Phenol O–H bond dissociation energy in water clusters

We are reporting ab initio and density functional theory (DFT) calculations for the phenol O–H bond dissociation energy in the gas phase and in phenol–water clusters. We have tested a series of recently proposed functionals and verified that DFT systematically underestimates the O–H bond dissociation energy of phenol. However, O–H bond dissociation energies in water clusters are in reasonable agreement with experimental data for phenol in solution. We have evaluated electronic difference densities in phenol–water, phenoxy–water, and water, and we are suggesting that the representation of this quantity gives an interesting picture of the electronic density rearrangement induced by hydrogen bond interactions in phenol–water clusters. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Structures and energetics of hydrated oxygen anion clusters

Hydration of the atomic oxygen radical anion is studied with computational electronic structure methods, considering (O(-))(H(2)O)(n) clusters and related proton-transferred (OH(-))(OH)(H(2)O)(n)(-)(1) clusters having n = 1-5. A total of 67 distinct local-minimum structures having various interesting hydrogen bonding motifs are obtained and analyzed. On the basis of the most stable form of each type, (O(-))(H(2)O)(n)) clusters are energetically favored, although for n > or = 3, there is considerable overlap in energy between other members of the (O(-))(H(2)O)(n) family and various members of the (OH(-))(OH)(H(2)O)(n)(-)(1) family. In the lower-energy (O(-))(H(2)O)(n) clusters, the hydrogen bonding arrangement about the oxygen anion center tends to be planar, leaving the oxygen anion p-like orbital containing the unpaired electron uninvolved in hydrogen bonding with any water molecule. In (OH(-))(OH)(H(2)O)(n)(-)(1) clusters, on the other hand, nonplanar arrangements are the rule about the anionic oxygen center that accepts hydrogen bonds. No instances are found of OH(-) acting as a hydrogen bond donor. Those OH bonds that form hydrogen bonds to an anionic O(-) or OH(-) center are significantly stretched from their equilibrium value in isolated water or hydroxyl. A quantitative inverse correlation is established for all hydrogen bonds between the amount of the OH bond stretch and the distance to the other oxygen involved in the hydrogen bond.     

A first principles molecular dynamics study of excess electron and lithium atom solvation in water-ammonia mixed clusters: structural, spectral, and dynamical behaviors of [(H2O)5NH3]- and Li(H2O)5NH3 at finite temperature

First principles molecular dynamics simulations are carried out to investigate the solvation of an excess electron and a lithium atom in mixed water-ammonia cluster (H(2)O)(5)NH(3) at a finite temperature of 150 K. Both [(H(2)O)(5)NH(3)](-) and Li(H(2)O)(5)NH(3) clusters are seen to display substantial hydrogen bond dynamics due to thermal motion leading to many different isomeric structures. Also, the structures of these two clusters are found to be very different from each other and also very different from the corresponding neutral cluster without any excess electron or the metal atom. Spontaneous ionization of Li atom occurs in the case of Li(H(2)O)(5)NH(3). The spatial distribution of the singly occupied molecular orbital shows where and how the excess (or free) electron is primarily localized in these clusters. The populations of single acceptor (A), double acceptor (AA), and free (NIL) type water and ammonia molecules are found to be significantly high. The dangling hydrogens of these type of water or ammonia molecules are found to primarily capture the free electron. It is also found that the free electron binding motifs evolve with time due to thermal fluctuations and the vertical detachment energy of [(H(2)O)(5)NH(3)](-) and vertical ionization energy of Li(H(2)O)(5)NH(3) also change with time along the simulation trajectories. Assignments of the observed peaks in the vibrational power spectra are done and we found a one to one correlation between the time-averaged populations of water and ammonia molecules at different H-bonding sites with the various peaks of power spectra. The frequency-time correlation functions of OH stretch vibrational frequencies of these clusters are also calculated and their decay profiles are analyzed in terms of the dynamics of hydrogen bonded and dangling OH modes. It is found that the hydrogen bond lifetimes in these clusters are almost five to six times longer than that of pure liquid water at room temperature.     

