by experiment and modelling"' by R. L. McCreery, S. K. Saxena, M. Supur and U. Tefashe, Phys. Chem. Chem. Phys., 2020, 22, DOI: 10.1039/d0cp02412k.

Our paper [Phys. Chem. Chem. Phys., 2019, 21, 16762] is the subject of a comment that clarifies a flaw in analysis of STM data. We accept the comment in regard to the aspect ratio considerations, but we also further clarify the main conclusions of our paper, and provide a molecular scale schematic using the data presented in the comment to help refine the original conclusions. Taken together, this shows that models presented in the literature may benefit from including more fine structure details, as better understanding may emerge from such considerations. This was the intent of our original article, and we thank the comment authors for the chance to clarify these points.

Evaluation of Polar Effects in Hydrogen Atom Transfer Reactions from Activated Phenols.

Evaluation of polar effects in hydrogen atom transfer (HAT) processes is made difficult by the fact that in most cases substrates characterized by lower bond dissociation energies (BDEs), activated from an enthalpic point of view, are also more activated by polar effects. In search of an exception to this general rule, we found that the introduction of a methoxy substituent in the 3-position of 2,6-dimethylphenol results in a small increase in the O-H BDE and a decrease of the ionization potential of the phenol. These findings suggest that the enthalpic effect associated with the addition of the m-methoxy group to 2,6-dimethylphenol will decrease reaction rates, while the polar effects will increase reaction rates. Our model analysis of polar effects has been experimentally validated by comparing the reactivity of 2,6-dimethylphenol with that of 2,6-dimethyl-3-methoxyphenol in HAT promoted by a series of radicals (cumyloxyl, galvinoxyl, 2,2-diphenylpycrylhydrazyl, phthalimide- N-oxyl, and benzotriazole- N-oxyl radicals). In line with our predictions, the ratio of HAT rate constants ( kH mOMe/ kHH) is larger in cases where there is a greater contribution of polar effects in the HAT reaction, i.e., in HAT promoted by N-oxyl radicals containing electron-withdrawing groups or when more polar solvents are employed.

Extent of conjugation in diazonium-derived layers in molecular junction devices determined by experiment and modelling.

This paper shows that molecular layers grown using diazonium chemistry on carbon surfaces have properties indicative of the presence of a variety of structural motifs. Molecular layers grown with aromatic monomers with thickness between 1 and ∼15 nm display optical absorption spectra with significant broadening but no change in band gap or onsets of absorption as a function of layer thickness. This suggests that there is no extended conjugation in these layers, contrary to the conclusions of previous work. Density-functional theory modelling of the non-conjugated versions of the constituent aromatic monomers reveals that the experimental trends in optical spectra can be recovered, thereby establishing limits to the degree of conjugation and the nature of the order of as-grown molecular layers. We conclude that the absence of both shifts in band gap and changes in absorption onset is a consequence of resonant conjugation within the layers being less than 1.5 monomer units, and that film disorder is the main origin of the optical spectra. These findings have important implications for understanding charge transport mechanisms in molecular junction devices, as the layers cannot be expected to behave as ideal, resonantly conjugated films, but should be viewed as a collection of mixed nonresonantly- and resonantly-conjugated monomers.

Extremely Fast Hydrogen Atom Transfer between Nitroxides and HOO· Radicals and Implication for Catalytic Coantioxidant Systems.

We report a novel coantioxidant system based on TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) that, in biologically relevant model systems, rapidly converts chain-carrying alkylperoxyl radicals to HOO·. Extremely efficient quenching of HOO· by TEMPO blocks the oxidative chain. Rate constants in chlorobenzene were measured to be 1.1 × 109 M-1 s-1 for the reductive reaction TEMPO + HOO· → TEMPOH + O2 and 5.0 × 107 M-1 s-1 for the oxidative reaction TEMPOH + HOO· → TEMPO + H2O2. These rate constants are significantly higher than that associated with the reaction of HOO· with α-tocopherol, Nature's best lipid soluble antioxidant ( k = 1.6 × 106 M-1 s-1). These data show that in the presence of ROO·-to-HOO· chain-transfer agents, which are common in lipophilic environments, the TEMPO/TEMPOH couple protects organic molecules from oxidation by establishing an efficient reductive catalytic cycle. This catalytic cycle provides a new understanding of the efficacy of the antioxidant capability of TEMPO in nonaqueous systems and its potential to act as a chemoprotective against radical damage.

