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Gd(5) Si(4-x) P(x): cambios estructurales dirigidos a través del aumento en el recuento de electrones de valencia.

Volodymyr Svitlyk1, Gordon J Miller, Yurij Mozharivskyj

  • 1Department of Chemistry, McMaster University, Hamilton, Ontario, L8S 4M1, Canada.

Journal of the American Chemical Society
|February 10, 2009
PubMed
Resumen

Se estudiaron las transformaciones de fase en los sistemas de fosfuro de silicio gadolinio (Gd(5) Si(4-x) P(x)). El aumento de la sustitución de fósforo rompe los dímeros entre las láminas, alterando la estructura cristalina y extendiendo las estructuras de tipo Sm ((5) Ge ((4).

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Área de la Ciencia:

  • Ciencia de los materiales Ciencia de los materiales.
  • Química del estado sólido.
  • La cristalografía es una técnica de cristalografía.

Sus antecedentes:

  • Los silicuros de gadolinio y sus aleaciones exhiben interesantes propiedades estructurales y electrónicas.
  • Comprender las transformaciones de fase es crucial para adaptar las características de los materiales.

Objetivo del estudio:

  • Para investigar las transformaciones de fase en el sistema Gd(5) Si(4-x) P(x).
  • Para correlacionar los cambios en la estructura cristalina con el recuento de electrones de valencia.
  • Para explorar la estabilidad de las estructuras de tipo Sm(5) Ge(4).

Principales métodos:

  • Difracción de rayos X (XRD) para el análisis estructural.
  • Sustitución sistemática de Si por P en Gd ((5) Si ((4-x) P ((x)).
  • Cálculos de órbitales lineales de unión estrecha (TB-LMTO, por sus siglas en inglés).

Principales resultados:

  • Transformaciones de fase observadas en los sistemas Gd(5) Si(4-x) P(x) (0 ≤ x ≤ 2).
  • El aumento del recuento de electrones de valencia a través de la sustitución P conduce a la ruptura de los dímeros interslab T-T.
  • La fase Gd{5) Si{2.75) P{1.25) muestra movimiento de cizallamiento de losas [Gd{5) T{4].
  • Las estructuras ortorrómbicas de tipo Sm(5) Ge(4) se estabilizan en recuentos de electrones de valencia > 31 e(-) / unidad de fórmula.

Conclusiones:

  • Existe un fuerte acoplamiento entre la estructura cristalina y el recuento de electrones de valencia en el sistema estudiado.
  • La sustitución de P influye en la unión entre las placas y en los arreglos de las placas.
  • Los cálculos de TB-LMTO confirman el origen electrónico de la escisión del dímero debido a la población del estado antienlace.