Effect of high coverages on proton transfer in the zeolite/water system

The density functional theory and Hartree–Fock methods were used to investigate the proton transfer reaction for a series of model clusters of zeolite/(H₂O)_n; n=1,2,3, and 4. Without promoted water, the hydrogen-bonded dimer of the water/zeolite system exists as a simple hydrogen-bonded complex, ZOH.(H₂O)₂, and no proton transfer occurs from zeolite to water. The third promoted water, ZOH(H₂O)₂H₂O, was found to induce a pathway for proton transfer, but at least addition two promoted molecules, ZO(H₃O⁺)H₂O(H₂O)₂, must be involved for complete proton transfer from zeolite to H₂O. The results show that the hydronium ion in water cluster adsorbed on zeolite, ZO(H₃O⁺)(H₂O)₃, can considerably affect the structure and bonding of the hydrogen-bonded dimer of water. The OO distance is contracted from 2.818 Å found in the neutral complex, ZOH(H₂O)₄, to 2.777 Å for ion-pair complex, ZO(H₃O⁺)(H₂O)₃. The distance between the oxygen of the hydronium ion and the zeolitic acid site oxygen is predicted to be 2.480 Å which is in good agreement with the experimentally observed value of 2.510 Å. The corresponding density functional adsorption energy of the high coverages of adsorbing molecules on zeolite is calculated to be −9.14 kcal/mol per molecule at B3LYP/6-311+G(d,p) level of theory and compares well with the experimental observation of −8.20 kcal/mol.     

Ab initio study of the two competitive channels HO2 + H → H2 + O2 and HO2 + H → H2O + O

Saddle point geometries and barrier heights have been calculated for the H abstraction reaction HO₂(²A″)+H(²S) → H₂(¹Σ⁺_g)+O₂(³Σ⁻_g) and the concerted H approach-O removing reaction HO₂ (²A″)+H(²S) → H₂O(¹A₁)+O(³P) by using SDCI wavefunctions with a valence double-zeta plus polarization basis set. The saddle points are found to be of C_s symmetry and the barrier heights are respectively 5.3 and 19.8 kcal by including size consistent correction. Moreoever kinetic parameters have been evaluated within the framework of the TST theory. So activation energies and the rate constants are estimated to be respectively 2.3 kcal and 0.4×10⁹ ℓ mol⁻¹ s⁻¹ for the first reaction, 20.0 kcal and 5.4.10⁻⁵ ℓ mol⁻¹ s⁻¹ for the second. Comparison of these results with experimental determinations shows that hydrogen abstraction on HO₂ is an efficient mechanism for the formation of H₂ + O₂, while the concerted mechanism envisaged for the formation of H₂O + O is highly unlikely.     

Multiphoton ionization vibrational state selection of H2O, D2O and HDO

We present a study of single color (2 + 1) resonance-enhanced multiphoton ionization (REMPI) of H₂O, D₂O, and HDO via several Rydberg states lying in the energy range from 80 000 to 86 000 cm⁻¹. Photoelectron spectra (PES) show that the corresponding cations can be vibrationally state-selected for most vibrational states. The exception is the bend of H₂O⁺ and HDO⁺, where mixing in the REMPI intermediate level results in weak ion intensity and only 50% state purity.     

On the existence of the protonated hydronium dication H4O in sulfolane solution

The enthalpy of solvation in sulfolane of the gaseous protonated hydronium dication is estimated as −628 kcal/mol at 298 K. Using literature data, a value ΔH^o = −212 kcal/mol is calculated for the reaction H₃O⁺ + H⁺→ H₄O²⁺ (in sulfolane), supporting the thermodynamic existence of H₄O²⁺ in sulfolane solution, as characterized previously by potentiometric and conductometric titrations. Some aspects of these results are discussed.     

