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R. Lefbvre 《Chemical physics letters》1980,70(3):430-433
The complex rotation method is applied to the determination of widths and shifts of an harmonic oscillator predissociated by a linear potential, for when exact analytical formulas are available in the limit of small interchannel coupling. Excellent agreement is obtained. 相似文献
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The 57Fe Mössbauer effect in [Fe(pythiaz)2] (BF4)2 (I) and [Fe(pythiaz)2] (C&O4)2 (II) has been studied between 298 and 4.2°K (pythiaz = 2,4-bis(2-pyridyl)thiazole). At 298°K compound I shows a doublet with ΔEQ(5T2) = 1.29 mm sec?1 and δ1S(5T2) = +0.93 mm sec?1 characteristic of a 5T2 ground state. At 236°K, a second doublet, typical for a 1A1 ground state appears. The transition 5T2 å 1A1 progresses as the temperature is lowered but levels off below ≈ 120°K. At 4.2°K, 59% of the intensity is due to the 1A1 state, and ΔEQ(1A1) = 1.59 mm sec?1 and δ1S(1A1) = +0.26 mm sec?1. In an applied magnetic field, Vzz(1A1) < 0 has been determined Similar results have been obtained with compound II.Debye-Waller factors f5T2 and f1A1. were determined from the Mössbauer spectra under the assumption of Curie-Weiss dependence of the magnetism for the 5T2 and constant μeff for the 1A1 ground state. The resulting temperature dependence of f1A1 is highly unusual thus suggesting complicated magnetic behaviour of both ground states in the transition region. Two mechanisms for the nature of the transition are discussed, a “spin-flip” mechanism being the physically more reasonable one. The assumption of a simple Boltzmann distribution (“spin equilibrium”) may be ruled out for the solid but could be encountered in solutions. 相似文献