Structure and vibrational analyses of LiP15

Nadine Eckstein, Laura Alice Jantke, Thomas F. Fässler, János Mink, Markus Drees, Tom Nilges

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Abstract

LiP15 was synthesized by reaction of the elements in the presence of CuCl2 as a mineralizer additive in sealed silica ampoules at 823 K. The product was characterized by powder and single-crystal X-ray diffraction experiments, quantum chemical calculations and IR and Raman spectroscopy. It crystallizes in the triclinic crystal system in space group P1¯ with the lattice parameters a = 6.974(1) Å, b = 9.008(1) Å, c = 11.294(2) Å, α = 104.51(1)°, β = 93.78(1)°, γ = 106.330(10)° and V = 652.1 Å3. The structure of the phosphorus-rich polyphosphide consists of tubular polyphosphide strands that are coordinated by lithium atoms to form double strands with an antiparallel arrangement. Quantum chemical investigations and structure optimizations were applied to localize the Li positions within the polyphosphide framework, and a full factor group analysis was done to understand the complex IR and Raman spectra of the title compound. LiP15 does not crystallize isotypically to compounds with the higher homologues of lithium but forms its own structure type, in contrast to previous reports. On the basis of our results, a LiP15 polymorph isotypic to KP15 might exist energetically separated by a few kJ/mol. We also predict that a second KP15 polymorph with the reported LiP15 structure would be energetically as favourable as the known one.

Original languageEnglish
Pages (from-to)5135-5144
Number of pages10
JournalEuropean Journal of Inorganic Chemistry
Volume2014
Issue number30
DOIs
Publication statusPublished - Oct 2014

Keywords

  • Density functional calculations
  • IR spectroscopy
  • Lithium
  • Phosphorus
  • Polyphosphides
  • Raman spectroscopy

ASJC Scopus subject areas

  • Inorganic Chemistry

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    Eckstein, N., Jantke, L. A., Fässler, T. F., Mink, J., Drees, M., & Nilges, T. (2014). Structure and vibrational analyses of LiP15. European Journal of Inorganic Chemistry, 2014(30), 5135-5144. https://doi.org/10.1002/ejic.201402383