Abstract
Sophisticated simulation techniques in combination with high-speed computing provide a very powerful tool for the elucidation of structural data and dynamics of solutions, which in several aspects can be superior to any experimental technique. A careful analysis and comparison of simulation results achieved at different levels of accuracy shows that classical simulations, even including 3-body corrections, do not supply sufficiently precise data for all structural details and dynamical processes. As simulation techniques based on small clusters and simple density functionals also fail in the prediction of ion solvate structures, mixed quantum mechanical/molecular mechanical (QM/MM) simulations at Hartree-Fock level with medium-sized basis sets appear as the only viable method within today’s computational affordability to achieve the necessary accuracy for a theoretical approach to the details of microspecies structures and their dynamics in electrolyte solutions. Results of QM/MM-MD simulations for numerous main group and transition metal cations presented here exemplify the capability of this method and clearly show the limits not only of classical simulation techniques, but also of the models being used for the interpretation of experimental measurements.
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References
Ahlrichs, R., M. Ear, M. Haser, H. Horn, and C. Kolmel: 1989, ‘Electronic Structure Calculations on Workstation Computers: The Program System TURBOMOLE’. Chem. Phys.Lett. 162(3), 165–169.
Ahlrichs, R. and M. von Arnim: 1995, ‘TURBOMOLE, parallel implementation of SCF, density functional, and chemical shift modules’. In: E. Clementi and G. Corongiu (eds.): Methodsand Techniques in Computational Chemistry: METECC-95. Cagliari: STEF, Chapt.13,pp.509–554.
Aquiro, M. A. S., W. Clegg, Q. T. Liu, and A. G. Sykes: 1995, ‘Hexaaquatitanium(III) Tris(p-Toluensulfonate) Trihydrate’. Acta Cryst. pp. 560–562.
Aqvist, J. and A. Warshel: 1993, ‘Simulation of Enzyme Reactions Using Valence Bond Force Fields and Other Hybrid Quantum/Classical Approaches’. Chem. Rev. 93(7), 2523–2544.
Armstrong, C.: 1998, ‘The Vision of the pore’. Science 280, 56.
Becke, A. D.: 1998, ‘Exploring the Limits of Gradient Corrections in Density Functional Theory’. J. Comput. Chem. 20, 63–69.
Berendsen, H. J. C., J. P. M. Postma, W. F. van Gunsteren, A. DiNola, and J. R. Haak: 1984, ‘Molecular Dynamics with coupling to an external bath’. J. Phys. Chem. 81, 3684–3690.
Bersuker, I. B.: 2001, ‘Modem Aspects of the Jahn-Teller Effect Theory and Applications To Molecular Problems’. Chem. Rev. 101(4), 1067–1114.
Bopp, P., G. Jansco, and K. Heinzinger: 1983, ‘AN IMPROVED POTENTIAL FOR NON-RIGID WATER MOLECULES IN THE LIQUID PHASE’. Chem. Phys. Lett. 98(2), 129–133.
Car, R. and M. Parinello: 1985, ‘Unified Approach for Molecular-Dynamics and Density Functional Theory’. Phys. Rev. Lett. 55(22), 2471–2474.
Clementi, E., H. Kistenmacher, W. Kolos, and S. Romano: 1980,‘Non-Additivity in Water-Ion-Water Interactions’. Theor. Chim. Acta 55, 257–266.
Cummins, P. L. and J. E. Gready: 1997, ‘Coupled Semiempirical Molecular Orbital and Molecular Mechanics Model (QM/MM) for Organic Molecules in Aqueous Solution’. J. Comput. Chem. 18(12), 1496–1512.
Curtiss, L., J. W. Halley, and X. R. Wang: 1992, ‘Jahn Teller effect in Liquids’. Phys. Rev. Lett. 69(16), 2435–2438.
Gao, J.: 1996, ‘Hybrid Quantum and Molecular Mechanical Simulations: An Alternative Avenue to Solvent Effects in Organics Chemistry’. Ace. Chem. Res. 29(6), 298–305.
Helm, L. and A. E. Merbach: 1999, ‘Water exchange on metal ions: experiments and simulations’. Coord. Chem. Rev. 187, 151–181.
Hertwig, R. H. and W. Koch: 1997, ‘On the parameterization of the local correlation functional. What is Becke-3-LYP?’. Chem. Phys. Lett. 268(5–6), 345–351.
