Theoretical Studies on the Structure, Thermochemistry, Vibrational Spectroscopy, and Other Features of HfX62- (X = F, Cl, Br, I). Electrostatic Energy in Hexahalogenohafnates

Gutowski, Maciej; Rak, Janusz; Dokurno, P.; Blazejowksi, Jerzy

doi:10.1021/ic00104a032

Cited by 14 publications

(7 citation statements)

References 4 publications

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“…commonly proposed in condensed media do not possess bound electronic states as isolated species. Nevertheless, it is often found that the geometries and vibrational frequencies calculated using modest, ab initio , bound-state-oriented methods are in qualitative agreement with corresponding condensed-phase data − on these species. It is believed that by artificially constraining the description of the anion's outermost electrons via a limited basis set, one can approximate the stabilizing influence of the condensed medium's solvent and/or counterions.…”

Section: Comparison Of Gas- and Condensed-phase Propertiesmentioning

confidence: 95%

Small Multiply Charged Anions as Building Blocks in Chemistry

1996

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Section: Comparison Of Gas- and Condensed-phase Propertiesmentioning

confidence: 95%

Small Multiply Charged Anions as Building Blocks in Chemistry

1996

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“…Similar regularities were noted in other systems. [37][38][39] Clearly, then, the charge distribution in polyatomic ions does not substantially affect electrostatic lattice energies. Nevertheless, one would like to know which atomic partial charges are the most suitable.…”

Section: Atomsmentioning

confidence: 99%

Crystal structure and lattice energetics of 10-methylacridinium halides

Storoniak¹,

Krzymiński²,

Dokurno³

et al. 2000

Aust. J. Chem.

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The crystal structures of 10-methylacridinium chloride monohydrate, bromide monohydrate and iodide were determined by X-ray analysis. The compounds crystallize in the triclinic space group, P¯1, with 2 molecules in the unit cell. The molecular arrangement in the crystals revealed that hydrogen bonds (in hydrates) and van der Waals contacts play a significant part in intermolecular interactions. To discover their nature, contributions to the crystal lattice energy arising from electrostatic (the most important since the compounds form ionic crystals), dispersive and repulsive interactions were calculated. Enthalpies of formation of the salts, their stability and susceptibility to decomposition could be predicted from a combination of crystal lattice energies with values of other thermochemical characteristics obtained theoretically or taken from the literature. The role of water in the stabilization of the crystal lattice of the hydrates is also explained. The information gathered has given an insight into the features and behaviour of compounds which can be regarded as models of a large group of aromatic quaternary nitrogen salts.

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“…Numerical tests described in the next section (see also refs , ,− suggested exploring the following sequence of one-electron basis sets: (a) the original SBKJ set (82 contracted Gaussian type orbitals (CGTO)); (b) the SBKJ set supplemented with the one-term of diffuse s and p functions on F, denoted SBKJ+d (106 CGTO's); (c) the SBKJ+d set supplemented with the one-term set of diffuse s, p, and d functions on M and one d polarization function on F, denoted SBKJ+ddp (152 CGTO's); and (d) the SBKJ+ddp set supplemented with the second set of diffuse s and p functions on F and denoted SBKJ+dddp (176 CGTO's).…”

Section: Computational Aspectsmentioning

confidence: 99%

Properties of Closed-Shell, Octahedral, Multiply-Charged Hexafluorometallates MF₆^3-, M = Sc, Y, La, ZrF₆^2-, and TaF₆^-

et al. 1996

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Properties of multiply-charged hexafluorometallates MF6 3-, M = Sc, Y, La, ZrF6 2-, and TaF6 -, have been examined at the SCF, MP2, and Becke3LYP levels of theory using the SBKJ pseudopotentials and extended one-electron basis sets. For MF6 3-, M = Sc, Y, La, our results suggest a different assignment of vibrational transitions than those quoted by Nakamoto1 and recorded by von Becker et al. For the series of isoelectronic complexes, we document that the discrepancy between the theoretical gas phase vibrational frequencies and those measured in condensed phase experiments increases as the Becke3LYP HOMO binding energies become more positive. The frequencies of stretching modes measured in condensed phase experiments are systematically higher than those calculated for the gas phase anions. We suggest that a partial charge transfer from the multiply-charged anions to countercations is responsible for the stiffening of vibrational modes in condensed phase environments. The vertical electron detachment energies were determined at the outer valence Green's function, MP2, and B3LYP levels. The binding energies of hexafluorometallates with respect to the energies of atomic ions were also calculated and only a small contribution of the electron correlation effects was found.

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Theoretical Studies on the Structure, Thermochemistry, Vibrational Spectroscopy, and Other Features of HfX62- (X = F, Cl, Br, I). Electrostatic Energy in Hexahalogenohafnates

Cited by 14 publications

References 4 publications

Small Multiply Charged Anions as Building Blocks in Chemistry

Small Multiply Charged Anions as Building Blocks in Chemistry

Crystal structure and lattice energetics of 10-methylacridinium halides

Properties of Closed-Shell, Octahedral, Multiply-Charged Hexafluorometallates MF₆^3-, M = Sc, Y, La, ZrF₆^2-, and TaF₆^-

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Theoretical Studies on the Structure, Thermochemistry, Vibrational Spectroscopy, and Other Features of HfX62- (X = F, Cl, Br, I). Electrostatic Energy in Hexahalogenohafnates

Cited by 14 publications

References 4 publications

Small Multiply Charged Anions as Building Blocks in Chemistry

Small Multiply Charged Anions as Building Blocks in Chemistry

Crystal structure and lattice energetics of 10-methylacridinium halides

Properties of Closed-Shell, Octahedral, Multiply-Charged Hexafluorometallates MF63-, M = Sc, Y, La, ZrF62-, and TaF6-

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Properties of Closed-Shell, Octahedral, Multiply-Charged Hexafluorometallates MF₆^3-, M = Sc, Y, La, ZrF₆^2-, and TaF₆^-