Ab initio characterization of coupling strength for all types of dangling-bond pairs on the hydrogen-terminated Si(100)-2 × 1 surface.

Recent work has suggested that coupled silicon dangling bonds sharing an excess electron may serve as building blocks for quantum-cellular-automata cells and quantum computing schemes when constructed on hydrogen-terminated silicon surfaces. In this work, we employ ab initio density-functional theory to examine the details associated with the coupling between two dangling bonds sharing one excess electron and arranged in various configurations on models of phosphorous-doped hydrogen-terminated silicon (100) surfaces. Our results show that the coupling strength depends strongly on the relative orientation of the dangling bonds on the surface and on the separation between them. The orientation of dangling bonds is determined by the anisotropy of the silicon (100) surface, so this feature of the surface is a significant contributing factor to variations in the strength of coupling between dangling bonds. The results demonstrate that simple models for approximating tunneling, such as the Wentzel-Kramer-Brillouin method, which do not incorporate the details of surface structure, are incapable of providing reasonable estimates of tunneling rates between dangling bonds. The results provide guidance to efforts related to the development of dangling-bond based computing elements.

Hydrogen Atom Transfer (HAT) Processes Promoted by the Quinolinimide-N-oxyl Radical. A Kinetic and Theoretical Study.

A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of organic compounds to the quinolinimide-N-oxyl radical (QINO) was performed in CH3CN. The HAT rate constants are significantly higher than those observed with the phthalimide-N-oxyl radical (PINO) as a result of enthalpic and polar effects due to the presence of the N-heteroaromatic ring in QINO. The relevance of polar effects is supported by theoretical calculations conducted for the reactions of the two N-oxyl radicals with toluene, which indicate that the HAT process is characterized by a significant degree of charge transfer permitted by the π-stacking that occurs between the toluene and the N-oxyl aromatic rings in the transition state structures. An increase in the HAT reactivity of QINO was observed in the presence of 0.15 M HClO4 and 0.15 M Mg(ClO4)2 due to the protonation or complexation with the Lewis acid of the pyridine nitrogen that leads to a further decrease in the electron density in the N-oxyl radical. These results fully support the use of N-hydroxyquinolinimide as a convenient substitute for N-hydroxyphthalimide in the catalytic aerobic oxidations of aliphatic hydrocarbons characterized by relatively high C-H bond dissociation energies.

Dispersion Corrections Improve the Accuracy of Both Noncovalent and Covalent Interactions Energies Predicted by a Density-Functional Theory Approximation.

The use of pairwise dispersion corrections together with dispersion-correcting potentials (DCPs) offers a computationally low-cost approach to improving the performance of a density-functional theory based method with respect to the prediction of important chemical properties. In this work, we develop DCPs for the C, H, N, and O atoms for use with the BLYP generalized gradient approximation functional coupled with "D3" pairwise dispersion corrections and 6-31+G(2d,2p) basis sets. The combined approach, referred to as BLYP-D3-DCP, offers generally improved performance over both unadorned BLYP and BLYP with D3 corrections with respect to the prediction of noncovalent binding energies (BEs) and covalent bond dissociation enthalpies (BDEs). Predicted barrier heights for a set of pericyclic and Diels-Alder reactions are improved in some instances, as are organic bond separation reaction energies and radical stabilization energies. It is also shown that the BLYP-D3-DCP approach outperforms B3LYP-D3 in the prediction of many chemical properties, in particular noncovalent BEs and BDEs, suggesting that the addition of D3 and DCP corrections, which have negligible computational cost, to simple density functionals like BLYP may elevate their performance to that of more complex functionals such as B3LYP.

Kinetics of the addition of olefins to Si-centered radicals: the critical role of dispersion interactions revealed by theory and experiment.