Impey, R. W., P. A. Madden, and I. R. McDonald: 1983, ‘Hydration and Mobility of Ions in Solution’. J. Phys. Chem. 87(25), 5071–5083.
Inada, Y., H. H. Loeffler, and B. M. Rode: 2002a, ‘Librational, vibrational, and exchange motions of water molecules in aqueous Ni(II) solution: Classical and QM/MM molecular dynamics simulations’. Chem. Phys. Lett. 358, 449–458.
Inada, Y., A. M. Mohammed, H. H. Loeffler, and B. M. Rode: 2002b, ‘Hydration Structure and Water Exchange Reaction of Nickel(II) Ion: Classical and QM/Mv Simulations’. J Phys. Chem. A 106(29), 6783–6791.
Kerdcharoen, T., K. R. Liedl, and B. M. Rode: 1996, ‘A QM/MM simulation method applied to the solution of Li+ in liquid ammonia’. Chem. Phys. 211, 313–323.
Loeffler, H. H. and B. M. Rode: 2002, The hydration structure of the lithium ion’. J. Chem.Phys. 117(1), 110–117.
Loeffler, H. H., J. I. Yague, and B. M. Rode: 2002a, ‘Many-Body Effects in Combined Quantum Mechanical/Molecular Mechanical Simulations of Hydrated Manganous Ion’. J. Phys. Chem. A 106, 9529–9532.
Loeffler, H. H., J. I. Yagtie, and B. M. Rode: 2002b, ‘QM/MM-MD Simulation of Hydrated Vanadium(H) Ion’. Chem. Phys. Lett. 363, 367–371.
Marcus, Y: 1987a, ‘Thermodynamics of ion hydration and its interpretation in terms of acommon model’. Pure & Appl. Cham. 59(9), 1093–1101.
Marcus, Y.: 1987b, ‘The Thermodynamics of Solcation of Ions’. J. Chem. Soc., Faraday Trans. 83, 339–349.
Marcus, Y.: 1991, ‘Thermodynamics of Solvation of Ions. Part 5.—Gibbs Free Energy of Hydration at 298.15 K’. J. Chem. Soc., Faraday Trans. 87(17), 2995–2999.
Marini, G. W., K. R. Liedl, and B. M. Rode: 1999, ‘Investigations of Cu2+ Hydration and the Jahn-Teller Effect in Solution by QM/MM Monte Carlo Simulations’. J. Phys. Chem.A 103(51), 11387–11393.
Nagypal, I. and F. Debreczeni: 1984, ‘NMR Relaxation Studies in Solution of Transition Metal Complexes. XL Dynamics of Equilibria in Aqueous Solutions of the Copper(II)-Ammonia System’. Inorg. Chim. Acta 81, 69–74.
Neilson, G. W. and J. E. Enderby: 1989, The Coordination of Metal Aquaions’. In: Advancesin Inorganic Chemistry, Vol. 34. Academic Press, Inc., pp. 195–218.
Ohtaki, H. and T. Radnai: 1993, ‘Structure and Dynamics of Hydrated Ions’. Chem. Rev. 93(3), 1157–1204.
Palinkas, G. and K. Heinzinger: 1986, ‘Hydration Shell Structure of the Calcium Ion’. Chem. Phys. Lett. 126, 251–254.
Pasquarello, A., I. Petri, P. S. Salmon, O. Parisel, R. Car, E. Toth, D. H. Powell, H. E. Fischer, L. Helm, and A. Merbach: 2001, ‘First Solvation Shell of the Cu(II) Aqua Ion: Evidence for Fivefold Coordination’. Science 291, 856–859.
Rode, B. M. and S. M. Islam: 1990, Monte Carlo Simulations with an Improved Potential Function for Cu(II)-Water Including Neighbour Ligand Corrections’. 46, 357–362.
Rode, B. M., C. F. Schwenk, R. Armunanto, T. Remsungnen, and C. Kritayakornupong, ‘unpublished results’.
Samios, J. (ed.): 2002, Novel Approaches to the Dynamics of Liquids: Experiments, Theories and Simulations. Advanced Study Institute.
Schwenk, C. F, H. H. Loeffler, and B. M. Rode: 2001a, ‘Dynamics of the solvation process of Ca2+ in water’. Chem. Phys. Lett. 349(1–2), 99–103.
