Vibrational spectra of hypophosphite ion and its deuterated species

Abénoza, M.; Tabacik, Vlado

doi:10.1016/0022-2860(75)80070-6

Cited by 19 publications

(4 citation statements)

References 5 publications

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“…The C 2 v symmetry hypophosphite ion possesses nine normal modes of vibration, all of which are Raman active and eight of which are infrared active. Deuteration studies, − the use of polarized radiation, , and normal coordinate analyses ,, have enabled firm assignments to be made for these modes of vibration, as exemplified for KH 2 PO 2 in Table . Subsequent proposed changes in assignments and neglect of the effects of the solid state 4 have been shown to be incorrect. , …”

Section: Resultsmentioning

confidence: 99%

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Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 1. Anhydrous and Monohydrated Lanthanide Hypophosphites

1999

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The lanthanide hypophosphite complexes Ln(H(2)PO(2))(3) (Ln = La, Pr, Nd) and Ln(H(2)PO(2))(3).H(2)O (Ln = La, Pr) crystallize in the space group P&onemacr; (No. 2), Z = 2. The lattice constants for La(H(2)PO(2))(3) are a = 6.7912(6) Å, b = 7.0801(8) Å, c = 8.863(1) Å, alpha = 82.64(1) degrees, beta = 74.43(1)( o), gamma = 71.91(1) degrees; for La(H(2)PO(2))(3).H(2)O, a = 7.2291(4) Å, b = 7.983(1) Å, c = 8.934(1) Å, alpha =110.57(1) degrees, beta = 98.26(1) degrees, gamma = 104.35(1) degrees. In both structures hypophosphite ions bridge adjacent 8-coordinate lanthanide ions to give infinite chains. Infrared and Raman spectra (300-20 K) are shown to be consistent with the crystallographic data, with 52 of the 54 fundamental hypophosphite modes of vibration assigned. The electronic spectra of the anhydrous compounds consist mainly of bands due to pure electronic electric dipole transitions. Two-center vibronic transitions observed in the (3)H(4) --> (1)D(2) spectrum of Pr(H(2)PO(2))(3) are not well-simulated by a model with dipole-dipole interaction terms between the two centers. The energy level scheme of Pr(3+) in Pr(H(2)PO(2))(3) was fitted to a model Hamiltonian for a C(2)(v)() site symmetry Pr(3+) ion, including configuration interaction of 4f(2) with 4f6p. Theoretical crystal field parameters were in reasonable agreement with those derived from the energy level fitting. The results highlight the C(2)(v)() (k even) and C(1) (k odd) distortions from the ideal D(4)(d)() antiprismal structure, which slightly modify the 4f(2) energy level scheme, and largely determine the spectral intensities in Pr(H(2)PO(2))(3), respectively. The derived energy level scheme of Nd(H(2)PO(2))(3) is similar to that for 8-coordinated Nd(3+) in NdCl(3).6H(2)O.

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Section: Resultsmentioning

confidence: 99%

“…Raman modes transform as A g , and IR modes as A u irreps for the C i unit cell group. b Data from refs −45. c,d Additional bands are resolved (c) at 120 K and (d) at 20 K.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 1. Anhydrous and Monohydrated Lanthanide Hypophosphites

1999

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“…A I'ttat libre, l'ion H,PO, a une symttrie V2" et ses vibrations fondamentales se rtpartissent en 4 A , (vl=v, [7]. Dans le cristal les ions hypophosophites se situent sur des sites de symttrie V, , l'axe de symttrie conservt ttant parallde soit aux axes Cix, soit aux axes C ;…”

Section: Classification Des Vibrationsunclassified

“…Sur les 23 modes fondamentaux du monocristal thboriquement actifs en diffusion Raman (voir tableau V), nous en avons decelC 22, la bande situCe a 2408 cm-' dans le spectre de symttrie E, qui comprend les modes de valence symttrique et antisymttrique de P-H n'ayant pu Etre didoublee. La repartition des modes en types de symCtrie et la comparaison avec le spectre de l'ion libre [7] permettent une attribution sans ambiguitC de ces modes normaux (tableaux I, I1 et III), en accord avec les rtsultats du spectre de reflexion infra-rouge de ce monocristal [4]. (Figure 4).…”

Section: Modes Internes Des Ions Hpo;unclassified

Spectres de diffusion Raman et structure des monocristaux de Mg(H₂PO₂)₂ 6H₂O et Co (H₂PO₂)₂ 6H₂O

Abénoza¹,

Martin²

1975

J Raman Spectroscopy

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Single crystal Raman spectra of Mg (H2P02)~ 6 HzO, Mg (HzP02)~ 6 DzO and Co (H2POz)z 6 HzO were recorded.A complete assignment of the bands to the zero wave vectors modes is proposed. The comparison between calculated and experimental Raman intensities shows the individuality of the HzPO; ions in the crystal. Various structure hypotheses are discussed: only the Lopez de Lerma's hypothesis and the 9 ' 0 4 site symmetry for the magnesium (or cobalt) atom are compatible with the Raman spectra data of the three single crystals.

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Synthesis and Structure of the First Carbyne Complex Functionalized Zwitterionic α-Carbenium Phosphinates [Tp′(CO)2M ≡ C−P(O)2−C(NR2)2] (M = Mo, W; R = Me, Et)

Weber¹,

Dembeck

Stammler

et al. 1998

Eur. J. Inorg. Chem.

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Vibrational spectra of hypophosphite ion and its deuterated species

Cited by 19 publications

References 5 publications

Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 1. Anhydrous and Monohydrated Lanthanide Hypophosphites

Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 1. Anhydrous and Monohydrated Lanthanide Hypophosphites

Spectres de diffusion Raman et structure des monocristaux de Mg(H₂PO₂)₂ 6H₂O et Co (H₂PO₂)₂ 6H₂O

Synthesis and Structure of the First Carbyne Complex Functionalized Zwitterionic α-Carbenium Phosphinates [Tp′(CO)2M ≡ C−P(O)2−C(NR2)2] (M = Mo, W; R = Me, Et)

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Vibrational spectra of hypophosphite ion and its deuterated species

Cited by 19 publications

References 5 publications

Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 1. Anhydrous and Monohydrated Lanthanide Hypophosphites

Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 1. Anhydrous and Monohydrated Lanthanide Hypophosphites

Spectres de diffusion Raman et structure des monocristaux de Mg(H2PO2)2 6H2O et Co (H2PO2)2 6H2O

Synthesis and Structure of the First Carbyne Complex Functionalized Zwitterionic α-Carbenium Phosphinates [Tp′(CO)2M ≡ C−P(O)2−C(NR2)2] (M = Mo, W; R = Me, Et)

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Spectres de diffusion Raman et structure des monocristaux de Mg(H₂PO₂)₂ 6H₂O et Co (H₂PO₂)₂ 6H₂O