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Volumn 50, Issue 1, 2011, Pages 299-308

Water versus acetonitrile coordination to uranyl. Density functional study of cooperative polarization effects in solution

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EID: 78650715734     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic101950d     Document Type: Article
Times cited : (50)

References (87)
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    • Barrier for water exchange:,; barrier for "yl-exchange"
    • Barrier for water exchange: Bühl, M. and Kabrede, H. Inorg. Chem. 2006, 45, 3834-3836; barrier for "yl-exchange"
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    • see the Supporting Information for details of the valence basis set used.
    • see the Supporting Information for details of the valence basis set used.
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    • This small-core ECP has been shown to reproduce all-electron scalar relativistic results very well, see
    • This small-core ECP has been shown to reproduce all-electron scalar relativistic results very well, see: Odoh, S. O. and Schreckenbach, G. J. Phys. Chem. A 2010, 114, 1957-1963
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    • The initial CPMD/BLYP simulations in the Parrinello group have afforded good descriptions of liquid water, see for instance:, although potential shortcomings of this functional are now better appreciated, see
    • The initial CPMD/BLYP simulations in the Parrinello group have afforded good descriptions of liquid water, see for instance: Sprik, M., Hutter, J., and Parrinello, M. J. Chem. Phys. 1996, 105, 1142-1152, although potential shortcomings of this functional are now better appreciated, see
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    • Wannier functions are a generalization to infinite periodic systems of the Boys localized orbitals [(c)
    • Silvestrelli, P. L., Marzari, N., Vanderbilt, D., and Parrinello, M. Solid State Commun. 1998, 107, 7; Wannier functions are a generalization to infinite periodic systems of the Boys localized orbitals [(c)
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    • Ed.; Academic Press: New York,; p ]. Wannier centers are the maxima of these localized orbitals denoting the highest negative charge concentration. For a review with some more background on Wannier functions and centers see
    • Boys, S. F. In Quantum Theory of Atoms, Molecules, and the Solid State; Löwdin, P.-O., Ed.; Academic Press: New York, 1966; p 253 ]. Wannier centers are the maxima of these localized orbitals denoting the highest negative charge concentration. For a review with some more background on Wannier functions and centers see
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    • Version 3.13.1; Copyright IBM Corp. 1990-2008, Copyright MPI für Festkörperforschung, Stuttgart, Germany, 1997-2001.
    • CPMD, Version 3.13.1; Copyright IBM Corp. 1990-2008, Copyright MPI für Festkörperforschung, Stuttgart, Germany, 1997-2001.
    • CPMD
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    • We are not claiming that this particular mechanism for ligand exchange would be the most favorable one for the complexes under scrutiny. The limited statistical significance of the single events notwithstanding, we are probing the apparent driving forces for systems in this transient region of phase space.
    • We are not claiming that this particular mechanism for ligand exchange would be the most favorable one for the complexes under scrutiny. The limited statistical significance of the single events notwithstanding, we are probing the apparent driving forces for systems in this transient region of phase space.
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    • The second maximum in the solid red curve above 3 Å stems from the distances between one water H atom and an acetonitrile bound to the other H atom.
    • The second maximum in the solid red curve above 3 Å stems from the distances between one water H atom and an acetonitrile bound to the other H atom.
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    • There are, arguably, many more possible isomers of 1B; it is unlikely, however, that they will be similar or even lower in energy than 1A. 1B can be considered representative for the solvation of the acetonitrile ligands in the CPMD simulation of the actual solution inasmuch as the solvent molecules around these ligands are rather mobile and are frequently found in "bridging" positions similar to the "upper" red MeCN molecule in 1B in Figure 3.
    • There are, arguably, many more possible isomers of 1B; it is unlikely, however, that they will be similar or even lower in energy than 1A. 1B can be considered representative for the solvation of the acetonitrile ligands in the CPMD simulation of the actual solution inasmuch as the solvent molecules around these ligands are rather mobile and are frequently found in "bridging" positions similar to the "upper" red MeCN molecule in 1B in Figure 3.
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    • Despite frequent claims that DFT would not be able to describe hydrogen bonding adequately, the accuracy of geometrical parameters and binding energies of H-bonded systems can be quite respectable: For example, for water clusters, the mean average errors in binding energies are below 1 and 0.5 kcal/mol with BLYP and B3LYP, respectively:, and for the HCNHF complex, a high-level coupled-cluster binding energy is reproduced within 0.5 kcal/mol with B3LYP