Treatment of dilute clusters of methanol and water by ab initio quantum mechanical calculations

Large molecular clusters can be considered as intermediate states between gas and condensed phases, and information about them can help us understand condensed phases. In this paper, ab initio quantum mechanical methods have been used to examine clusters formed of methanol and water molecules. The main goal was to obtain information about the intermolecular interactions and the structure of methanol/water clusters at the molecular level. The large clusters (CH(4)O...(H(2)O)(12) and H(2)O...(CH(4)O)(10)) containing one molecule of one component (methanol or water) and many (12, 10) molecules of the other component were considered. M?ller-Plesset perturbation theory (MP2) was used in the calculations. Several representative cluster geometries were optimized, and nearest-neighbor interaction energies were calculated for the geometries obtained in the first step. The results of the calculations were compared to the available experimental information regarding the liquid methanol/water mixtures and to the molecular dynamics and Monte Carlo simulations, and good agreement was found. For the CH(4)O...(H(2)O)(12) cluster, it was shown that the molecules of water can be subdivided into two classes: (i) H bonded to the central methanol molecule and (ii) not H bonded to the central methanol molecule. As expected, these two classes exhibited striking energy differences. Although they are located almost the same distance from the carbon atom of the central methanol molecule, they possess very different intermolecular interaction energies with the central molecule. The H bonding constitutes a dominant factor in the hydration of methanol in dilute aqueous solutions. For the H(2)O...(CH(4)O)(10) cluster, it was shown that the central molecule of water has almost three H bonds with the methanol molecules; this result differs from those in the literature that concluded that the average number of H bonds between a central water molecule and methanol molecules in dilute solutions of water in methanol is about two, with the water molecules being incorporated into the chains of methanol. In contrast, the present predictions revealed that the central water molecule is not incorporated into a chain of methanol molecules, but it can be the center of several (2-3) chains of methanol molecules. The molecules of methanol, which are not H bonded to the central water molecule, have characteristics similar to those of the methane molecules around a central water molecule in the H(2)O...(CH(4))(10) cluster. The ab initio quantum mechanical methods employed in this paper have provided detailed information about the H bonds in the clusters investigated. In particular, they provided full information about two types of H bonds between water and methanol molecules (in which the water or the methanol molecule is the proton donor), including information about their energies and lengths. The average numbers of the two types of H bonds in the CH(4)O...(H(2)O)(12) and H(2)O...(CH(4)O)(10) clusters have been calculated. Such information could hardly be obtained with the simulation methods.     

Interactions between organic molecules and water: rotational spectrum of the 1:1 oxetane-water complex

The 1:1 molecular complex between oxetane and water has been investigated by using free-jet millimeter-wave spectroscopy. The rotational spectra of five isotopomers (with H(2)O, D(2)O, DOH, HOD and H(2) (18)O) have been assigned. Partial r(0) and r(s) structures of the complex have been derived. The water moiety lies in the plane of symmetry of oxetane, with the "free" hydrogen E with respect to the ring. The oxetane ring appears to be slightly nonplanar, with the C(beta) carbon tilted on the opposite side of the water unity. The three atoms involved in the hydrogen bond adopt a linear arrangement with an O(ring).H distance of about 1.86 A, and the angle between the COC bisector and the O(ring).H bond being congruent with 106 degrees. Additionally, quantum-chemical calculations for the complex were performed and were found to be in agreement with the experimental results.     

The investigation on the relative stability of different clusters of thiourea dioxide in water using gas phase quantum chemical calculations

The relative stability of different clusters of thiourea dioxide (TDO) in water is examined using gas phase quantum chemical calculations at the MP2 and B3LYP level with 6‐311++G(d,p) basis set. The possible equilibrium structures and other energetic and geometrical data of the thiourea dioxide clusters, TDO‐(H₂O)_n (n is the number of water molecules), are obtained. The calculation results show that a strong interaction exists between thiourea dioxide and water molecules, as indicated by the binding energies of the TDO clusters progressively increased by adding water molecules. PCM model is used to investigate solvent effect of TDO. We obtained a negative hydration energy of ?20.6 kcal mol^?1 and free‐energy change of ?21.0 kcal mol^?1 in hydration process. On the basis of increasing binding energies with adding water molecules and a negative hydration energy by PCM calculation, we conclude thiourea dioxide can dissolve in water molecules. Furthermore, the increases of the C? S bond distance by the addition of water molecules show that the strength of the C? S bonds is attenuated. We find that when the number of water molecules was up to 5, the C? S bonds of the clusters, TDO‐(H₂O)₅ and TDO‐(H₂O)₆ were ruptured. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Structure, stability and spectral signatures of monoprotic carborane acid-water clusters (CBW(n), where n = 1-6)