Quantum chemical study of the hydrogen-bonded HXeOH–H2O complex

A combined MP2 and DFT/B3LYP study of the HXeOH–H₂O complex is presented. These computational methods have been used to extract information on the structural, energetical and vibrational properties of the complex. Additionally, we have applied anharmonic vibrational calculations based on the MP2-computed intermolecular potential energy surface. Large perturbations both on the subunit structures and their fundamental vibrational modes are found upon complexation. Large changes of anharmonicity of the HXeOH subunit reflects the perturbation of the molecule's electronic structure. The computed BSSE-corrected interaction energies are −40.23 and −38.94 kJ mol⁻¹ at the CCSD(T)//MP2 and CCSD(T)//B3LYP levels of theory, respectively. The estimated deformation energy contribution to the interaction energy is about 5%, which is very large compared with classical hydrogen-bonded complexes. The topological analysis of the Electron Localization Function (ELF) was applied to study further the hydrogen-bonded interaction between the two complex partners. The obtained interaction pattern suggests that the interaction between HXeOH and H₂O is a typical hydrogen bond interaction driven mainly by electrostatic interactions.     

A Gaussian-2 ab initio study of [C2H5S] ions: III. H2 and CH4 eliminations from CH3CHSH and CH3SCH2

Gaussian-2 ab initio calculations were performed to examine the six modes of unimolecular dissociation of cis-CH₃CHSH⁺ (1⁺), trans-CH₃CHSH⁺ (2⁺), and CH₃SCH₂⁺ (3⁺): 1⁺→CH₃⁺+trans-HCSH (1); 1⁺→CH₃+trans-HCSH⁺ (2); 1⁺→CH₄+HCS⁺ (3); 1⁺→H₂+c-CH₂CHS⁺ (4); 2⁺→H₂+CH₃CS⁺ (5); and 3⁺→H₂+c-CH₂CHS⁺ (6). Reactions (1) and (2) have endothermicities of 584 and 496 kJ mol⁻¹, respectively. Loss of CH₄ from 1⁺ (reaction (3)) proceeds through proton transfer from the S atom to the methyl group, followed by cleavage of the C–C bond. The reaction pathway has an energy barrier of 292 kJ mol⁻¹ and a transition state with a wide spectrum of nonclassical structures. Reaction (4) has a critical energy of 296 kJ mol⁻¹ and it also proceeds through the same proton transfer step as reaction (3), followed by elimination of H_2. Formation of CH₃CS⁺ from 2⁺ (reaction (5)) by loss of H₂ proceeds through protonation of the methine (CH) group, followed by dissociation of the H₂ moiety. Its energy barrier is 276 kJ mol⁻¹. On both the MP2/6-31G* and QCISD/6-31G* potential-energy surfaces, the H₂ 1,1-elimination from 3⁺ (reaction (6)) proceeds via a nonclassical intermediate resembling c-CH₃SCH₂⁺ and has a critical energy of 269 kJ mol⁻¹.     

A crossed-beam study of low energy Ar + H2O collisions: Charge transfer and chemical reaction

Dynamics of Ar⁺ + H₂O collisions, charge transfer (H₂O⁺ formation) and chemical reaction (ArH⁺ formation), was investigated in crossed-beam experiments in the collision energy range 1–3 eV. The charge transfer occurs both by a simple-electron-jump mechanism and in impulsive intimate collisions. The distributions of relative translational energy of the products show that, most probably, the collisions are only slightly superelastic (by about 0.1 eV), and thus the product H₂O⁺ is highly internally excited. Formation of a small amount of H₂O⁺(B²B₂) in very inelastic collisions was observed. The chemical reaction is a direct process with characteristics of the spectator stripping mechanism.     

