Valence temperature dependence

Temperature The level of the temperature measurement (4 K, 20 K, 77 K, or higher) is the first issue to be considered. The second issue is the range needed (e.g., a few degrees around 90 K or 1 to 400 K). If the temperature level is that of air separation or liquefact-ing of natural gas (LNG), then the favorite choice is the platinum resistance thermometer (PRT). Platinum, as with all pure metals, has an electrical resistance that goes to zero as the absolute temperature decreases to zero. Accordingly, the lower useful limit of platinum is about 20 K, or liquid hydrogen temperatures. Below 20 K, semiconductor thermometers (germanium-, carbon-, or silicon-based) are preferred. Semiconductors have just the opposite resistance-temperature dependence of metals—their resistance increases as the temperature is lowered, as fewer valence electrons can be promoted into the conduction band at lower temperatures. Thus, semiconductors are usually chosen for temperatures from about 1 to 20 K. 

Fig. 14. Comparison of the VTMCD spectra ( 1.6 K and 6 T) of the valence-delocalized S = 9/2 [Fe2S2] cluster in the aUtEdine form of the C60S mutemt of C. pasteurianum 2Fe Fd with those of the [ZnFesSJ Emd [Fe3S4] clusters in P. furiosus Fd. Magnetization and temperature dependence studies show that the bands marked with an asterisk in the valence-delocEdized S = 9/2 [Fe2S2] spectra result from a valence-localized S = 1/2 component.

A major discrepancy that remains unresolved in the excited-state properties of the [Fe384]° cluster in D. gigas Fdll concerns the existence of a low-lying, fully valence-delocalized state that becomes populated at temperatures above 25 K. 8uch a state is clearly apparent in the temperature-dependent Mossbauer studies of reduced D. gigas Fdll (29) and P. furiosus 3Fe Fd (198) and is represented by one quad-rupole doublet with AEq 0.9 mm/s and S = 0.45 mm/s. 8uch a... 

Contact shifts give information on the electronic structure of the iron atoms, particularly on the valence distribution and on the magnetic coupling within polymetallic systems. The magnetic coupling scheme, which is considered later, fully accounts for the variety of observed hyperfine shifts and the temperature dependence. Thus, through the analysis of the hyperfine shifts, NMR provides detailed information on the metal site(s) of iron-sulfur proteins, and, thanks to the progress in NMR spectroscopy, also the solution structure 23, 24 ). 

The recoil-free fraction depends on the oxidation state, the spin state, and the elastic bonds of the Mossbauer atom. Therefore, a temperature-dependent transition of the valence state, a spin transition, or a phase change of a particular compound or material may be easily detected as a change in the slope, a kink, or a step in the temperature dependence of In f T). However, in fits of experimental Mossbauer intensities, the values of 0 and Meff are often strongly covariant, as one may expect from a comparison of the traces shown in Fig. 2.5b. In this situation, valuable constraints can be obtained from corresponding fits of the temperature dependence of the second-order-Doppler shift of the Mossbauer spectra, which can be described by using a similar approach. The formalism is given in Sect. 4.2.3 on the temperature dependence of the isomer shift. 

A quantitative consideration on the origin of the EFG should be based on reliable results from molecular orbital or DPT calculations, as pointed out in detail in Chap. 5. For a qualitative discussion, however, it will suffice to use the easy-to-handle one-electron approximation of the crystal field model. In this framework, it is easy to realize that in nickel(II) complexes of Oh and symmetry and in tetragonally distorted octahedral nickel(II) complexes, no valence electron contribution to the EFG should be expected (cf. Fig. 7.7 and Table 4.2). A temperature-dependent valence electron contribution is to be expected in distorted tetrahedral nickel(n) complexes for tetragonal distortion, e.g., Fzz = (4/7)e(r )3 for com-... 

Both Fe(ll)(TPP) and Fe(II)(OEP) have positive electric quadrupole splitting without significant temperature dependence which, however, cannot be satisfactorily explained within the crystal field model [117]. Spin-restricted and spin-unrestricted Xoi multiple scattering calculations revealed large asymmetry in the population of the valence orbitals and appreciable 4p contributions to the EFG [153] which then was further specified by ab initio and DFT calculations [154,155]. 