The gas phase structure, stability, spectra, and proton transfer properties of monoprotic carborane acid-water clusters [CB(11)F(m)H(11-m)(OH(2))(1)]-(H(2)O)(n) (where m = 0, 5, and 10; n = 1-6) have been calculated using density functional theory (DFT) with the Becke's three-parameter hybrid exchange functional and Lee-Yang-Parr correlation functional (B3LYP) using 6-31+G* basis set. Results reveal that Eigen cation defects are found in CBW(n) (where n = 2-6) clusters and these clusters are significantly more stable than the non-Eigen geometry. In addition to the conventional hydrogen bond (H-bond) the role of dihydrogen bond (DHB) and halogen bond (XB) in the stabilization of these clusters can be observed from the molecular graphs derived from the atoms in molecules (AIM) analysis. Spectral information shows the features of Eigen cation and proton oscillation involved in the proton transfer process. The dissociation of proton from the perfluoro derivatives with two water molecules is more favorable when compared to the other derivatives.     

Theoretical study of the desorption of neutral and ionic alkali metal atoms from the excited Li+(H2O)n = 1-4 and Na+(H2O)n = 1-4 cluster models: Electronic excitation charge transfer

In this work, the potential energy curves of several low-lying excited states of M⁺(H₂O)_{n = 1-4} (M = Li and Na) clusters with one M─O bond, related to the stretching of their M─O bond, were calculated in the gas phase. The time-dependent density functional theory and direct-symmetry-adapted cluster-configuration interaction were used in this study separately. Theoretical calculations showed that the charge transfer occurred between M⁺ and (H₂O)_n in the excited clusters so that the neutral metal atom was obtained at the dissociation limit of the potential curves. The excited potential curves of clusters were also calculated in the presence of the electrostatic field of water (EFW), and it was found that the charge transfer was blocked in the presence of EFW. The effect of the size of the (H₂O)_n cluster on the shape of the excited potential curves was investigated to observe how the M─O bond was affected in the excited states depending on the (H₂O)_n size. It was found that the increase in the size of the (H₂O)_n cluster increased the number of bonding excited potential curves. The difference between the electron density of the excited and ground electronic states was calculated to see how the charge transfer was affected by the size of the (H₂O)_n cluster.     

Isolation of an oxomanganese(V) porphyrin intermediate in the reaction of a manganese(III) porphyrin complex and H2O2 in aqueous solution

The reaction of [Mn(TF(4)TMAP)](CF(3)SO(3))(5) (TF(4)TMAP=meso-tetrakis(2,3,5,6-tetrafluoro-N,N,N-trimethyl-4-aniliniumyl)porphinato dianion) with H(2)O(2) (2 equiv) at pH 10.5 and 0 degrees C yielded an oxomanganese(V) porphyrin complex 1 in aqueous solution, whereas an oxomanganese(IV) porphyrin complex 2 was generated in the reactions of tert-alkyl hydroperoxides such as tert-butyl hydroperoxide and 2-methyl-1-phenyl-2-propyl hydroperoxide. Complex 1 was capable of epoxidizing olefins and exchanging its oxygen with H(2) (18)O, whereas 2 did not epoxidize olefins. From the reactions of [Mn(TF(4)TMAP)](5+) with various oxidants in the pH range 3-11, the O-O bond cleavage of hydroperoxides was found to be sensitive to the hydroperoxide substituent and the pH of the reaction solution. Whereas the O-O bond of hydroperoxides containing an electron-donating tert-alkyl group is cleaved homolytically, an electron-withdrawing substituent such as an acyl group in m-chloroperoxybenzoic acid (m-CPBA) facilitates O-O bond heterolysis. The mechanism of the O-O bond cleavage of H(2)O(2) depends on the pH of the reaction solution: O-O bond homolysis prevails at low pH and O-O bond heterolysis becomes a predominant pathway at high pH. The effect of pH on (18)O incorporation from H(2) (18)O into oxygenated products was examined over a wide pH range, by carrying out the epoxidation of carbamazepine (CBZ) with [Mn(TF(4)TMAP)](5+) and KHSO(5) in buffered H(2) (18)O solutions. A high proportion of (18)O was incorporated into the CBZ-10,11-oxide product at all pH values but this proportion was not affected significantly by the pH of the reaction solution.     

