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Solids in which the atoms, ions, or molecules are arranged in a definite repeating pattern are known as crystalline solids. Metals and ionic compounds typically form ordered, crystalline solids. A crystalline solid has a precise melting temperature because each atom or molecule of the same type is held in place with the same forces or energy. Amorphous solids or non-crystalline solids (or, sometimes, glasses) which lack an ordered internal structure and are randomly arranged. Substances that...
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Memoria sólida: preferencias estructurales en los monómeros, dímeros y sólidos del grupo 2 del dihaluro.

Kelling J Donald1, Roald Hoffmann

  • 1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.

Journal of the American Chemical Society
|August 24, 2006
PubMed
Resumen

Las preferencias estructurales en los monómeros y dímeros del grupo 2 del dihaluro influyen fuertemente en sus estructuras de estado sólido. Los monómeros doblados forman sólidos de alta coordinación, mientras que los monómeros lineales producen sólidos de baja coordinación.

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Área de la Ciencia:

  • Química Inorgánica La Química Inorgánica es la química inorgánica.
  • Química del estado sólido.
  • Química computacional es la química computacional.

Sus antecedentes:

  • Los dihaluros del grupo 2 (MX(2) exhiben diversos comportamientos estructurales en monómeros de fase gaseosa, dímeros y estados sólidos.
  • Comprender la relación entre la geometría de las pequeñas moléculas y las propiedades de los sólidos a granel es crucial para el diseño de materiales.

Objetivo del estudio:

  • Investigar teóricamente la conexión entre las preferencias estructurales de los monómeros, dímeros y dihaluros del grupo 2 y sus estructuras de estado sólido resultantes.
  • Para determinar qué tan bien se conservan las propiedades geométricas de la fase gaseosa en la fase sólida condensada.

Principales métodos:

  • Examen teórico de las preferencias estructurales en el grupo 2 monómeros de dihaluro (MX(2) y dímeros (M(2)X(4)).
  • Utilizando el nivel computacional B3LYP para analizar las geometrías de monómeros y dímeros.
  • Explorando las interacciones orbitales de frontera para comprender las relaciones monómero-oligómero.

Principales resultados:

  • Existe un claro vínculo entre la flexión de los monómeros y la estructura de los dímeros: los monómeros doblados favorecen a los dímeros C(3)(v) (triple puente), mientras que los monómeros lineales prefieren a los dímeros D(2)(h) (doble puente).
  • La flexibilidad de los monómeros influye en la preferencia de los dímeros, y los monómeros floppy muestran preferencias débiles.
  • Las tendencias estructurales en monómeros y dímeros se correlacionan con los tipos de estructura de estado sólido.

Conclusiones:

  • Los monómeros altamente doblados conducen a sólidos de alto número de coordinación (por ejemplo, fluorita, estructuras de PbCl2).
  • Los monómeros rígidamente lineales se condensan en sólidos de bajo número de coordinación (números de coordinación 4 o 6).
  • El estudio aclara las razones fundamentales detrás de estas correlaciones estructura-propiedad en el grupo 2 dihalides.