Ryason and Russel measured the temperature dependence of the IR absorption band halfwidth for valence vibrations of hydroxyl groups on the silica surface.200 At T > 325 K, the least squares method permits a straight line to be drawn through experimental points of the dependence In Avv2 (Tl), the equation of the line appearing as follows 200... 

Fig. A2.2. Temperature dependences measured for the haliwidths Av n of the IR absorption bands for valence vibrations of OH(D) groups on Si02 surface (filled markers) and recalculated for the halfwidths w of three components of Lorentzian lines (empty markers) for OH (1) and (OD) groups of high concentration (2), and for (OD) groups of low concentration (3).2"2...

Oxides play many roles in modem electronic technology from insulators which can be used as capacitors, such as the perovskite BaTiOs, to the superconductors, of which the prototype was also a perovskite, Lao.sSro CutT A, where the value of x is a function of the temperature cycle and oxygen pressure which were used in the preparation of the material. Clearly the chemical difference between these two materials is that the capacitor production does not require oxygen partial pressure control as is the case in the superconductor. Intermediate between these extremes of electrical conduction are many semiconducting materials which are used as magnetic ferrites or fuel cell electrodes. The electrical properties of the semiconductors depend on the presence of transition metal ions which can be in two valence states, and the conduction mechanism involves the transfer of electrons or positive holes from one ion to another of the same species. The production problem associated with this behaviour arises from the fact that the relative concentration of each valence state depends on both the temperature and the oxygen partial pressure of the atmosphere. 

Does T differ significantly from unity in typical electron transfer reactions It is difficult to get direct evidence for nuclear tunnelling from rate measurements except at very low temperatures in certain systems. Nuclear tunnelling is a consequence of the quantum nature of oscillators involved in the process. For the corresponding optical transfer, it is easy to see this property when one measures the temperature dependence of the intervalence band profile in a dynamically-trapped mixed-valence system. The second moment of the band,... 

Figure 6. Temperature dependence of half-width of intervalence transfer absorption for [(NHS)sRu(4-cyanopyridine) Ru(NHs)5]5 mixed-valence (24, 25).

One experimental source of these essential data (for mixed-valence systems) is the intervalence transfer absorption band. The moments of the envelope (particularly the first and second moments) can be interpreted to yield values for x and (from a study of temperature dependence) for an effective coupling frequency. The study of effects of solvent variation can also lead to separation of x into intramolecular and environmental components. ... 

Some transition metal complexes are excellent conductors. Thin films of cyto-chrome-C3, which contains four heme moieties coordinated by protein, exhibited a high conductivity with mixed valence state (Fe /Fe ) and showed an increase in conductivity as the temperature was decreased (2 x 10 S cm at 268 K) [68-70]. The temperature dependence of conductivity in the highly conductive region is the opposite of that of semiconductors and may preclude the ionic conduction as a dominant contribution. However, since the high conductivity is realized in the presence of hydrogenase and hydrogen, the system is not strictly a single but rather a multicomponent molecular solid. 

That the effective hole masses, or the density of states, is a complicated matter in SiC is well described in a review by Gardner et al. [118]. This article treats in some detail the valence band and estimates the contribution from the three top-most bands to the density of states, including the temperature dependence. Using the estimated effective mass the authors attempt to calculate the activation (i.e., the ratio of implanted and electrically active Al ions), and they achieve an activation of 37% of the implanted Al concentration of 10 cm after an anneal at 1,670°C for about 10 minutes. 

While many complexes feature V0(IV)-0-V0(IV) moieties, and VO(IV) —O—VO(V) represent the largest class of mixed-valence compounds known [100], electrochemically characterized VO(V)—O —VO(V) are rare [112]. A series of three such complexes has been prepared, including [(abd)OV—O—VO(abd)] which features tridentate abd ligands and square-pyramidal coordination geometry around each V atom. These complexes are reduced in the range —0.25 < Ef" < —0.16 V versus Cp2Fe/CH2Cl2 and the mixed-valence products are stable on the bulk electrolysis timescale and they display temperature-dependent delocalization of the unpaired electron. 

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