C28 (D2): Fullerene growth mechanism

Reactions among the mono‐ to polycyclic carbon clusters have been analyzed using semiempirical AM1 and HF/6‐31G* methods. The C₂₈ (D₂) fullerene cage has been considered. Various precursors are chosen with the appropriate carbon belts. It is observed that the reactions between the precursors and the belts are essentially endoergic in nature, whereas the reactions between the stable intermediates and the final belts are exoergic. Further, the second step of the process is really akin to an annealing mechanism. Also, it has been observed that, in the annealing process, a cascade type of bond‐forming mechanism is in operation. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Photoinduced heterolysis of the carbon-oxygen bond in bichromophoric 1-arylmethyloxy-2-pyridones

Irradiation of the title compound having a 9-anthryl (1a) or a 1-pyrenyl group (1b) in methanol was found to give the heterolytic C---O bond cleavage products: 1-hydroxy-2-pyridone and arylmethyl methyl ether, (which predominate for the reaction of 1a), along with 2-pyridone, aryl-substituted methanol and aryl aldehyde derived from the homolysis of the N---O bond (that mainly occurs in the photolysis of 1b). Spectroscopic analysis of the ground-state and excited singlet-state behavior of 1 revealed that a non-emissive intramolecular exciplex (whose formation rate is much faster in 1a than in 1b) plays a key role in inducing the C---O bond heterolysis.     

Mechanism of dioxygen activation in 2-oxoglutarate-dependent enzymes: a hybrid DFT study

The reaction mechanism for dioxygen activation in 2-oxoglutarate-dependent enzymes has been studied by means of hybrid density functional theory. The results reported here support a mechanism in which all chemical transformations take place on a quintet potential-energy surface. More specifically, the activated dioxygen species attacks the carbonyl group of the co-substrate producing the Fe(II)-persuccinate-CO(2) complex, which readily releases the carbon dioxide molecule. The step in which the Fe(II)-peracid-CO(2) complex is formed is found to be rate-limiting and irreversible. Subsequent heterolysis of the Obond;O bond in the Fe(II)-persuccinate complex proceeds in two one-electron steps and produces the high-valent iron-oxo species Fe(IV)dbond;O, which is most likely to be responsible for oxidative reactions catalyzed by 2-oxoglutarate-dependent enzymes. The concerted pathway for simultaneous Obond;O and Cbond;C bond cleavage on the septet potential-energy surface is found to be less favorable. The relative stability of different forms of the active iron-oxo species is assessed, and the quintet five-coordinate complex is found to be most stable.     

Clusters of hydrated methane sulfonic acid CH3SO3H.(H2O)n (n = 1-5): a theoretical study

Ab initio and density functional methods have been used to examine the structures and energetics of the hydrated clusters of methane sulfonic acid (MSA), CH3SO3H.(H2O)n (n = 1-5). For small clusters with one or two water molecules, the most stable clusters have strong cyclic hydrogen bonds between the proton of OH group in MSA and the water molecules. With three or more water molecules, the proton transfer from MSA to water becomes possible, forming ion-pair structures between CH3SO3- and H3O+ moieties. For MSA.(H2O)3, the energy difference between the most stable ion pair and neutral structures are less than 1 kJ/mol, thus coexistence of neutral and ion-pair isomers are expected. For larger clusters with four and five water molecules, the ion-pair isomers are more stable (>10 kJ/mol) than the neutral ones; thus, proton transfer takes place. The ion-pair clusters can have direct hydrogen bond between CH3SO3- and H3O+ or indirect one through water molecule. For MSA.(H2O)5, the energy difference between ion pairs with direct and indirect hydrogen bonds are less than 1 kJ/mol; namely, the charge separation and acid ionization is energetically possible. The calculated IR spectra of stable isomers of MSA.(H2O)n clusters clearly demonstrate the significant red shift of OH stretching of MSA and hydrogen-bonded OH stretching of water molecules as the size of cluster increases.     