Solution-phase rate constants for the addition of selected olefins to the triethylsilyl and tris(trimethylsilyl)silyl radicals are measured using laser-flash photolysis and competition kinetics. The results are compared with predictions from density functional theory (DFT) calculations, both with and without dispersion corrections obtained from the exchange-hole dipole moment (XDM) model. Without a dispersion correction, the rate constants are consistently underestimated; the errors increase with system size, up to 10(6) s(-1) for the largest system considered. Dispersion interactions preferentially stabilize the transition states relative to the separated reactants and bring the DFT-calculated rate constants into excellent agreement with experiment. Thus, dispersion interactions are found to play a key role in determining the kinetics for addition reactions, particularly those involving sterically bulky functional groups.

Absolute rate constants for hydrogen atom transfer from tertiary amides to the cumyloxyl radical: evaluating the role of stereoelectronic effects.

A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from a series of alkanamides to the cumyloxyl radical (CumO(•)) was carried out. With N,N-dialkylformamides HAT preferentially occurs from the formyl C-H bond, while in N-formylpyrrolidine HAT mostly occurs from the ring α-C-H bonds. With the acetamides and the alkanamides almost exclusive HAT from the C-H bonds that are α to nitrogen was observed. The results obtained show that alignment between the C-H bond being broken and the amide π-system can lead to significant increases in the HAT rate constant (kH). This finding points toward the important role of stereoelectronic effects on the HAT reactivity and selectivity. The highest kH values were measured for the reactions of CumO(•) with N-acylpyrrolidines. These substrates have ring α-C-H bonds that are held in a conformation that is optimally aligned with the amide π-system, thus allowing for the relatively facile HAT reaction. The lowest kH value was measured for the reaction of N,N-diisobutylacetamide, wherein the steric bulk associated with the N-isobutyl groups increases the energy barrier required to reach the most suitable conformation for HAT. The experimental results are well supported by the computed BDEs for the C-H bonds of the most representative substrates.

Importance of π-stacking interactions in the hydrogen atom transfer reactions from activated phenols to short-lived N-oxyl radicals.

A kinetic study of the hydrogen atom transfer from activated phenols (2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols, 2,2,5,7,8-pentamethylchroman-6-ol, caffeic acid, and (+)-cathechin) to a series of N-oxyl radical (4-substituted phthalimide-N-oxyl radicals (4-X-PINO), 6-substituted benzotriazole-N-oxyl radicals (6-Y-BTNO), 3-quinazolin-4-one-N-oxyl radical (QONO), and 3-benzotriazin-4-one-N-oxyl radical (BONO)), was carried out by laser flash photolysis in CH3CN. A significant effect of the N-oxyl radical structure on the hydrogen transfer rate constants (kH) was observed with kH values that monotonically increase with increasing NO-H bond dissociation energy (BDENO-H) of the N-hydroxylamines. The analysis of the kinetic data coupled to the results of theoretical calculations indicates that these reactions proceed by a hydrogen atom transfer (HAT) mechanism where the N-oxyl radical and the phenolic aromatic rings adopt a π-stacked arrangement. Theoretical calculations also showed pronounced structural effects of the N-oxyl radicals on the charge transfer occurring in the π-stacked conformation. Comparison of the kH values measured in this study with those previously reported for hydrogen atom transfer to the cumylperoxyl radical indicates that 6-CH3-BTNO is the best N-oxyl radical to be used as a model for evaluating the radical scavenging ability of phenolic antioxidants.

Dispersion-correcting potentials can significantly improve the bond dissociation enthalpies and noncovalent binding energies predicted by density-functional theory.

