Experimental (FT-IR and FT-RS) and theoretical (DFT) studies of molecular structure and internal modes of [Mn(NH3)6](NO3)2

Drużbicki, Kacper; Mikuli, Edward

doi:10.1016/j.saa.2010.06.001

Cited by 19 publications

(6 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…To mitigate the above difficulties, as well as to avoid the arbitrariness and deficiencies of semiempirical vdW corrections, we have adopted a fixed-cell methodology, using the cell parameters measured with SXRD at 120 K. We have shown earlier a high robustness and versatility of such an approach in combination with standard (PBE) and hard-GGA (rPBE) GGA-type XC functionals for the prediction of the vibrational spectra. The adequacy of the approach has been confirmed for a number of diversely bonded, flexible, and complex molecular as well as ionic systems, studied over a broad frequency range and compared to both optical and INS data. ,− This is also corroborated by our previous experience in the modeling of solids containing nitrate ions , and nitro moieties. , The adequacy of the adopted methodology in our particular case is examined in Figures S7 and S8, showing a zone-center mechanical stability of the Pmmn model. The reliability of our computational methodology is confirmed further in Figure , presenting theoretical spectra at intermediate energies calculated for both [N 0 0 2 2 ][NO 3 ] and [N 0 0 D D ][NO 3 ] specimens.…”

Section: Resultssupporting

confidence: 69%

“…The adequacy of the approach has been confirmed for a number of diversely bonded, flexible, and complex molecular as well as ionic systems, studied over a broad frequency range and compared to both optical and INS data. 56,68−72 This is also corroborated by our previous experience in the modeling of solids containing nitrate ions 55,73 and nitro moieties. 74,75 The adequacy of the adopted methodology in our particular case is examined in Figures S7 and S8, showing a zone-center mechanical stability of the Pmmn model.…”

Section: Resultssupporting

confidence: 65%

See 1 more Smart Citation

Spectroscopic Signatures of Hydrogen-Bonding Motifs in Protonic Ionic Liquid Systems: Insights from Diethylammonium Nitrate in the Solid State

et al. 2021

Self Cite

View full text Add to dashboard Cite

Diethylammonium nitrate, [N 0 0 2 2 ][NO 3 ], and its perdeuterated analogue, [N D D 2 2 ] [NO 3 ], were structurally characterized and studied by infrared, Raman, and inelastic neutron scattering (INS) spectroscopy. Using these experimental data along with state-of-the-art computational materials modeling, we report unambiguous spectroscopic signatures of hydrogen-bonding interactions between the two counterions. An exhaustive assignment of the spectral features observed with each technique has been provided, and a number of distinct modes related to NH···O dynamics have been identified. We put a particular emphasis on a detailed interpretation of the high-resolution, broadband INS experiments. In particular, the INS data highlight the importance of conformational degrees of freedom within the alkyl chains, a ubiquitous feature of ionic liquid (IL) systems. These findings also enable an in-depth physicochemical understanding of protonic IL systems, a first and necessary step to the tailoring of hydrogen-bonding networks in this important class of materials.

show abstract

Section: Resultssupporting

confidence: 69%

Section: Resultssupporting

confidence: 65%

Spectroscopic Signatures of Hydrogen-Bonding Motifs in Protonic Ionic Liquid Systems: Insights from Diethylammonium Nitrate in the Solid State

et al. 2021

Self Cite

View full text Add to dashboard Cite

show abstract

“…The assignments of these vibrations were proposed by comparing their frequencies with the literature data collected for titled compounds and similar ionic perchlorate amminemetal(II) complexes [10,[23][24][25][26][27]. All characteristic bands frequencies of the internal vibrations were found.…”

Section: Resultsmentioning

confidence: 96%

Thermal properties of polycrystalline [Mn(NH3)6](ClO4)2

Hetmańczyk

Migdał-Mikuli

et al. 2014

J Therm Anal Calorim

Self Cite

View full text Add to dashboard Cite

The X-ray powder diffraction (XRPD) pattern of [Mn(NH 3 ) 6 ](ClO 4 ) 2 at room temperature can be indexed in the regular (cubic) system (Fm3m space group) with lattice cell parameter a = 11.5729 Å and with four molecules per unit cell. The XRPD pattern at 100 K is evidently different, and it indicates lowering of the crystal structure. One phase transition at T h C1 = 143.5 K (on heating) and at T c C1 = 137.6 K (on cooling) was detected by DSC for [Mn(NH 3 ) 6 ](ClO 4 ) 2 in the range of 120-300 K. The following thermodynamic parameters for phase I $ phase II transition were obtained: DH = 3.1 ± 0.2 kJ mol -1 and DS = 21.6 ± 0.3 J mol -1 K -1 . The large value of entropy changes (DS) indicates considerable configurational disorder in the high temperature phase. The presence of 5.9 K hysteresis of the phase transition temperature at T C and sharpness of the heat flow anomaly attest that the detected phase transition is of the first-order type. Appearing of the two new bands (splitting of d s (HNH)F 1u mode) in FT-MIR spectra at the vicinity of 1200 cm -1 suggests that the phase transition undergoes a change of the crystal structure.

