Interpretation of the Moessbauer spectra of mixed-hexahalo complexes of tin(IV)

Clausen, C.A.; Good, Mary L.

doi:10.1021/ic50086a025

Cited by 41 publications

(10 citation statements)

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“…The IS values of the Sn 4+ ions with I -, Brand Clenvironments in the Cs 2 SnX 6 series also follow a trend (similar as that found for the "model" SnX 4 compounds, 22 where the decrease in IS values is related to the decrease in 5s electron density at the 119 Sn nucleus, due to the decreasing covalency of the Sn-X bond as the p-orbital configuration changes from 5p (I) to 4p (Br) to 3p (Cl). 23 On the other hand, the spectra of II A second trend that appears from the XANES spectra comes from the intensity of the exciton peak as a function of the halide ligand.…”

Section: A the Mössbauer Spectroscopy And Its Dft Interpretationsupporting

confidence: 76%

Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

Dalpian

Liu

Stoumpos

et al. 2017

Phys. Rev. Materials

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Shifting the Fermi energy in solids by doping, defect formation or gating generally results in changes in the charge density distribution, which reflect the ability of the bonding pattern in solids to adjust to such external perturbations. In the traditional textbook chemistry, such changes are often described by the formal oxidation states (FOS) whereby a single atom type is presumed to absorb the full burden of the perturbation (change in charge) of the whole compound. In the present paper, we analyze the changes in the position-dependence charge density due to shifts of the Fermi energy on a general physical basis, comparing with the view of the FOS picture. We use the halide perovskites CsSnX 3 (X=F, Cl, Br, I) as examples for studying the general principle. When the solar absorber CsSnI 3 (termed 113) loses 50 % of its Sn atoms, thereby forming the ordered vacancy compound Cs 2 SnI 6 (termed 216), the Sn is said in the FOS picture to change from Sn 2+ to Sn 4+ . To understand the electronic properties of these two groups we studied the 113/216 compound pairs CsSnCl 3 /Cs 2 SnCl 6 , CsSnBr 3 /Cs 2 SnBr 6 , and CsSnI 3 /Cs 2 SnI 6 , complementing them by CsSnF 3 /Cs 2 SnF 6 in the hypothetical cubic structure for completing the chemical trends. These materials were also synthesized by chemical routes and characterized by X-ray diffraction, 119 Sn-Mössbauer spectroscopy and K-edge X-ray Absorption Spectroscopy. We find that indeed in going from 113 to 216 (equivalent to the introduction of two holes per unit) there is a decrease in the s charge on Sn, in agreement with the FOS picture. However, at the same time, we observe an increase of the p charge via downshift of the otherwise unoccupied p level, an effect that tends to replenish much of the lost s charge. At the end, the change in the charge on the Sn site as a result of adding two holes to the unit cell is rather small. This effect is theoretically explained as a 'self-regulating response ' [H. Raebiger, S. Lany, and A. Zunger, Nature 453, 763 (2008)] whereby the system re-hybridizes to minimize the effect of the charge perturbation created by vacancy formation. Rather than having a single preselected atom (here, Sn) absorb the full brunt of the perturbation producing two holes/cell, we find that the holes are distributed in a complex pattern throughout the octahedral systems of X 6 ligands, forming hole orbitals with some specific symmetries. This clarifies the relation between FOS and charge transfer that can be applied to a wide variety of materials.2

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Section: A the Mössbauer Spectroscopy And Its Dft Interpretationsupporting

confidence: 76%

Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

Dalpian

Liu

Stoumpos

et al. 2017

Phys. Rev. Materials

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“…Generally, however, experiments typically focus on atoms or groups of atoms bound in a molecule, making it desirable to be able to correlate results from such measurements to electronegativity. For example, experimental observables measured by a variety of techniques, including bond-stretching frequencies obtained from infrared spectroscopy, 18 NMR chemical shifts, 19 isomer shifts in Mössbauer spectroscopy, 20 and substituent constants due to field-induced effects (F 21 and σ F 22 ) in benzene derivatives, have been shown to correlate with electronegativity. Numerous reports also have correlated χ , and its related parameters (e.g., Hammett constants, which incorporate electronegativity and other factors such as polarizability and inductive effects), to core or valence binding energies measured via xray or UV photoelectron spectroscopy (XPS or UPS).…”

Section: Q N ) =mentioning

confidence: 99%

A new method to derive electronegativity from resonant inelastic x-ray scattering

Carniato

Journel

Guillemin

et al. 2012

The Journal of Chemical Physics

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Electronegativity is a well-known property of atoms and substituent groups. Because there is no direct way to measure it, establishing a useful scale for electronegativity often entails correlating it to another chemical parameter; a wide variety of methods have been proposed over the past 80 years to do just that. This work reports a new approach that connects electronegativity to a spectroscopic parameter derived from resonant inelastic x-ray scattering. The new method is demonstrated using a series of chlorine-containing compounds, focusing on the Cl 2p(-1)LUMO(1) electronic states reached after Cl 1s → LUMO core excitation and subsequent KL radiative decay. Based on an electron-density analysis of the LUMOs, the relative weights of the Cl 2p(z) atomic orbital contributing to the Cl 2p(3/2) molecular spin-orbit components are shown to yield a linear electronegativity scale consistent with previous approaches.

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“…The QS of SnFJMeCN), ( [27], v SnO should be around 513 cni-l. This is in the range of v SnF ( Table 3), and so strong couplings are expected.…”

Section: Resultsmentioning

confidence: 98%

Reactions of Tin(II) Fluoride with Halogens

Tudela

Rey

1989

Zeitschrift anorg allge chemie

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By oxidative‐addition of X2 (X = Cl, Br) to SnF2 in acetonitrile, monomeric SnF2Cl2(MeCN)2 and polymeric or oligomeric SnF2Br2(MeCN)2 are obtained. The corrected v CN IR frequencies provide a good indication of the Sn–N bond strength. The reactions of SnF2 with Br2 and I2 in the presence of DMSO, and with I2 in the presence of pyridine yield the disproportionation products rather than the mixed‐halide compounds. That suggests that the stability of the mixedhalide compounds decreases when the difference between the halides increases. The reaction of SnF2 with I2 in acetonitrile gives rise to SnF4(MeCN)2, and provides a simple and inexpensive route to SnF4 and its complexes, as MeCN is lost under mild conditions or substituted by other ligands. In this way we have prepared SnF4L2 (L = DMF, DMSO, THF, Py). The structure of the compounds is discussed in terms of the IR and 119Sn Mössbauer spectra and, in the case of SnF4L2, the Mössbauer isomer shift and the IR v Sn–F compared to the corresponding SnCl4L2 compounds.

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Interpretation of the Moessbauer spectra of mixed-hexahalo complexes of tin(IV)

Cited by 41 publications

References 0 publications

Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

Changes in charge density vs changes in formal oxidation states: The case of Sn halide perovskites and their ordered vacancy analogues

A new method to derive electronegativity from resonant inelastic x-ray scattering

Reactions of Tin(II) Fluoride with Halogens

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