Vibrational spectrum of I(H2O)

The infrared spectrum of the ionic cluster I⁻(H₂O) was recorded from 3170 to 3800 cm⁻¹ by vibrational predissociation spectroscopy. A strong multiplet observed at 3415 cm⁻¹ and a narrow band at 3710 cm⁻¹ were assigned as a hydrogen-bonded OH stretch and free OH stretch respectively, indicating that H₂O forms a single hydrogen bond with the iodide anion. Ab initio vibrational frequencies and intensities were computed at the second-order Møller-Plesset (MP2) level for the minimum energy configuration, a nearly linear hydrogen-bonded isomer, and for a low-lying saddlepoint, a symmetric C_2v bridged isomer. The spectrum predicted for the hydrogen-bonded isomer agreed well with experiment.     

Synthesis and enthalpy of formation of SrB4O7·3H2O

Hydrated strontium borate, SrB₄O₇·3H₂O, has been synthesized and characterized by XRD, FT-IR, DTA-TG and chemical analysis. The molar enthalpy of solution of SrB₄O₇·3H₂O in 1 mol dm⁻³ HCl(aq) was measured to be (21.15 ± 0.29) kJ mol⁻¹. With incorporation of the previously determined enthalpies of solution of Sr(OH)₂·8H₂O(s) in [HCl(aq) + H₃BO₃(aq)] and H₃BO₃ in HCl(aq), and the enthalpies of formation of H₂O(l), Sr(OH)₂·8H₂O(s) and H₃BO₃(s), the enthalpy of formation of SrB₄O₇·3H₂O was found to be −(4286.7 ± 3.3) kJ mol⁻¹.     

Kinetic study of the reaction H2O2+H→H2O+OH by ab initio and density functional theory calculations

Theoretical investigations on the kinetics of the elementary reaction H₂O₂+H→H₂O+OH were performed using the transition state theory (TST). Ab initio (MP2//CASSCF) and density functional theory (B3LYP) methods were used with large basis set to predict the kinetic parameters; the classical barrier height and the pre-exponential factor. The ZPE and BSSE corrected value of the classical barrier height was predicted to be 4.1 kcal mol⁻¹ for MP2//CASSCF and 4.3 kcal mol⁻¹ for B3LYP calculations. The experimental value fitted from Arrhenius expressions ranges from 3.6 to 3.9 kcal mol⁻¹. Thermal rate constants of the title reaction, based on the ab initio and DFT calculations, was evaluated for temperature ranging from 200 to 2500 K assuming a direct reaction mechanism. The modeled ab initio-TST and DFT–TST rate constants calculated without tunneling were found to be in reasonable agreement with the observed ones indicating that the contribution of the tunneling effect to the reaction was predicted to be unimportant at ambient temperature.     

Low-temperature heat capacity and thermodynamic properties of crystalline [Re2(Ala)4(H2O)8](ClO4)6 (Re = Eu, Er; Ala = alanine)

[Re₂(Ala)₄(H₂O)₈](ClO₄)₆ (Re=Eu, Er; Ala=alanine) were synthesized, and the low-temperature heat capacities of the two complexes were measured with a high-precision adiabatic calorimeter over the temperature range from 80 to 370 K. For [Eu₂(Ala)₄(H₂O)₈](ClO₄)₆, two solid–solid phase transitions were found, one in the temperature range from 234.403 to 249.960 K, with peak temperature 243.050 K, the other in the range from 249.960 to 278.881 K, with peak temperature 270.155 K. For [Er₂(Ala)₄(H₂O)₈](ClO₄)₆, one solid–solid phase transition was observed in the range from 270.696 to 282.156 K, with peak temperature 278.970 K. The molar enthalpy increments, ΔH_m, and entropy increments,ΔS_m, of these phase transitions, were determined to be 455.6 J mol⁻¹, 1.87 J K⁻¹ mol⁻¹ at 243.050 K; 2277 J mol⁻¹, 8.43 J K⁻¹ mol⁻¹ at 270.155 K for [Eu₂(Ala)₄(H₂O)₈](ClO₄)₆; and 4442 J mol⁻¹, 15.92 J K⁻¹ mol⁻¹ at 278.970 K for [Er₂(Ala)₄(H₂O)₈](ClO₄)₆. Thermal decompositions of the two complexes were investigated by use of the thermogravimetric (TG) analysis. A possible mechanism for the thermal decomposition is suggested.     

