Thermodynamic clarification of the curious ferric/potassium ion exchange accompanying the electrochromic redox reactions of prussian blue, iron(III) hexacyanoferrate(II)

The recent Glasser-Jenkins method for lattice-energy prediction, applied to an examination of the solid-state thermodynamics of the cation exchanges that occur in electrochromic reactions of Prussian Blue, provides incisive thermodynamic clarification of an ill-understood ion exchange that accompanies particularly the early electrochromic cycles. A volume of 0.246 +/- 0.017 nm(3) formula unit(-1) for the ferrocyanide ion, Fe(II)[(CN)(6)],(4-) is first established and then used, together with other formula unit-volume data, to evaluate the changes of standard enthalpy, entropy, and Gibbs energy in those ion-exchange reactions. The results impressively show by how much the exchange of interstitial Fe(3+) ions by alkali metal ions, usually exemplified by K+, is thermodynamically favored.     

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Volume-based thermoelasticity: consequences of the (near) proportionality of isothermal compressibility to formula-unit volume

Groups of structurally related materials, including the alkali halides, exhibit a proportionality of isothermal compressibility to formula-unit volume. The relationship has recently been explored by Glasser and by Recio et al. In this paper, we present the consequences of such proportionality on the relationships of Born-Lande? and Born-Mayer parameters to the formula-unit volume. These relationships have then been tested separately on (i) alkali (excluding cesium) halides and (ii) cesium halides. We conclude that the equations fit the NaCl-type materials satisfactorily, but less well for the CsCl-type materials, and that the Born-Mayer equation is more applicable. These results confirm the conclusion that volume is intimately linked to thermodynamic quantities, as already demonstrated by our development of volume-based thermodynamics (VBT).     

One Dimensional Models with a Singular Potential of the Type −<Emphasis Type="Italic">αδ</Emphasis>(<Emphasis Type="Italic">x</Emphasis>)+<Emphasis Type="Italic">βδ</Emphasis>′(<Emphasis Type="Italic">x</Emphasis>)

We study a one-dimensional singular potential plus two types of regular interactions: constant electric field and harmonic oscillator. In order to search for the bound state energies, we shall use the Lippman-Schwinger Green function technique. Another direct method will be mentioned for the harmonic oscillator. In the electric field case the unique bound state coincides with that found in an earlier study as the field is switched off. For non-zero field the ground state is shifted and positive energy “quasibound states” appear. The harmonic oscillator demonstrates the general result that for a symmetric potential the odd states are not altered whereas the even states energies are lowered or raised accordingly as the delta perturbation is attractive or repulsive. No states are created or annihilated.     

Transition from the ballistic to the diffusive regime in a turbid medium

By varying the absorption coefficient and width of an intralipid-India ink solution in a quasi-one-dimensional experiment, we investigate the transition between the ballistic and the diffusive regimes. The medium's attenuation coefficient changes abruptly between two different values within a single mean free path. This problem is analyzed both experimentally and theoretically, and it is demonstrated that the transition location depends on the scattering coefficient as well as on the measuring solid angle.     

DHVA magnetic susceptibility of a 2D free electron gas

Summary The grand potential and energy of a noninteracting uncorrelated two-dimensional electron gas subject to Landau quantization in a magnetic field are examined here at low temperatures. The DeHaas-Van Alphen oscillatory magnetic susceptibility for the free 2D gas is calculated and the results presented here incorporate the effects of spin (by allowing that spin splitting may not, in general, equal Landau level separation) in formulae that have the same analytic structure for both even and odd numbers of filled Landau levels.

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Riassunto Il gran potenziale e l'energia di un gas elettronico bidimensionale non correlato non interagente, soggetto a quantizzazione di Landau in un campo magnetico, sono esaminate qui a basse temperature. La suscettibilità magnetica oscillatoria di De Haas-Van Alphen per il gas libero 2D è calcolata e i risultati presentati qui incorporano gli effetti di spin (tenendo conto che il taglio di spin non può, in generale, eguagliare uguale separazione del livello di Landau) in formule che hanno la stessa struttura analitica per numeri sia pari che dispari dei livelli completi di Landau.

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Резюме В зтой работе при низких температурах исследуется потенсиал и знергия невзаимодействующего некоррелированного двумерного злектроннного газа, подчинющегося квантованию Ландау в магнитном поле. Вычисляется осцилляторная магнитная восприимчивость де Гааза-ван Альфена для свободнго двумерного газа. Полученные результаты учитывают спиновые зффекты (допуская, что спиновое расщепление в общем случае может быть не равно интервалу между уровнями Ландау) в формулах, которые имеют ту же аналитическую структуру для четного и нечетного числа заполненных уровней Ландау.

     

Proposal for experimental observation of the “Kohn Anomaly”

Due to the enhancement of the singularity of q = 2k_F in the RPA dielectric function of an electron gas by a magnetic field the change in the penetration depth of an electric field in a thin metal film may lead to a detectable change in capacitance. A possible means for studying the Kohn anomaly is proposed on this basis.