Schwenk, C. F., H. H. Loeffler, and B. M. Rode: 2001b, ‘Molecular dynamics simulations of Ca + in water: Comparison of a classical simulation including threebody corrections and Born-Oppenheimer ab initio and density functional theory quantum mechanical/molecular mechanics simulations’. J. Chem. Phys. 115(23), 10808–10813.
Stillinger, F. H. and A. Rahman: 1978, ‘Revised central force potentials for water’. J. Chem. Phys. 68(2), 666–670.
Texler, N. R. and B. M. Rode: 1997, ‘Monte Carlo simulations of copper chloride solutions at various concentrations including full 3-body corrections terms’. Chem. Phys. 222, 281–288.
Tongraar, A., K. R. Liedl, and B. M. Rode: 1997, ‘Solvation of Ca2+ in Water Studied by Born-Oppenheimer ab Initio QM/MM Dynamics’. J. Phys. Chem. A 101(35), 6299–6309.
Tongraar, A., K. R. Liedl, and B. M. Rode: 1998a, ‘Born-Oppenheimer ab Initio QM/MM Dynamics Simulations of Na+ and IC in Water: From Structure Making to Structure Breaking Effects’. J. Phys. Chem. A 102(50), 10340–10347.
Tongraar, A., K. R. Liedl, and B. M. Rode: 1998b, ‘The hydration shell structure of Li+ investigated by Born-Oppenheimer ab initio QM/MM dynamics’. Chem. Phys. Lett. 286, 56–64.
Tongraar, A. and B. M. Rode: 1999, ‘Preferential Solvation of Li+ in 18.45% Aqueous Ammonia: A Born-Oppenheimer ab Initio Quantum Mechanics/Molecular Mechanics MD Simulation’. J. Phys. Chem. A 103(42). 8524–8527.
Tongraar, A. and B. M. Rode: 2001, ‘A Born-Oppenheimer Ab Initio Quantum Mechanical/Molecular Mechanical Molecular Dynamics Simulation of Preferential Solvation of Na+ in Aqueous Ammonia Solution’. J.Phys. Chem. A 105(2), 506–510.
Tongraar, A., K. Sagarik, and B. M. Rode: 2001a, ‘Effects of Many-Body Interactions on the Preferential Solvation of Mg2+ in Aqueous Ammonia Solution: A BornOppenheimer ab Initio QM/MM Dynamics Study’. J. Phys. Chem. B 105(54), 10559–10564.
Tongraar, A., K. Sagarik, and B. M. Rode: 2001 b, ‘Non-additive contributions on the Hydration Shell structure of Mg2+ studied by Born-Oppenheimer ab Initio Qnauntum Mechanical/Molecular Mechanical Molecular Dynamics Simulation’. Chem. Phys. Lett. 346, 485–491.
Tongraar, A., K. Sagarik, and B. M. Rode: 2002, Preferential solvation of Ca2+ in aqueous ammonia solution: Classical and combined ab initio quantum mechanical/molecular mechanical molecular dynamics simulations’. 4, 628–634.
Vizoso, S., M. G. Heinzle, and B. M. Rode: 1994, ‘Tlydroxylamine-water: Intermolecular Potential Functionand Simulation of hydrated NH2OH’. J Chem. Soc., Faraday Trans. 90(16), 2377–2344.
von Arnim, M. and R. Ahlrichs: 1998, ‘Performance of Parallel TURBOMOLE for Density Functional Calculations’. J. Comput. Chem. 19(15), 1746–1757.
Yagüe, J. I., A. M. Mohammed, H. Loeffler, and B. M. Rode: 2001, ‘Classical and Mixed Quantum Mechanical/Molecular Mechanical Simulation of Hydrated Manganous Ion’. J. Phys. Chem. A 105(32), 7646–7650.
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Rode, B.M., Schwenk, C.F., Randolf, B.R. (2004). Classical Versus Quantum Mechanical Simulations: The Accuracy of Computer Experiments in Solution Chemistry. In: Samios, J., Durov, V.A. (eds) Novel Approaches to the Structure and Dynamics of Liquids: Experiments, Theories and Simulations. NATO Science Series, vol 133. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-2384-2_3
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DOI: https://doi.org/10.1007/978-1-4020-2384-2_3
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