Electric Field-driven Acid-base Transformation: Proton Transfer from Acid(HBr/HF) to Base(NH3/H2O)

The proton-transfer between ammonia/water and HF/HBr without and with the stimulus of external electric fields(E_ext) was investigated with the ab initio calculations. When external electric field is applied, the proton transfer occurs, resulting in ion-paired H₄N⁺X^- and H₃O⁺X^-(X=Br and F) from hydrogen-bonded complexes in view of the great changes of geometrical structures, dipole moments, frontier molecular orbitals and potential energy surfaces in the critical external electric fields(E_c) of 1.131×107 V/cm for H₃N-HBr, 1.378×108 V/cm for H₃N-HF, 9.358×107 V/cm for H₂O-HBr and 2.304×108 V/cm for H₂O-HF, respectively. Furthermore, one or three excess electrons can trigger the proton transfer from H₃N-HBr and H₃N-HF to H₄N⁺Br^- and H₄N⁺F^-, while two and four excess electrons can induce the proton transfer from H₂O-HBr and H₂O-HF to H₃O⁺Br^- and H₃O⁺F^-, respectively. Compared with that of the analogous NH₃/H₂O-HCl systems, the strength of E_c of proton transfer increases from HBr to HCl and HF for either H₃N-HX or H₂O-HX series, which is understandable by the fact that the acidity sequence is HBr>HCl>HF. And the larger of acidity of conjugated acid, the smaller of needed E_c. On the other hand, the E_c for the systems of NH₃ with a stronger basicity is generally smaller than that of H₂O systems for the same conjugated acid.     

Ab initio and density function theory computational studies of the CH4 + H → CH3 + H2 reaction

The activation barrier for the CH₄ + H → CH₃ + H₂ reaction was evaluated with traditional ab initio and Density Functional Theory (DFT) methods. None of the applied ab initio and DFT methods was able to reproduce the experimental activation barrier of 11.0-12.0 kcal/mol. All ab initio methods (HF, MP2, MP3, MP4, QCISD, QCISD(T), G1, G2, and G2MP2) overestimated the activation energy. The best results were obtained with the G2 and G2MP2 ab initio computational approaches. The zero-point corrected energy was 14.4 kcal mol⁻¹. Some of the exchange DFT methods (HFB) computed energies which were similar to the highly accurate ab initio methods, while the B3LYP hybrid DFT methods underestimated the activation barrier by 3 kcal mol⁻¹. Gradient-corrected DFT methods underestimated the barrier even more. The gradient-corrected DFT method that incorporated the PW91 correlational functional even generated a negative reaction barrier. The suitability of some computational methods for accurately predicting the potential energy surface for this hydrogen radical abstraction reaction was discussed.     

Can chlorine anion catalyze the reaction of HOCl with HCl?

The reaction of HOCl + HCl → Cl₂ + H₂O in the presence of chlorine anion Cl⁻ has been studied using ab initio methods. The overall exothermicity is 15.5 kcal mol⁻¹ and this reaction has been shown to have a high activation barrier of 46.5 kcal mol⁻¹. Cl⁻ is found to catalyze the reaction via the formation of HOCl·Cl⁻, ClH·HOCl·Cl⁻ and Cl⁻·H₂) intermediate ion-molecule complexes or by interacting with a concerted four-center transition state of the reaction of HOCl + HCl.     