Dispersion-correcting potentials (DCPs) are atom-centered Gaussian functions that are applied in a manner that is similar to effective core potentials. Previous work on DCPs has focussed on their use as a simple means of improving the ability of conventional density-functional theory methods to predict the binding energies of noncovalently bonded molecular dimers. We show in this work that DCPs developed for use with the LC-ωPBE functional along with 6-31+G(2d,2p) basis sets are capable of simultaneously improving predicted noncovalent binding energies of van der Waals dimer complexes and covalent bond dissociation enthalpies in molecules. Specifically, the DCPs developed herein for the C, H, N, and O atoms provide binding energies for a set of 66 noncovalently bonded molecular dimers (the "S66" set) with a mean absolute error (MAE) of 0.21 kcal/mol, which represents an improvement of more than a factor of 10 over unadorned LC-ωPBE/6-31+G(2d,2p) and almost a factor of two improvement over LC-ωPBE/6-31+G(2d,2p) used in conjunction with the "D3" pairwise dispersion energy corrections. In addition, the DCPs reduce the MAE of calculated X-H and X-Y (X,Y = C, H, N, O) bond dissociation enthalpies for a set of 40 species from 3.2 kcal/mol obtained with unadorned LC-ωPBE/6-31+G(2d,2p) to 1.6 kcal/mol. Our findings demonstrate that broad improvements to the performance of DFT methods may be achievable through the use of DCPs.

Effect of metal ions on the reactions of the cumyloxyl radical with hydrogen atom donors. Fine control on hydrogen abstraction reactivity determined by Lewis acid-base interactions.

A time-resolved kinetic study on the effect of metal ions (M(n+)) on hydrogen abstraction reactions from C-H donor substrates by the cumyloxyl radical (CumO(•)) was carried out in acetonitrile. Metal salt addition was observed to increase the CumO(•) ß-scission rate constant in the order Li(+) > Mg(2+) > Na(+). These effects were explained in terms of the stabilization of the ß-scission transition state determined by Lewis acid-base interactions between M(n+) and the radical. When hydrogen abstraction from 1,4-cyclohexadiene was studied in the presence of LiClO(4) and Mg(ClO(4))(2), a slight increase in rate constant (k(H)) was observed indicating that interaction between M(n+) and CumO(•) can also influence, although to a limited extent, the hydrogen abstraction reactivity of alkoxyl radicals. With Lewis basic C-H donors such as THF and tertiary amines, a decrease in k(H) with increasing Lewis acidity of M(n+) was observed (k(H)(MeCN) > k(H)(Li(+)) > k(H)(Mg(2+))). This behavior was explained in terms of the stronger Lewis acid-base interaction of M(n+) with the substrate as compared to the radical. This interaction reduces the degree of overlap between the α-C-H σ* orbital and a heteroatom lone-pair, increasing the C-H BDE and destabilizing the carbon centered radical formed after abstraction. With tertiary amines, a >2-order of magnitude decrease in k(H) was measured after Mg(ClO(4))(2) addition up to a 1.5:1 amine/Mg(ClO(4))(2) ratio. At higher amine concentrations, very similar k(H) values were measured with and without Mg(ClO(4))(2). These results clearly show that with strong Lewis basic substrates variations in the nature and concentration of M(n+) can dramatically influence k(H), allowing for a fine control of the substrate hydrogen atom donor ability, thus providing a convenient method for C-H deactivation. The implications and generality of these findings are discussed.

Reactions of the cumyloxyl and benzyloxyl radicals with tertiary amides. Hydrogen abstraction selectivity and the role of specific substrate-radical hydrogen bonding.

A time-resolved kinetic study in acetonitrile and a theoretical investigation of hydrogen abstraction reactions from N,N-dimethylformamide (DMF) and N,N-dimethylacetamide (DMA) by the cumyloxyl (CumO(•)) and benzyloxyl (BnO(•)) radicals was carried out. CumO(•) reacts with both substrates by direct hydrogen abstraction. With DMF, abstraction occurs from the formyl and N-methyl C-H bonds, with the formyl being the preferred abstraction site, as indicated by the measured kH/kD ratios and by theory. With DMA, abstraction preferentially occurs from the N-methyl groups, whereas abstraction from the acetyl group represents a minor pathway, in line with the computed C-H BDEs and the kH/kD ratios. The reactions of BnO(•) with both substrates were best described by the rate-limiting formation of hydrogen-bonded prereaction complexes between the BnO(•) α-C-H and the amide oxygen, followed by intramolecular hydrogen abstraction. This mechanism is consistent with the very large increases in reactivity measured on going from CumO(•) to BnO(•) and with the observation of kH/kD ratios close to unity in the reactions of BnO(•). Our modeling supports the different mechanisms proposed for the reactions of CumO(•) and BnO(•) and the importance of specific substrate/radical hydrogen bond interactions, moreover providing information on the hydrogen abstraction selectivity.

Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: the contribution of π-stacking interactions to hydrogen atom transfer rates.

The kinetics of reactions of the phthalimide N-oxyl radical (PINO) with a series of activated phenols (2,2,5,7,8-pentamethylchroman-6-ol (PMC), 2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols) were investigated by laser flash photolysis in CH(3)CN and PhCl in order to establish if the reactions with PINO can provide a useful tool for evaluating the radical scavenging ability of phenolic antioxidants. On the basis of the small values of deuterium kinetic isotope effects, the relatively high and negative ρ values in the Hammett correlations and the results of theoretical calculations, we suggest that these reactions proceed by a hydrogen atom transfer (HAT) mechanism having a significant degree of charge transfer resulting from a π-stacked conformation between PINO and the aromatic ring of the phenols. Kinetic solvent effects were analyzed in detail for the hydrogen transfer from 2,4,6-trimethylphenol to PINO and the data obtained are in accordance with the Snelgrove-Ingold equation for HAT. Experimental rate constants for the reactions of PINO with activated phenols are in accordance with those predicted by applying the Marcus cross relation.

Performance of conventional and dispersion-corrected density-functional theory methods for hydrogen bonding interaction energies.

The approximate CCSD(T)/CBS binding energies for the set of 23 hydrogen-bonded dimers (HB23) of the S66 set reported by Rezác et al. (J. Chem. Theory Comput. 2011, 7, 2427-2438) were expected to be under-estimated based on the known under-binding tendency of the counterpoise correction combined with small basis sets. In this work, we present binding energies for the HB23 set of dimers obtained using a composite approach recently described by Mackie and DiLabio (J. Chem. Phys. 2011, 135, 134318) that averages the counterpoise- and non-counterpoise-corrected energies, while utilizing standard approaches to obtain CCSD(T)/CBS-type energies. The binding energies for the HB23 set are revised upward by an average of 0.12 kcal mol(-1) and as much as 0.35 kcal mol(-1). We use these improved benchmark-level binding energies to evaluate the ability of pure, hybrid, long-range-corrected, and dispersion-corrected density-functional theory (DFT) methods to accurately predict the binding energies of hydrogen-bonded dimers. We find that, in general, the inclusion of dispersion into the DFT approach is required in order to obtain reasonable results for the HB23 set. We find that the dispersion-corrected DFT methods we tested produce results of variable quality, as measured by mean absolute deviation relative to the revised reference values we computed: B97D, 0.57 kcal mol(-1); B3LYP-D3, 0.44 kcal mol(-1); ωB97XD, 0.25 kcal mol(-1); LC-ωPBE-D3, 0.24 kcal mol(-1); M06-2X, 0.21 kcal mol(-1); B3LYP-DCP, 0.23 kcal mol(-1); B971-XDM, 0.18 kcal mol(-1).

Modeling noncovalent radical-molecule interactions using conventional density-functional theory: beware erroneous charge transfer.

Conventional density-functional theory (DFT) has the potential to overbind radical-molecule complexes because of erroneous charge transfer. We examined this behavior by exploring the ability of various DFT approximations to predict fractional charge transfer and by quantifying the overbinding in a series of complexes. It is demonstrated that too much charge is transferred from molecules to radicals when the radical singly unoccupied molecular orbitals are predicted to be erroneously too low in energy relative to the molecule highest occupied molecular orbitals, leading to excessive Coulombic attraction. In this respect, DFT methods formulated with little or no Hartree-Fock exchange perform most poorly. The present results illustrate that the charge-transfer problem is much broader than may have been previously expected and is not limited to conventional (i.e., molecule-molecule) donor-acceptor complexes.