Charge transfer on the metallic atom-pair bond, and the crystal structures adopted by intermetallic compounds

• Published in: Acta crystallographica. Section A, Foundations of crystallography Foundations of crystallography, 2012-01, Vol.68 (1), p.156-165
• Main Authors: Rajasekharan, T., Seshubai, V.
• Format: Article
• Language: English
• Subjects: Alloy development; Alloying; alloys; Atoms & subatomic particles; Bonding; Charge transfer; Crystal structure; Electronegativity; Intermetallic compounds; Intermetallics; Mathematical analysis; metals; superalloy design
• ISSN: 0108-7673; 1600-5724; 2053-2733
• DOI: 10.1107/S0108767311044151

It has been argued in our recent papers that the heat of formation of intermetallic compounds is mostly concentrated in the nearest neighbor unlike atom‐pair bonds, and that the positive term in Miedema's equation is associated with charge transfer on the bond to maintain electroneutrality. In this paper, taking examples of some well populated crystal‐structure types such as MgCu2, AsNa3, AuCu3, MoSi2 and SiCr3 types, the effect of such charge transfer on the crystal structures adopted by intermetallic compounds is examined. It is shown that the correlation between the observed size changes of atoms on alloying and their electronegativity differences is supportive of the idea of charge transfer between atoms. It is argued that the electronegativity and valence differences need to be of the required magnitude and direction to alter, through charge transfer, the elemental radius ratios RA/RB to the internal radius ratios rA/rB allowed by the structure types. Since the size change of atoms on alloying is highly correlated to how different RA/RB is from the ideal radius ratio for a structure type, the lattice parameters of intermetallic compounds can be predicted with excellent accuracy knowing RA/RB. A practical application of the approach developed in our recent papers to superalloy design is presented.