Extraction and DFT study on the complexation of H3O with hexaethyl p-tert-butylcalix[6]arene hexaacetate

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium H₃O⁺(aq) + 1· Na⁺(nb)  1·H₃O⁺(nb) + Na⁺(aq) taking place in the two-phase water–nitrobenzene system (1 = hexaethyl p-tert-butylcalix[6]arene hexaacetate; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K_ex (H₃O⁺, 1·Na⁺) = −0.6 ± 0.1. Further, the stability constant of the 1·H₃O⁺ complex in water saturated nitrobenzene was calculated for a temperature of 25 °C as log β_nb (1·H₃O⁺) = 6.8 ± 0. 2. By using quantum mechanical DFT calculations, the most probable structure of the 1·H₃O⁺ complex species was predicted. In this complex, the hydroxonium ion H₃O⁺ is bound partly to three carbonyl oxygen atoms by strong hydrogen bonds and partly to three alternate phenoxy oxygens by somewhat weaker hydrogen bonds.     

Hydrothermal synthesis, crystal structure and characterization of [Zn(H2O)4]2 [H2As6V15O42(H2O)]·2H2O

The compound [Zn(H₂O)₄]₂[H₂As₆V₁₅O₄₂(H₂O)]·2H₂O (1) has been synthesized and characterized by elemental analysis, IR, ESR, magnetic measurement, third-order nonlinear property study and single crystal X-ray diffraction analysis. The compound 1 crystallizes in trigonal space group R3, a=b=12.0601(17) Å, c=33.970(7) Å, γ=120°, V=4278.8(12) Å³, Z=3 and R1(wR2)=0.0512 (0.1171). The crystal structure is constructed from [H₂As₆V₁₅O₄₂(H₂O)]⁴⁻ anions and [Zn(H₂O)₄]²⁺ cations linked through hydrogen bonds into a network. The [H₂As₆V₁₅O₄₂(H₂O)]⁶⁻ cluster consists of 15 VO₅ square pyramids linked by three As₂O₅ handle-like units.     

Ab initio MO study on the global minimum structure of C3H3 anion: propynl-1-yl versus allenyl anions

The geometrical structures of the C₃H⁻₃ anion are surveyed at the coupled-cluster doubles (CCD) level of theory with the aug-cc-pVDZ basis set. To clarify the CCD geometries, the stable two isomers -- propynl-l-yl 1 and allenyl 2 anions -- are further optimized at the coupled-cluster singles, doubles (triples) (CCSD(T)) level of theory both with the aug-cc-pVDZ and aug-cc-pVTZ basis sets. The final energies are calculated at the CCSD(T) and the complete active space self-consistent field (CASSCF) multi-reference internally contracted CI (MRCI) levels of theory with the aug-cc-pVTZ basis set. At the MRCI level of theory including both the corrections due to the cluster energies (MRCI+Q) and the zero-point vibrational energies, the allenyl anion 2 is about 1.3 kcal mol⁻¹ lower in energy than the propynl-l-yl anion 1. These results contrast with the previous theoretical estimates, where the propynl-l-yl anion 1 is 2-3 kcal mol⁻¹ lower in energy than the allenyl anion 2. The activation energies of the intramolecular hydrogen transfer in the 1 → 2 conversion reactions are 63.5 kcal mol⁻¹ at the MRCI+Q level of theory with the aug-cc-pVTZ basis set including the zero-point energy corrections. The adiabatic electron affinity of the planer propargyl (H₂CCCH) radical, which is the global minimum of the C₃H₃ radical, is calculated to be 0.976 eV (after correction for the zero-point energy changes) at the CCSD(T) level of theory with the aug-cc-pVTZ basis set. The present electron affinity is in fairly good agreement with the experimental one (0.893 eV) observed by Oakes and Ellison.     

An ab initio and density functional theory study of the dimethylzinc-hydrogen selenide adduct: (CH3)2Zn:SeH2

The molecular structure (equilibrium geometry) and binding energy of the dimethylzinc (DMZn)-hydrogen selenide (H₂Se) adduct, (CH₃)₂Zn:SeH₂, have been computed with ab initio molecular orbital and density functional theory (DFT) methods and, where possible, compared with experimental results. The structure of the precursors DMZn and H₂Se are perturbed to only a small extent upon adduct formation. (CH₃)₂Zn:SeH₂ was found to be 3 kcal mol⁻¹ less stable than the precursors at the B3LYP/6-311 + G(2d,p)//B3LYP/6-311 + G(2d,p) level of computation, indicating that the (CH₃)₂Zn:SeH₂ adduct is unlikely to be a stable gas-phase species under chemical vapour deposition conditions. Further calculations at the B3LYP/6-311 + G(2d,p)//B3LYP/6-311 + G(2d,p) level of computation suggest that the 1:2 adduct species, (CH₃)₂Zn:(SeH₂)₂, is much less stable than the 1:1 adduct and consequently the precursors by 19 kcal mol⁻¹.     

