In search of CS2(H2O)(n=1-4) clusters.

Gaussian-3 and MP2/aug-cc-pVnZ methods have been used to calculate geometries and thermochemistry of CS(2)(H2O)n, where n=1-4. An extensive molecular dynamics search followed by optimization using these two methods located two dimers, six trimers, six tetramers, and two pentamers. The MP2/aug-cc-pVDZ structure matched best with the experimental result for the CS(2)(H2O) dimer, showing that diffuse functions are necessary to model the interactions found in this complex. For larger CS(2)(H2O)n clusters, the MP2/aug-cc-pVDZ minima are significantly different from the MP2(full)6-31G* structures, revealing that the G3 model chemistry is not suitable for investigation of sulfur containing van der Waals complexes. Based on the MP2/aug-cc-pVTZ free energies, the concentration of saturated water in the atmosphere and the average amount of CS(2) in the atmosphere, the concentrations of these clusters are predicted to be on the order of 10(5) CS(2)(H2O) clusters.cm(-3) and 10(2) CS(2)(H2O)(2) clusters.cm(-3) at 298.15 K. The MP2/aug-cc-pVDZ scaled harmonic and anharmonic frequencies of the most abundant dimer cluster at 298 K are presented, along with the MP2/aug-cc-pVDZ scaled harmonic frequencies for the CS(2)(H(2)O)(n) structures predicted to be present in a low-temperature molecular beam experiment.

[1]  J. E. Headrick,et al.  Physicochemical Properties of Hydrated Complexes in the Earth's Atmosphere , 2000 .

[2]  Junmei Wang,et al.  Development and testing of a general amber force field , 2004, J. Comput. Chem..

[3]  Frank C. Pickard,et al.  Comparison of model chemistry and density functional theory thermochemical predictions with experiment for formation of ionic clusters of the ammonium cation complexed with water and ammonia; atmospheric implications. , 2005, The journal of physical chemistry. A.

[4]  Adrian F. Tuck,et al.  Atmospheric absorption of near infrared and visible solar radiation by the hydrogen bonded water dimer , 2001 .

[5]  G. Shields,et al.  The ability of the Gaussian-2, Gaussian-3, Complete Basis Set–QB3, and Complete Basis Set–APNO model chemistries to model the geometries of small water clusters , 2004 .

[6]  G. Shields,et al.  Pople's Gaussian‐3 model chemistry applied to an investigation of (H2O)8 water clusters , 2005 .

[7]  Vincenzo Barone,et al.  Anharmonic vibrational properties by a fully automated second-order perturbative approach. , 2005, The Journal of chemical physics.

[8]  L. Curtiss,et al.  Gaussian-3 (G3) theory for molecules containing first and second-row atoms , 1998 .

[9]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[10]  G. Shields,et al.  Exploration of the potential energy surfaces, prediction of atmospheric concentrations, and prediction of vibrational spectra for the HO2...(H2O)n (n = 1-2) hydrogen bonded complexes. , 2006, The journal of physical chemistry. A.

[11]  Richard J. Saykally,et al.  Building Solutions--One Molecule at a Time , 2003, Science.

[12]  Michael W. Mahoney,et al.  A five-site model for liquid water and the reproduction of the density anomaly by rigid, nonpolarizable potential functions , 2000 .

[13]  Antonio Vila,et al.  On the different origin of the stabilisation of oxygen versus sulphur H-bond complexes with water , 2003 .

[14]  J. Stewart.  Optimization of parameters for semiempirical methods I. Method , 1989 .

[15]  Ira S. Buckner,et al.  Basis set effects in ab initio studies of sulfur trioxide–water complexes , 2004 .

[16]  M. Mckee,et al.  Theoretical Study of OH and H2O Addition to SO2 , 1997 .

[17]  D. Donaldson,et al.  AB INITIO STUDY OF SO2 + H2O , 1998 .

[18]  G. Shields,et al.  Thermodynamics of forming water clusters at various temperatures and pressures by Gaussian-2, Gaussian-3, complete basis set-QB3, and complete basis set-APNO model chemistries; implications for atmospheric chemistry. , 2004, Journal of the American Chemical Society.

[19]  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 .

[20]  G. Shields,et al.  Prediction of accurate anharmonic experimental vibrational frequencies for water clusters, (H2O)n, n=2-5. , 2006, The journal of physical chemistry. A.

[21]  M. Molina,et al.  Gas Phase Reaction of Sulfur Trioxide with Water Vapor , 1994 .

[22]  Frank C. Pickard,et al.  Comparison of CBS-QB3, CBS-APNO, G2, and G3 thermochemical predictions with experiment for formation of ionic clusters of hydronium and hydroxide ions complexed with water. , 2005, The Journal of chemical physics.

[23]  G. Shields,et al.  Global search for minimum energy (H2O)n clusters, n = 3-5. , 2005, The journal of physical chemistry. A.

[24]  Angela K. Wilson,et al.  Harmonic Vibrational Frequencies: Scaling Factors for HF, B3LYP, and MP2 Methods in Combination with Correlation Consistent Basis Sets , 2004 .

[25]  V. Vaida,et al.  Hydrated Complexes: Relevance to Atmospheric Chemistry and Climate , 2003 .

[26]  K. Pfeilsticker,et al.  Atmospheric Detection of Water Dimers via Near-Infrared Absorption , 2003, Science.

[27]  K. Morokuma,et al.  AB INITIO MOLECULAR ORBITAL STUDY OF THE MECHANISM OF THE GAS PHASE REACTION SO3 + H2O : IMPORTANCE OF THE SECOND WATER MOLECULE , 1994 .

[28]  Holger Gohlke,et al.  The Amber biomolecular simulation programs , 2005, J. Comput. Chem..

[29]  K. Liedl,et al.  Toward elimination of discrepancies between theory and experiment: the rate constant of the atmospheric conversion of SO3 to H2SO4. , 2000, Proceedings of the National Academy of Sciences of the United States of America.

[30]  F. Lovas,et al.  Microwave Fourier transform spectrum of the water-carbon disulfide complex , 1993 .

[31]  R. Stull,et al.  Meteorology for Scientists and Engineers , 1999 .

[32]  M. Wójcik,et al.  Ab initio study of energies, structures and vibrational spectra of the complexes of water with carbon oxysulfide and nitrous oxide , 2001 .

[33]  R. Suenram,et al.  The microwave spectrum and structure of the H2O–SO2 complex , 1989 .

[34]  M. Molina,et al.  Pressure and Temperature Dependence of the Gas-Phase Reaction of SO3 with H2O and the Heterogeneous Reaction of SO3 with H2O/H2SO4 Surfaces , 1997 .

[35]  G. Shields,et al.  Do hydroxyl radical-water clusters, OH(H2O)n, n = 1-5, exist in the atmosphere? , 2006, The journal of physical chemistry. A.

[36]  O. Schrems,et al.  Ab initio and DFT study of the molecular mechanisms of SO3 and SOCl2 rections with water in the gas phase , 2004 .

[37]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1997 .

[38]  J. S. Francisco,et al.  Experimental Evidence for the Existence of the HO 2 -H 2 O Complex , 2000 .

[39]  Yoshio Tatamitani,et al.  Microwave Fourier transform spectrum of the water-carbonyl sulfide complex. , 2004, The Journal of chemical physics.