Study of Cl−(H2O)n (n = 1–4) using basin‐hopping method coupled with density functional theory

Cl−(H2O)n (n = 1–4) clusters were investigated using a basin‐hopping (BH) algorithm coupled with density functional theory (DFT). Structures, energetics, thermodynamics, vertical detachment energies, and vibrational frequencies were obtained from high‐level ab initio calculations. Through comparisons with previous theoretical and experimental data, it was demonstrated that the combination of the BH method and DFT could accurately predict the global and local minima of Cl−(H2O)n (n = 1–4). Additionally, to optimize larger Cl−(H2O)n (n > 4) clusters, several popular density functionals as well as DF‐LMP2 (Schütz et al., J. Chem. Phys. 2004, 121, 737) (second‐order Møller‐Plesset perturbation theory using local and density fitting approximations) were tested with appropriate basis sets through comparisons with MP2 optimized results. DF‐LMP2 will be used in future studies because its overall performance in describing the relative binding energies and the geometrical parameters of Cl−(H2O)n (n = 1–4) was outstanding in this study. © 2013 Wiley Periodicals, Inc.

[1]  Xiao Cheng Zeng,et al.  Isomer identification and resolution in small gold clusters. , 2010, The Journal of chemical physics.

[2]  Han Myoung Lee,et al.  Comparative ab initio study of the structures, energetics and spectra of X−⋅(H2O)n=1–4 [X=F, Cl, Br, I] clusters , 2000 .

[3]  Frederick R Manby,et al.  Analytical energy gradients for local second-order Møller-Plesset perturbation theory using density fitting approximations. , 2004, The Journal of chemical physics.

[4]  Frederick R. Manby,et al.  Fast Hartree–Fock theory using local density fitting approximations , 2004 .

[5]  S. Goedecker.  Minima hopping: an efficient search method for the global minimum of the potential energy surface of complex molecular systems. , 2004, The Journal of chemical physics.

[6]  Shinichi Yamabe,et al.  Solvation of halide ions with water and acetonitrile in the gas phase , 1988 .

[7]  Howard R. Mayne,et al.  Global geometry optimization of atomic clusters using a modified genetic algorithm in space‐fixed coordinates , 1996 .

[8]  H. Werner,et al.  Chapter 4 On the Selection of Domains and Orbital Pairs in Local Correlation Treatments , 2006 .

[9]  J. Doye,et al.  Global Optimization by Basin-Hopping and the Lowest Energy Structures of Lennard-Jones Clusters Containing up to 110 Atoms , 1997, cond-mat/9803344.

[10]  Soumya Ganguly Neogi,et al.  Structure and spectroscopy of water‐fluoride microclusters: A combined genetic algorithm and DFT‐based study , 2012, J. Comput. Chem..

[11]  Marvin Johnson,et al.  An infrared study of the competition between hydrogen-bond networking and ionic solvation: Halide-dependent distortions of the water trimer in the X−⋅(H2O)3, (X=Cl, Br, I) systems , 1999 .

[12]  Iwao Watanabe,et al.  Vertical ionization potentials and CTTS energies for anions in water and acetonitrile , 1995 .

[13]  William A. Goddard,et al.  Bonding Properties of the Water Dimer: A Comparative Study of Density Functional Theories , 2004 .

[14]  Gregory S. Tschumper,et al.  Characterizing the potential energy surface of the water dimer with DFT: failures of some popular functionals for hydrogen bonding. , 2006, The journal of physical chemistry. A.

[15]  Soumya Ganguly Neogi,et al.  Structure and spectroscopic aspects of water‐halide ion clusters: A study based on a conjunction of stochastic and quantum chemical methods , 2013, J. Comput. Chem..

[16]  Kevin E. Riley,et al.  What is the best density functional to describe water clusters: evaluation of widely used density functionals with various basis sets for (H2O)n (n = 1–10) , 2011 .

[17]  Martin Schütz,et al.  Molpro: a general‐purpose quantum chemistry program package , 2012 .

[18]  Jerzy Leszczynski,et al.  Properties and nature of interactions in Cl−(H2O)nn=1,6 clusters: a theoretical study , 2000 .

[19]  Marvin Johnson,et al.  Precursor of the Iaq− charge‐transfer‐to‐solvent (CTTS) band in I−⋅(H2O)n clusters , 1996 .

[20]  Nicholas A Besley,et al.  Structural optimization of molecular clusters with density functional theory combined with basin hopping. , 2012, The Journal of chemical physics.

[21]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[22]  Stefan Grimme,et al.  Accurate description of van der Waals complexes by density functional theory including empirical corrections , 2004, J. Comput. Chem..

[23]  Wei Huang,et al.  Probing the interactions of O(2) with small gold cluster anions (Au(n)(-), n = 1-7): chemisorption vs physisorption. , 2010, Journal of the American Chemical Society.

[24]  Alexander I Boldyrev,et al.  A concentric planar doubly π-aromatic B₁₉⁻ cluster. , 2010, Nature chemistry.

[25]  Han Myoung Lee,et al.  Structures and spectra of iodide-water clusters I-(H2O)(n=1-6): An ab initio study , 2001 .

[26]  Marvin Johnson,et al.  Vibrational Spectroscopy of the Ionic Hydrogen Bond: Fermi Resonances and Ion−Molecule Stretching Frequencies in the Binary X-·H2O (X = Cl, Br, I) Complexes via Argon Predissociation Spectroscopy , 1998 .

[27]  Gil Markovich,et al.  Photoelectron spectroscopy of Cl−, Br−, and I− solvated in water clusters , 1994 .

[28]  Steen Brøndsted Nielsen,et al.  Spectroscopic Observation of Ion-Induced Water Dimer Dissociation in the X-·(H2O)2 (X = F, Cl, Br, I) Clusters , 1999 .

[29]  Sotiris S. Xantheas,et al.  Quantitative Description of Hydrogen Bonding in Chloride−Water Clusters , 1996 .

[30]  B. Delley.  An all‐electron numerical method for solving the local density functional for polyatomic molecules , 1990 .

[31]  Jong-Ho Choi,et al.  Vibrational Spectroscopy of the Cl.(H2O)n Anionic Clusters, n = 1-5 , 1998 .

[32]  M. Arshadi,et al.  Hydration of the halide negative ions in the gas phase. II. Comparison of hydration energies for the alkali positive and halide negative ions , 1970 .

[33]  Wei Huang,et al.  Relativistic effects and the unique low-symmetry structures of gold nanoclusters. , 2008, ACS nano.

[34]  Nicholas A Besley,et al.  Structure and bonding in ionized water clusters. , 2013, The journal of physical chemistry. A.

[35]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[36]  Wei Huang,et al.  Probing the 2D to 3D structural transition in gold cluster anions using argon tagging. , 2009, Physical review letters.

[37]  Jordi Mestres,et al.  Genetic algorithms: A robust scheme for geometry optimizations and global minimum structure problems , 1995, J. Comput. Chem..

[38]  Ho,et al.  Molecular geometry optimization with a genetic algorithm. , 1995, Physical review letters.

[39]  Han Myoung Lee,et al.  Structures, spectra, and electronic properties of halide-water pentamers and hexamers, X−(H2O)5,6 (X=F,Cl,Br,I): Ab initio study , 2002 .