Proton solvates, H·nH2O·mL, formed by diphosphine dioxides with chlorinated cobalt(III) dicarbollide acid

Interaction of hydrated proton, H₅O₂⁺·(H₂O)₄, in dichloroethane solutions with diphosphine dioxides (L) having methyl (Ph₄Me), ethyl (Ph₄Et) and polyoxyethylene chains (Ph₄PEG) linking two diphenyl phosphine oxide groups has been investigated. A bulky counter ion: chlorinated cobalt(III) bis(dicarbollide), [Co(C₂B₉H₈Cl₃)₂]⁻, minimizes perturbation of the cation. At low concentrations, Ph₄Et and Ph₄PEG form anhydrous 1:1 complexes with (P)O–H⁺–O(P) fragment having very strong symmetrical H-bonds. At these conditions Ph₄Me form another compound, H₅O₂⁺·L(H₂O)₂, due to lower PO basicity and optimal geometry of the chelate cycle. At higher concentrations, Ph₄Me and Ph₄Et form isostructural complexes H₅O₂⁺·L₂, whereas Ph₄PEG forms only a 1:1 complex with proton dihydrate, H₃O⁺·H₂O. In excess of free Ph₄Me and Ph₄Et a water molecule is introduced to the first coordination sphere of H₅O₂⁺ and the average molar ratio L/H₅O₂⁺ of the complexes exceeds 2. The composition of these complexes as a function of L and its concentration is discussed.     

Structures and energetics of C3H6S isomers: a Gaussian-3 ab initio study

Twenty-two isomers/conformers of C₃H₆S^+√ radical cations have been identified and their heats of formation (ΔH_f) at 0 and 298 K have been calculated using the Gaussian-3 (G3) method. Seven of these isomers are known and their ΔH_f data are available in the literature for comparison. The least energy isomer is found to be the thioacetone radical cation (4⁺) with C_2v symmetry. In contrast, the least energy C₃H₆O^+√ isomer is the 1-propen-2-ol radical cation. The G3 ΔH_f298 of 4⁺ is calculated to be 859.4 kJ mol⁻¹, ca. 38 kJ mol⁻¹ higher than the literature value, ≤821 kJ mol⁻¹. For allyl mercaptan radical cation (7⁺), the G3 ΔH_f298 is calculated to be 927.8 kJ mol⁻¹, also not in good agreement with the experimental estimate, 956 kJ mol⁻¹. Upon examining the experimental data and carrying out further calculations, it is shown that the G3 ΔH_f298 values for 4⁺ and 7⁺ should be more reliable than the compiled values. For the five remaining cations with available experimental thermal data, the agreement between the experimental and G3 results ranges from fair to excellent.

Cation CH₃CHSCH₂^+√ (10⁺) has the least energy among the eleven distonic radical cations identified. Their ΔH_f298 values range from 918 to 1151 kJ mol⁻¹. Nevertheless, only one of them, CH₂=SCH₂CH₂^+√ (12⁺), has been observed. Its G3 ΔH_f298 value is 980.9 kJ mol⁻¹, in fair agreement with the experimental result, 990 kJ mol⁻¹.

A couple of reactions involving C₃H₆S^+√ isomers CH₂=SCH₂CH₂^+√ (12⁺) and trimethylene sulfide radical cation (13⁺) have also been studied with the G3 method and the results are consistent with experimental findings.