Microwave dynamics of quasiparticles and critical fields in superconducting films

The microwave response of the superconducting state in equilibrium and non-equilibrium configurations was examined experimentally and analytically. Thin film superconductors were mostly studied in order to explore spatial effects. The response parameter measured was the surface impedance.

For small microwave intensity the surface impedance at 10 GHz was measured for a variety of samples (mostly Sn) over a wide range of sample thickness and temperature. A detailed analysis based on the BCS theory was developed for calculating the surface impedance for general thickness and other experimental parameters. Experiment and theory agreed with each other to within the experimental accuracy. Thus it was established that the samples, thin films as well as bulk, were well characterised at low microwave powers (near equilibrium).

Thin films were perturbed by a small dc supercurrent and the effect on the superconducting order parameter and the quasiparticle response determined by measuring changes in the surface resistance (still at low microwave intensity and independent of it) due to the induced current. The use of fully superconducting resonators enabled the measurement of very small changes in the surface resistance (< 10^-9 Ω/sq.). These experiments yield information regarding the dynamics of the order parameter and quasiparticle systems. For all the films studied the results could be described at temperatures near T_c by the thermodynamic depression of the order parameter due to the static current leading to a quadratic increase of the surface resistance with current.

For the thinnest films the low temperature results were surprising in that the surface resistance decreased with increasing current. An explanation is proposed according to which this decrease occurs due to an additional high frequency quasiparticle current caused by the combined presence of both static and high frequency fields. For frequencies larger than the inverse of the quasiparticle relaxation time this additional current is out of phase (by π) with the microwave electric field and is observed as a decrease of surface resistance. Calculations agree quantitatively with experimental results. This is the first observation and explanation of this non-equilibrium quasiparticle effect.

For thicker films of Sn, the low temperature surface resistance was found to increase with applied static current. It is proposed that due to the spatial non-uniformity of the induced current distribution across the thicker films, the above purely temporal analysis of the local quasiparticle response needs to be generalised to include space and time non-equilibrium effects.

The nonlinear interaction of microwaves arid superconducting films was also examined in a third set of experiments. The surface impedance of thin films was measured as a function of the incident microwave magnetic field. The experiments exploit the ability to measure the absorbed microwave power and applied microwave magnetic field absolutely. It was found that the applied surface microwave field could not be raised above a certain threshold level at which the absorption increased abruptly. This critical field level represents a dynamic critical field and was found to be associated with the penetration of the app1ied field into the film at values well below the thermodynamic critical field for the configuration of a field applied to one side of the film. The penetration occurs despite the thermal stability of the film which was unequivocally demonstrated by experiment. A new mechanism for such penetration via the formation of a vortex-antivortex pair is proposed. The experimental results for the thinnest films agreed with the calculated values of this pair generation field. The observations of increased transmission at the critical field level and suppression of the process by a metallic ground plane further support the proposed model.

Bicyclo[3.2.0]hepta-1,4,6-triene: synthesis, thermal rearrangement, and anion formation

In order to determine the properties of the bicycloheptatrienyl anion (Ia) (predicted to be conjugatively stabilized by Hückel Molecular Orbital Theory) the neutral precursor, bicyclo[3. 2. 0] hepta-1, 4, 6-triene (I) was prepared by the following route.

Reaction of I with potassium-t-butoxide, potassium, or lithium dicyclohexylamide gave anion Ia in very low yield. Reprotonation of I was found to occur solely at the 1 or 5 position to give triene II, isolated as to its dimers.

A study of the acidity of I and of other conjugated hydrocarbons by means of ion cyclotron resonance spectroscopy resulted in determination of the following order of relative acidities:

H₂S ˃ C₅H₆ ˃ CH₃NO₂ ˃ 1, 4- C₅H₈ ˃ I ˃ C₂H₅OH ˃ H₂O; cyclo-C₇H₈ ˃ C₂ H₅OH; фCH₃ ˃ CH₃OH

In addition, limits for the proton affinities of the conjugate bases were determined:

350 kcal/mole ˂ PA(C₅ H₅^-) ˂ 360 kcal/mole

362 kcal/mole ˂ PA(C₅H₇^-, Ia, cyclo-C₇H₇^-) ˂ 377 kcal/mole PA(фCH₂^-) ˂ 385 kcal/mole

Gas phase kinetics of the trans-XVIII to I transformation gave the following activation parameters: E_a = 43.0 kcal/mole, log A = 15.53 and ∆S^ǂ (220°) = 9.6 cu. The results were interpreted as indicating initial 1,2 bond cleavage to give the 1,3-diradical which closed to I. Similar studies on cis-XVIII gave results consistent with a surface component to the reaction (E_a = 22.7 kcal/mole; log A = 9.23, ∆S^ǂ (119°) = -18.9 eu).

The low pressure (0.01 to 1 torr) pyrolysis of trans-XVIII gave in addition to I, fulvenallene (LV), ethynylcyclopentadiene (LVI) and heptafulvalene (LVII). The relative ratios of the C₇H₆ isomers were found to be dependent upon temperature and pressure, higher relative pressure and lower temperatures favoring formation of I. The results were found to be consistent with the intermediacy of vibrationally excited I and subsequent reaction to give LV and LVI.