    • Despite frequent claims that DFT would not be able to describe hydrogen bonding adequately, the accuracy of geometrical parameters and binding energies of H-bonded systems can be quite respectable: For example, for water clusters, the mean average errors in binding energies are below 1 and 0.5 kcal/mol with BLYP and B3LYP, respectively: Santra, B., Michaelides, A., and Scheffler, M. J. Chem. Phys. 2007, 127, 184104, and for the HCNHF complex, a high-level coupled-cluster binding energy is reproduced within 0.5 kcal/mol with B3LYP
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    • This procedure affords a very simple point-charge model, where the positive atomic charges (screened by the core if present) are placed at the nuclear positions, and negative charges of -2 at the positions of the Wannier centers. The total dipole moment is then calculated from this distribution of point charges.
    • This procedure affords a very simple point-charge model, where the positive atomic charges (screened by the core if present) are placed at the nuclear positions, and negative charges of -2 at the positions of the Wannier centers. The total dipole moment is then calculated from this distribution of point charges.
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    • See: Silvestrelli, P. L. and Parrinello, M. J. Chem. Phys. 1999, 111, 3572-3580, and references cited herein
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    • The importance of polarization effects on the energy profile of uranyl-water dissociation has been noted previously
    • The importance of polarization effects on the energy profile of uranyl-water dissociation has been noted previously: Hemmingsen, L., Amara, P., Ansoborlo, E., and Field, M. J. J. Phys. Chem. A 2000, 104, 4095-4101
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    • These species always contained additional, coordinated anions (such as nitrate or perchlorate from the stock solutions); see, for example
    • These species always contained additional, coordinated anions (such as nitrate or perchlorate from the stock solutions); see, for example, Anbalagan, V., Chien, W., Gresham, G. L., Groenewold, G. S., and Van Stipdonk, M. J. Rapid Commun. Mass. Spectrom. 2004, 18, 3028-3034
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    • 2-NCMe fragments with U-N distances between 2.51 Å and 2.61 Å were found in the Cambridge Structure Database
    • 2-NCMe fragments with U-N distances between 2.51 Å and 2.61 Å were found in the Cambridge Structure Database: Hall, T. J. J. Crystallogr. Spectrosc. Res. 1989, 19, 499
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    • refocodes HEYYAM, SAZDOM, YALSAG, YALSOU
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    • For more accurate PCM results, the second solvation shell may have to be included explicitly, cf. the situation in aqueous uranyl hydrate
    • For more accurate PCM results, the second solvation shell may have to be included explicitly, cf. the situation in aqueous uranyl hydrate: Shamov, G. A. and Schreckenbach, G. J. Phys. Chem. A 2005, 109, 10961-10974
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    • Attraction between the uranyl moiety and second-shell solvent molecules further compresses the first solvation shell ("constriction effect").
    • Attraction between the uranyl moiety and second-shell solvent molecules further compresses the first solvation shell ("constriction effect").
  • 73
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    • Atoms-in-Molecules analyses of water clusters, on the other hand, have indicated charge transfer between atoms as origin of polarization
    • Atoms-in-Molecules analyses of water clusters, on the other hand, have indicated charge transfer between atoms as origin of polarization: Devereux, M. and Popelier, P. L. A. J. Phys. Chem. A 2007, 111, 1536-1544
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    • Devereux, M.1    Popelier, P.L.A.2
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    • 3 fragments in the Cambridge Structure Database with any other atom approaching hydrogen to within the sum of van-der-Waals radii returns ca. 16,400 and 3000 hits, respectively.
    • 3 fragments in the Cambridge Structure Database with any other atom approaching hydrogen to within the sum of van-der-Waals radii returns ca. 16,400 and 3000 hits, respectively.
  • 76
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    • Despite their relative weakness, the importance of C- H···X interactions for determining crystal structures is well recognized; see, for example
    • Despite their relative weakness, the importance of C- H···X interactions for determining crystal structures is well recognized; see, for example, Biradha, K. CrystEngComm 2003, 5, 374-384
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    • A full account of these computations will be published separately.
    • A full account of these computations will be published separately.
  • 86
  • 87
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    • A spherical cavity as in the simple Kirkwood-Onsager model results in a bond elongation in the continuum; see, for example
    • A spherical cavity as in the simple Kirkwood-Onsager model results in a bond elongation in the continuum; see, for example, Martinez, J. M. M., Pappalardo, R. R., Marcos, E. S., Mennucci, B., and Tomasi, J. J. Phys. Chem. B 2002, 106, 1118-1123
    • (2002) J. Phys. Chem. B , vol.106 , pp. 1118-1123
    • Martinez, J.M.M.1    Pappalardo, R.R.2    Marcos, E.S.3    Mennucci, B.4    Tomasi, J.5


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