Theoretical study of the protolytic dissociation of HCl in water clusters

Reaction mechanisms for the acidic dissociation of HCl in water clusters are considered. Intermediates in the reaction are obtained from stationary points on the potential energy surface of the systems HCl–(H2O)n with n=4 and 5. These points have been determined by the B3LYP density functional method in an aug-cc-pVDZ atomic orbital (AO) basis. The total energies of the stationary points are checked by the coupled cluster single-double-triple [CCSD(T)] method in the same AO basis. For the case of n=4 a multibody analysis of the interaction energies is performed by the CCSD(T) method as well as by symmetry adapted perturbation theory. The clusters have a completely dissociated form as their energetically lowest minimum.

[1]  B. Ault,et al.  Infrared spectrum of the water-hydrochloric acid complex in solid nitrogen , 1973 .

[2]  D. Clary,et al.  Interaction of HCl with water clusters: (H2O)nHCl, n = 1-3 , 1995 .

[3]  P. Wormer,et al.  Hydrogen bonding in water clusters: Pair and many-body interactions from symmetry-adapted perturbation theory , 1999 .

[4]  M. Molina,et al.  Antarctic Stratospheric Chemistry of Chlorine Nitrate, Hydrogen Chloride, and Ice: Release of Active Chlorine , 1987, Science.

[5]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[6]  Juan J. Novoa,et al.  A theoretical study of the ionic dissociation of HF, HCl, and H2S in water clusters , 1996 .

[7]  L. Delzeit,et al.  Infrared spectra of hydrogen chloride complexed/ionized in amorphous hydrates and at ice surfaces in the 15-90 K range , 1993 .

[8]  Sl,et al.  Many‐body theory of intermolecular induction interactions , 1994 .

[9]  M. Isakson,et al.  Adsorption and Desorption of HCl on Ice , 1999 .

[10]  F. Geiger,et al.  Ab Initio Study of HOCl, HCl, H2O, and Cl2 Interacting with Four Water Molecules , 1998 .

[11]  T. Chiavassa,et al.  Ab initio model study of the mechanism of hydrogen chloride ionization on ice: Reactivity of C{sub 3}O{sub 2} with ionized HCl , 2000 .

[12]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[13]  D. Maillard,et al.  Spectrum and structure of water-rich water—hydracid complexes from matrix isolation spectroscopy: evidence for proton transfer , 1988 .

[14]  G. Kroes,et al.  Adsorption of HCL on ice under stratospheric conditions: A computational study , 1992 .

[15]  A. van der Avoird,et al.  Symmetry‐adapted perturbation theory of nonadditive three‐body interactions in van der Waals molecules. I. General theory , 1995 .

[16]  G. Kroes,et al.  Sticking of hydrogen chloride and chlorine hydroxide to ice: a computational study , 1992 .

[17]  K. Szalewicz,et al.  Many‐body theory of exchange effects in intermolecular interactions. Density matrix approach and applications to He–F−, He–HF, H2–HF, and Ar–H2 dimers , 1994 .

[18]  P. Ugliengo,et al.  Ab initio study of HCl and HF interaction with crystalline ice. I. Physical adsorption , 1998 .

[19]  Youhei Suzuki,et al.  Structures and stability of hydrated clusters of hydrogen chloride, HCl(H2O)n, n=1–5 , 1998 .

[20]  D. C. Clary,et al.  Time‐dependent wave‐packet studies on the sticking of HCl to an ice surface , 1996 .

[21]  R. Turco,et al.  Application of physical adsorption thermodynamics to heterogeneous chemistry on polar stratospheric clouds , 1991 .

[22]  M. Head‐Gordon,et al.  A fifth-order perturbation comparison of electron correlation theories , 1989 .

[23]  MartynC.R. Symons,et al.  Book reviewsThe chemical physics of solvation : Part B. Spectroscopy of solvation. R.R. Dogonadze, E. Kálmán, A.A. Kornyshev and J. Ulstmp (Editors). Elsevier, Amsterdam, 1986, ISBN 0-444-42674-4, XXVI + 560 pp., US$124.00, Dfl.335.00 , 1988 .

[24]  D. Clary.  Molecules on Ice , 1996, Science.

[25]  P. Wormer,et al.  Many‐body perturbation theory of frequency‐dependent polarizabilities and van der Waals coefficients: Application to H2O–H2O and Ar–NH3 , 1992 .

[26]  Juan J. Novoa,et al.  Kinetics of the Proton Transfer in X···(H2O)4 Clusters (X = H2O, NH3, H2S, and HCl): Evidence of a Concerted Mechanism , 1996 .

[27]  Hans Peter Lüthi,et al.  The MP2 limit correction applied to coupled cluster calculations of the electronic dissociation energies of the hydrogen fluoride and water dimers , 1999 .

[28]  G. Kroes,et al.  New predictions on the sticking of HCl to ice at hyperthermal energies , 1999 .

[29]  Stanisl,et al.  Many‐body perturbation theory of electrostatic interactions between molecules: Comparison with full configuration interaction for four‐electron dimers , 1993 .

[30]  Mark A. Vincent,et al.  Mechanism of Acid Dissociation in Water Clusters: Electronic Structure Studies of (H2O)nHX (n = 4, 7; X = OH, F, HS, HSO3, OOSO2H, OOH·SO2) , 1999 .

[31]  U. Starke,et al.  Molecular Surface Structure of a Low-Temperature Ice Ih(0001) Crystal , 1995 .

[32]  J. Hynes,et al.  Molecular Mechanism of HCl Acid Ionization in Water: Ab Initio Potential Energy Surfaces and Monte Carlo Simulations , 1997 .

[33]  Jeffrey T. Roberts,et al.  Interaction of hydrogen chloride with an ultrathin ice film. Observation of adsorbed and absorbed states , 1994 .

[34]  Hybrid quantum and classical mechanical Monte Carlo simulations of the interaction of hydrogen chloride with solid water clusters , 1997, physics/9710042.

[35]  C. Chipot,et al.  Proton Transfer in the Mono- and the Dihydrated Complexes of HF and HCl: An MP2/6-31+G ab Initio Study in the Self-Consistent Reaction Field Model of Solvation , 1994 .

[36]  Stanisl,et al.  Many‐body symmetry‐adapted perturbation theory of intermolecular interactions. H2O and HF dimers , 1991 .

[37]  R. C. Binning,et al.  AB INITIO MONTE CARLO SIMULATED ANNEALING STUDY OF HCL(H2O)N (N = 3, 4) CLUSTERS , 1999 .