Physical Chemistry

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By G. V. Samsonov

The e-book we're offering to American and different English­ talking readers is a evaluate of the paintings at the electron struc­ ture of parts, alloys, and compounds, which was once all started again within the fifties. This paintings progressively grew right into a approach of principles at the electron constitution of condensed subject that's referred to now because the configurational version. This version is predicated at the assumption of the preferential formation of the main sturdy configurations of the localized va­ lence electrons in condensed subject. The lifestyles of those sturdy configurations and the alternate of electrons with the de­ localized (collective-state) subsystem determines these prop­ erties that are relating to the electron constitution. The conclu­ sions which might be drawn from the purposes of the configura­ tional version are just qualitative yet they clarify really in actual fact the character of assorted houses of condensed subject, and they're useful within the look for fabrics with specific homes. the yankee version has been corrected and supplemented in lots of minor respects. additionally, the chance was once taken to revise completely the part at the basics of the configura­ tional version within the gentle of the newest theoretical advancements. different elements of the ebook were shortened to do away with fabric which isn't of basic value or has now not but been de­ veloped sufficiently fully.

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The presence of the d 5 states in manganese gives rise to simple cubic ()! and {3 modifications and to a tetragonal face-centered y modification. Technetium and rhenium are characterized by a higher stability of the d 5 configurations and by a Mott transition in the electron subsystem. These two metals have hcp structures. CRYSTAL STRUCTURE AND POLYMORPHISM 41 Iron is characterized by even lower values of the statistical weight of the d 5 configuration and of the intermediate configurations, by a small fraction of the sp electrons, and by the existence of localized magnetic moments which do not favor the appearance of an hcp structure.

The overlap occurs between orbitals with antiparallel spins. This point is stressed by Goodenough: ·With relatively small overlap of localized orbitals, the probability of electron transfer is small so that the electrons remain essentially localized; however, the superexchange stabilization introduces antiferromagnetic coupling and an incipient covalency. With relatively large orbital overlap, there is a large probability of electron transfer so that the electrons at any atom are essentially spin-paired" (p.

22 CHAPTER I. CONFIGURATIONAL MODEL OF SOLIDS to the condensed state. A more rigorous many-electron approach utilizing the Hamiltonian of Eq. (1) predicts the same features in the energy spectra, except that the concept of the sand d functions should be replaced by the predominant s or d nature of the total functions resulting from the hybridization of the quasilocalized d n states with the s band. It follows from our discussion that the influence of temperature on the energy spectra of the metals characterized by the highest values of the statistical weights of the d 5 or the d 10 configurations is quite different from the influence of temperature on the other metals (Fig.

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