Large polarization but small electron transfer for water around Al3+ in a highly hydrated crystal

Mitev, Pavlin D.; Bakó, Imre; Eriksson, Anders; Hermansson, Kersti

doi:10.1039/c3cp55358b

Cited by 4 publications

(12 citation statements)

References 39 publications

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“…For a detailed discussion of the differences between r e and r 0 (vibrational ground state) distances, and r (OH) and r (OD) distances, see section 3.2 in Ref. [ ].…”

Section: Results and Discussion—the H Location And Vibrationmentioning

confidence: 99%

“…For completeness, also Bader-type dipole moments were calculated, based on the Bader charges and the local dipole moments within each Bader volume, as described in Ref. 20. They are listed in Table 4 along with the Bader charges.…”

Section: Dipole Moment Calculations From Wannier Centersmentioning

confidence: 99%

“…Two of the four crystals in focus here have not been studied by QM methods before in the literature as far as we are aware, namely Na 2 CO 3 ·10H 2 O and MgSO 2 ·11H 2 O, while Mg(SO 4 )·7H 2 O was recently studied by Fang et al, and Al(NO 3 ) 3 ·9H 2 O by us in Refs. [ ].…”

Section: Introductionmentioning

confidence: 99%

“…A selection (i.e., not a complete list) of simple crystalline ionic hydrate studies by means of periodic-crystal calculations in the past decade are those of Refs. [13][14][15][16][17][18][19][20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

“…a) Correlations based on the X-ray and neutron diffraction experiments referred to inTable 1. References to the experimental gas-phase values can be found in Ref 20…”

mentioning

confidence: 99%

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H‐bond and electric field correlations for water in highly hydrated crystals

Sen

Mitev

Eriksson

et al. 2015

Int J of Quantum Chemistry

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We present periodic plane‐wave density functional theory (DFT) Perdew–Burke–Ernzerhof (PBE‐D2) calculations for four highly hydrated crystals, Na2CO3·10H2O, MgSO4·7H2O, MgSO4·11H2O, and Al(NO3)3·9H2O, containing 37 structurally unique water molecules and 74 unique hydrogen bonds. The calculated R(H···O) distances lie in the range 1.60–2.05 Å, the anharmonic OH frequencies in the range 2570–3425 cm−1, and the water dipole moments lie in the range 2.9–4.3 Debye, as calculated from the Wannier function centers and the nuclei. We present the following findings. (i) Our optimized intramolecular r(OH) distances are always larger than the gas‐phase value and thus more accurate than those derived from neutron diffraction experiments; (ii) The local in situ electric field over the molecule, calculated from the positions of the nuclei and the Wannier centers in the surrounding crystal, appears to be a good descriptor of the pertturbation from the water molecule's surroundings as the internal molecular properties (re, ν, μ) are found to correlate well with the crystal‐generated electric field; (iii) We have added DFT‐calculated data points to the well‐known experimental ‘OH frequency versus R(H···O)' correlation curve in a region where the experimental data points are scarce; (iv) For all 37 water molecules, the Wannier centers located in the lone‐pair region, and those located in the OH bonds, displace about equally much due to the polarizing environment. Finally, we propose that our resulting 'OH frequency versus Wannier‐type electric field' correlation curve may constitute a useful tool for predicting OH vibrational frequencies from snapshots from PBE‐D2‐based ab initio molecular dynamics simulations of water‐containing systems. © 2015 Wiley Periodicals, Inc.

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“…For a detailed discussion of the differences between r e and r 0 (vibrational ground state) distances, and r (OH) and r (OD) distances, see section 3.2 in Ref. [ ].…”

Section: Results and Discussion—the H Location And Vibrationmentioning

confidence: 99%

Section: Dipole Moment Calculations From Wannier Centersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…a) Correlations based on the X-ray and neutron diffraction experiments referred to inTable 1. References to the experimental gas-phase values can be found in Ref 20…”

mentioning

confidence: 99%

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H‐bond and electric field correlations for water in highly hydrated crystals

Sen

Mitev

Eriksson

et al. 2015

Int J of Quantum Chemistry

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The influence of cations on the dipole moments of neighboring polar molecules

Bakó

Csókás

Mayer

et al. 2021

Int J of Quantum Chemistry

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In this article we show how the dipole moment of a single molecule in a cluster can be calculated and used for describing the polarization effect. Additionally, we review the accuracy of the calculation of the dipole moment of several simple protic and aprotic molecules. It is shown that the dipole moment of polar (water, methanol, formamide, acetone and acetonitrile) molecules in the neighborhood of a cation is increased primarily by polarization from the bare electrostatic charge of the cation, although the effective value of the latter is somewhat reduced by "back donation" of electrons from neighboring polar molecules. In other words, the classical picture may be viewed as if a point charge slightly smaller than the nominal charge of the cation would be placed at the cation site. It was found that the geometrical arrangement of the polar molecules in the first solvation shell is such that their mutual polarization reduces the dipole moments of individual molecules, so that in some cases they become smaller than the dipole moment of the free protic or aprotic molecule. We conjecture, for the first time, that this behavior, namely the about 10%-20% decrease of the dipole moment of water in the first shell of cations, with the cation itself removed, is essentially a manifestation of the Le Chatelier-Braun principle. We also remark that if the cation-molecule bond order is too large then the calculated dipole moment for these complexes can be questionable, due to the questionable definition of a single molecule within the "supermolecule"-like cluster.

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Effects of H-bond asymmetry on the electronic properties of liquid water – An AIMD analysis

Bakó

Daru

Pothoczki

et al. 2019

Journal of Molecular Liquids

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Three molecular electronic properties (local electronic density of states, molecular dipole moment distribution of the Bader and Wannier types, and net molecular charges) were examined from the collected water trajectories from ab initio molecular dynamics simulations of liquid water at 300 and 350 K using the BLYP-D3 functional. All three molecular electronic properties are found to be sensitive not only to the number of H-bonded neighbours surrounding the molecule but also the nature of the asymmetry of the coordination. That this is the case for the electronic DOS is known from the literature but here we compare the three properties and find that the electronic DOS and the net molecular charge are more affected by the asymmetry than bythe number of H-bonded neighbours. The reverse is true for the dipole moment. Moreover, we consistently find that for all three properties, a 3-coordinated water molecule is more perturbed by accepting two H-bonds and donating 1.

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Large polarization but small electron transfer for water around Al3+ in a highly hydrated crystal

Cited by 4 publications

References 39 publications

H‐bond and electric field correlations for water in highly hydrated crystals

H‐bond and electric field correlations for water in highly hydrated crystals

The influence of cations on the dipole moments of neighboring polar molecules

Effects of H-bond asymmetry on the electronic properties of liquid water – An AIMD analysis

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