Reinvestigation of intramolecular hydrogen bond in malonaldehyde derivatives: An ab initio,AIM and NBO study

The RAHB systems in malonaldehyde and its derivatives at MP2/ 6‐311++G(d,p) level of theory were studied and their intramolecular hydrogen bond energies by using the related rotamers method was obtained. The topological properties of electron density distribution in O? H···O intramolecular hydrogen bond have been analyzed in term of quantum theory of atoms in molecules (QTAIM). Correlations between the H‐bond strength and topological parameters are probed. The results of QTAIM clearly showed that the linear correlation between the electron density distribution at HB critical point and RAHB ring critical point with the corresponding hydrogen bond energies was obtained. Moreover, it was found a linear correlation between the electronic potential energy density, V(r_cp), and hydrogen bond energy which can be used as a simple equation for evaluation of HB energy in complex RAHB systems. Finally, the similar linear treatment between the geometrical parameters, such as O···O or O? H distance, and Lp(O)→σ*_OH charge transfer energy with the intramolecular hydrogen bond energy is observed. © 2010 Wiley Periodicals, Inc., Int J Quantum Chem, 2011     

Dynamics of dilute water in carbon tetrachloride

A dilute solution of water in a hydrophobic solvent, such as carbon tetrachloride (CCl4), presents an opportunity to study the rotational properties of water without the complicating effects of hydrogen bonds. We report here the results of theoretical, experimental, and semiempirical studies of a 0.03 mole percent solution of water in CCl4. It is shown that for this solution there are negligible water-water interactions or water-CCl4 interactions; theoretical and experimental values for proton NMR chemical shifts (deltaH) are used to confirm the minimal interactions between water and the CCl4. Calculated ab initio values and semiempirical values for oxygen-17 and deuterium quadrupole coupling constants (chi) of water/CCl4 clusters are reported. Experimental values for the 17O, 2H, and 1H NMR spin-lattice relaxation times, T1, of 0.03 mole percent water in dilute CCl4 solution at 291 K are 94+/-3 ms, 7.0+/-0.2 s, and 12.6+/-0.4 s, respectively. These T1 values for bulk water are also referenced. "Experimental" values for the quadrupole coupling constants and relaxation times are used to obtain accurate, experimental values for the rotational correlation times for two orthogonal vectors in the water molecule. The average correlation time, tauc, for the position vector of 17O (orthogonal to the plane of the molecule) in monomer water, H2(17)O, is 91 fs. The average value for the deuterium correlation time for the deuterium vector in 2H2O is 104 fs; this vector is along the OD bond. These values indicate that the motion of monomer water in CCl4 is anisotropic. At 291 K, the oxygen rotational correlation time in bulk 2H2(17)O is 2.4 ps, the deuterium rotational correlation time in the same molecule is 3.25 ps. (Ropp, J.; Lawrence, C.; Farrar, T. C.; Skinner, J. L. J. Am. Chem. Soc. 2001, 123, 8047.) These values are a factor of about 20 longer than the tauc value for dilute monomer water in CCl4.     

A "push-pull" mechanism for heterolytic o-o bond cleavage in hydroperoxo manganese porphyrins

A water-soluble manganese porphyrin, 5,10,15,20-tetrakis-(1,3-dimethylimidazolium-2-yl)porphyrinatomanganese(III) (Mn(III)TDMImP) is shown to react with H(2)O(2) to generate a relatively stable dioxomanganese(V) porphyrin complex (a compound I analog). Stopped-flow kinetic studies revealed Michaelis Menton-type saturation kinetics for H(2)O(2). The visible spectrum of a compound 0 type intermediate, assigned as Mn(III)(OH)(OOH)TDMImP, can be directly observed under saturating H(2)O(2) conditions (Soret band at 428 nm and Q bands at 545 and 578 nm). The rate-determining O-O heterolysis step was found to have a very small activation enthalpy (ΔH(≠) = 4.2 ± 0.2 kcal mol(-1)) and a large, negative activation entropy (ΔS(≠) = -36 ± 1 cal mol(-1) K(-1)). The O-O bond cleavage reaction was pH independent at 8.8 < pH < 10.4 with a first-order rate constant of 66 ± 12 s(-1). These observations indicate that the O-O bond in Mn(III)(OH)(OOH)TDMImP is cleaved via a concerted "push-pull" mechanism. In the transition state, the axial (proximal) (-)OH is partially deprotonated ("push"), while the terminal oxygen in (-)OOH is partially protonated ("pull") as a water molecule is released to the medium. This mechanism is reminiscent of O-O bond cleavage in heme enzymes, such as peroxidases and cytochrome P450, and similar to the fast, reversible O-Br bond breaking and forming reaction mediated by similar manganese porphyrins. The small enthalpy of activation suggests that this O-O bond cleavage could also be made reversible.     