show abstract

“…In our calculations, the initial distance Mn–O was between 2.101 and 2.161 Å; we assumed a high spin state for Mn 2+ . The calculations and computational details for the similar compounds were presented in the literature …”

Section: Resultsmentioning

confidence: 99%

“…The calculations and computational details for the similar compounds were presented in the literature. [1,2,17] The influence of the spin of Mn in manganese octahedral complexes of the type MnX 6 , where X = H 2 O, F − , CN − , was also the subject of quantum chemical DFT calculations performed by Trzaskowski et al [18] The selected values of the bond lengths calculated for model Mn(H 2 O) 2 (ReO 4 ) 2 and angles and corresponding experimental values for this model are presented in Table S1 (Supporting Information). The atomic labelling sequence used in these studies is shown in Figure 1.…”

Section: Molecular Structure and Vibrational Spectramentioning

confidence: 99%

Dynamics of H₂O ligands and ReO₄⁻ anions at the phase transition in [Mn(H₂O)₂](ReO₄)₂ studied by complementary spectroscopic methods

Hetmańczyk

2017

J Raman Spectroscopy

View full text Add to dashboard Cite

The vibrational and reorientational motions of H2O ligands and ReO4− anions in high‐ and low‐temperature phases were investigated by means of Fourier transform far‐ and mid‐infrared and Raman light‐scattering spectroscopy and neutron scattering (inelastic/quasi‐elastic incoherent neutron scattering) methods. The dynamics of H2O and ReO4− molecules in high‐ (I) and low‐temperature (II) phases was investigated by means of band shape analysis performed for Raman and IR bands. The temperature dependencies of full width at half maximum values of the Raman bands at 874 (νas(ReO)) and 943 cm−1 (νs(ReO)) exhibit changes in their behaviour in the vicinity of transformation, suggesting that the observed phase transition is connected with a change in the reorientational dynamics of ReO4−. However, anions also perform fast (τR ≈ 10−12 to 10−13 s) stochastic reorientational motions in Phase II. The estimated mean value of activation energy for ReO4− anions in the low‐temperature phase is Ea(II) = 8.1 kJmol−1. In infrared band shape analysis it was found that H2O ligands perform fast (picosecond correlation time scale) motions in both phases with a mean value of activation energies of 7.68 kJmol−1. These reorientational motions of H2O ligands do not contribute to the phase transition mechanism. Moreover, the observed phase transition was accompanied by the splitting of some bands, suggesting a reduction in crystal structure symmetry. Quasi‐elastic neutron scattering measurements furnished evidence that H2O motion in Phase I can be fairly accurately described by a simple model of 180° jumps around a twofold axis within a picosecond time scale. Additionally, infrared, Raman light‐scattering spectra were calculated using the density functional theory method for the isolated equilibrium model Mn(H2O)2(ReO4)2, and qualitative agreement with the experimental data was achieved. The theoretical vibrational spectra of the title compound were interpreted by means of potential energy distributions using the VEDA 4 program.

show abstract

Experimental (FT-IR and FT-RS) and theoretical (DFT) studies of molecular structure and internal modes of [Mn(NH3)6](NO3)2

Cited by 19 publications

References 34 publications

Spectroscopic Signatures of Hydrogen-Bonding Motifs in Protonic Ionic Liquid Systems: Insights from Diethylammonium Nitrate in the Solid State

Spectroscopic Signatures of Hydrogen-Bonding Motifs in Protonic Ionic Liquid Systems: Insights from Diethylammonium Nitrate in the Solid State

Thermal properties of polycrystalline [Mn(NH3)6](ClO4)2

Dynamics of H₂O ligands and ReO₄⁻ anions at the phase transition in [Mn(H₂O)₂](ReO₄)₂ studied by complementary spectroscopic methods

Contact Info

Product

Resources

About

Experimental (FT-IR and FT-RS) and theoretical (DFT) studies of molecular structure and internal modes of [Mn(NH3)6](NO3)2

Cited by 19 publications

References 34 publications

Spectroscopic Signatures of Hydrogen-Bonding Motifs in Protonic Ionic Liquid Systems: Insights from Diethylammonium Nitrate in the Solid State

Spectroscopic Signatures of Hydrogen-Bonding Motifs in Protonic Ionic Liquid Systems: Insights from Diethylammonium Nitrate in the Solid State

Thermal properties of polycrystalline [Mn(NH3)6](ClO4)2

Dynamics of H2O ligands and ReO4− anions at the phase transition in [Mn(H2O)2](ReO4)2 studied by complementary spectroscopic methods

Contact Info

Product

Resources

About

Dynamics of H₂O ligands and ReO₄⁻ anions at the phase transition in [Mn(H₂O)₂](ReO₄)₂ studied by complementary spectroscopic methods