Kinetics and Mechanism of Monomolecular Heterolysis of Commercial Organohalogen Compounds: XXXIV. Solvent Effect on the Heterolysis Rate of 1-Chloro-1-methylcyclohexane. Correlation Analysis of Solvation Effects in Heterolysis of 1-Chloro-1-methylcyclohexane and 1-Chloro-1-methylcyclopentane

The kinetics of heterolysis of 1-chloro-1-methylcyclohexane in 9 protic and 25 aprotic solvents at 25°C were studied by the verdazyl method. The kinetic equation is v = k[RCl] (E1 mechanism). The heterolysis rate of 1-chloro-1-methylcyclohexane in protic solvents is two orders of magnitude lower than that of 1-chloro-1-methylcyclopentane, whereas in low-polarity and nonpolar aprotic solvents the rates are close. A correlation analysis was made to reveal the solvation effects in heterolysis of both chlorides in a set of 9 protic and 25 aprotic solvents, and separately in protic and aprotic solvents.     

Theoretical investigation of gas phase ethanol–(water)n (n = 1–5) clusters and comparison with gas phase pure water clusters (water)n (n = 2–6)

Various properties (such as optimal structures, structural parameters, hydrogen bonds, natural bond orbital charge distributions, binding energies, electron densities at hydrogen bond critical points, cooperative effects, and so on) of gas phase ethanol–(water)_n (n = 1–5) clusters with the change in the number of water molecules have been systematically explored at the MP2/aug‐cc‐pVTZ//MP2/6‐311++G(d,p) computational level. The study of optimal structures shows that the most stable ethanol‐water heterodimer is the one where exists one primary hydrogen bond (O? H…O) and one secondary hydrogen bond (C? H …O) simultaneously. The cyclic geometric pattern formed by the primary hydrogen bonds, where all the molecules are proton acceptor and proton donor simultaneously, is the most stable configuration for ethanol–(water)_n (n = 2–4) clusters, and a transition from two‐dimensional cyclic to three‐dimensional structures occurs at n = 5. At the same time, the cluster stability seems to correlate with the number of primary hydrogen bonds, because the secondary hydrogen bond was extremely weaker than the primary hydrogen bond. Furthermore, the comparison of cooperative effects between ethanol–water clusters and gas phase pure water clusters has been analyzed from two aspects. First of all, for the cyclic structure, the cooperative effect in the former is slightly stronger than that of the latter with the increasing of water molecules. Second, for the ethanol–(water)₅ and (water)₆ structure, the cooperative effect in the former is also correspondingly stronger than that of the latter except for the ethanol–(water)₅ book structure. © 2012 Wiley Periodicals, Inc.     

Microsolvation of DMSO: Density functional study on the structure and polaraizabilities

The structure and stability for the association of water with dimethyl sulfoxide (DMSO) are investigated using the density functional M06‐2X level theory. Stable complexes are formed by the formation of hydrogen bonding between water and oxygen atom of DMSO molecule, while the electrostatic force between water and DMSO plays a vital role in deciding the structure. The water‐DMSO interactions are stronger than the interwater hydrogen bonds, which can be inferred from the shorter DMSO‐water bond distance compared with the water–water bond distance. The calculated solvent association energy does not saturate, and it remains favorable to attach additional water molecules to the existing water network. The calculated IR spectra shifts supports the formation stronger hydrogen bonding, while the electrostatic potential (ESP) plot supports the existence of weaker electrostatic interaction in the studied clusters. The polarizabilities for the ground state clusters were found to increase monotonically with the cluster size. The presence of additional electrostatic bonding between water and DMSO, devastates the linear hydrogen‐bonding network. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011