On the origin of the forward peak and backward oscillations in the F + H2(v = 0) to HF(v' = 2) + H reaction

We present a semiclassical complex angular momentum (CAM) analysis of the forward scattering peak which occurs at a translational collision energy around 32 meV in the quantum mechanical calculations for the F + H2(v = 0, j = 0) ? HF(v' = 2, j' = 0) + H reaction on the Stark–Werner potential energy surface. The semiclassical CAM theory is modified to cover the forward and backward scattering angles. The peak is shown to result from constructive/destructive interference of the two Regge states associated with two resonances, one in the transition state region and the other in the exit channel van der Waals well. In addition, we demonstrate that the oscillations in the energy dependence of the backward differential cross section are caused by the interference between the direct backward scattering and the decay of the two resonance complexes returning to the backward direction after one full rotation.

Nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties by means of electrical property expansions: Application to HF, CH4, CF4, and SF6

Electrical property derivative expressions are presented for the nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties. For CF4 and SF6, as opposed to HF and CH4, a term that is quadratic in the vibrational anharmonicity (and not previously evaluated for any molecule) makes an important contribution to the static second vibrational hyperpolarizability of CF4 and SF6. A comparison between calculated and experimental values for the difference between the (anisotropic) Kerr effect and electric field induced second-harmonic generation shows that, at the Hartree-Fock level, the nuclear relaxation/infinite frequency approximation gives the correct trend (in the series CH4, CF4, SF6) but is of the order of 50% too small

Counterpoise-corrected geometries and harmonic frequencies of N-body clusters: application to (HF)n (n=3,4)

A study was conducted on the methods of basis set superposition error (BSSE)-free geometry optimization and frequency calculations in clusters larger than a dimer. In particular, three different counterpoise schemes were critically examined. It was shown that the counterpoise-corrected supermolecule energy can be easily obtained in all the cases by using the many-body partitioning of energy

Comparison of D-region Doppler drift winds measured by the SuperDARN Finland HF radar over an annual cycle using the Kiruna VHF meteor radar

The SuperDARN chain of oblique HF radars has provided an opportunity to generate a unique climatology of horizontal winds near the mesopause at a number of high latitude locations, via the Doppler shifted echoes from sources of ionisation in the D-region. Ablating meteor trails form the bulk of these targets, but other phenomena also contribute to the observations. Due to the poor vertical resolution of the radars, care must be taken to reduce possible biases from sporadic-E layers and Polar Mesospheric Summer echoes that can affect the effective altitude of the geophysical parameters being observed. Second, there is strong theoretical and observational evidence to suggest that the radars are picking up echoes from the backward looking direction that will tend to reduce the measured wind strengths. The effect is strongly frequency dependent, resulting in a 20% reduction at 12 MHz and a 50% reduction at 10 MHz. A comparison of the climatologies observed by the Super-DARN Finland radar between September 1999 and September 2000 and that obtained from the adjacent VHF meteor radar located at Kiruna is also presented. The agreement between the two instruments was very good. Extending the analysis to the SuperDARN Iceland East radar indicated that the principles outlined above could be applied successfully to the rest of the SuperDARN network.

Nightside studies of coherent HF Radar spectral width behaviour

A previous case study found a relationship between high spectral width measured by the CUTLASS Finland HF radar and elevated electron temperatures observed by the EISCAT and ESR incoherent scatter radars in the postmidnight sector of magnetic local time. This paper expands that work by briefly re-examining that interval and looking in depth at two further case studies. In all three cases a region of high HF spectral width (>200 ms−1) exists poleward of a region of low HF spectral width (<200 ms^{−1}). Each case, however, occurs under quite different geomagnetic conditions. The original case study occurred during an interval with no observed electrojet activity, the second study during a transition from quiet to active conditions with a clear band of ion frictional heating indicating the location of the flow reversal boundary, and the third during an isolated substorm. These case studies indicate that the relationship between elevated electron temperature and high HF radar spectral width appears on closed field lines after 03:00 magnetic local time (MLT) on the nightside. It is not clear whether the same relationship would hold on open field lines, since our analysis of this relationship is restricted in latitude. We find two important properties of high spectral width data on the nightside. Firstly the high spectral width values occur on both open and closed field lines, and secondly that the power spectra which exhibit high widths are both single-peak and multiple-peak. In general the regions of high spectral width (>200 ms−1) have more multiple-peak spectra than the regions of low spectral widths whilst still maintaining a majority of single-peak spectra. We also find that the region of ion frictional heating is collocated with many multiplepeak HF spectra. Several mechanisms for the generation of high spectral width have been proposed which would produce multiple-peak spectra, these are discussed in relation to the data presented here. Since the regions of high spectral width are observed both on closed and open field lines the use of the boundary between low and high spectral width as an ionospheric proxy for the open/closed field line boundary is not a simple matter, if indeed it is possible at all.

Simplified estimation of ray-path mirroring height for HF radiowaves reflected from the ionospheric F-region

From Milsom's equations, which describe the geometry of ray-path hops reflected from the ionospheric F-layer, algorithms for the simplified estimation of mirror-reflection height are developed. These allow for hop length and the effects of variations in underlying ionisation (via the ratio of the F2- and E-layer critical frequencies) and F2-layer peak height (via the M(3000)F2-factor). Separate algorithms are presented which are applicable to a range of signal frequencies about the FOT and to propagation at the MUF. The accuracies and complexities of the algorithms are compared with those inherent in the use of a procedure based on an equation developed by Shimazaki.

A simple model of the effects of the mid-latitude total ion trough in the bottomsideFlayer on HF radiowave propagation

Observations of the amplitudes and Doppler shifts of received HF radio waves are compared with model predictions made using a two-dimensional ray-tracing program. The signals are propagated over a sub-auroral path, which is shown to lie along the latitudes of the mid-latitude trough at times of low geomagnetic activity. Generalizing the predictions to include a simple model of the trough in the density and height of the F2 peak enables the explanation of the anomalous observed diurnal variations. The behavior of received amplitude, Doppler shift, and signal-to-noise ratio as a function of the Kp index value, the time of day, and the season (in 17 months of continuous recording) is found to agree closely with that predicted using the statistical position of the trough as deduced from 8 years of Alouette satellite soundings. The variation in the times of the observation of large signal amplitudes with the Kp value and the complete absence of such amplitudes when it exceeds 2.75 are two features that implicate the trough in these effects.

The SPARC Data Initiative: comparisons of CFC-11, CFC-12, HF and SF6 climatologies from international satellite limb sounders

A quality assessment of the CFC-11 (CCl3F), CFC-12 (CCl2F2), HF, and SF6 products from limb-viewing satellite instruments is provided by means of a detailed intercomparison. The climatologies in the form of monthly zonal mean time series are obtained from HALOE, MIPAS, ACE-FTS, and HIRDLS within the time period 1991–2010. The intercomparisons focus on the mean biases of the monthly and annual zonal mean fields and aim to identify their vertical, latitudinal and temporal structure. The CFC evaluations (based on MIPAS, ACE-FTS and HIRDLS) reveal that the uncertainty in our knowledge of the atmospheric CFC-11 and CFC-12 mean state, as given by satellite data sets, is smallest in the tropics and mid-latitudes at altitudes below 50 and 20 hPa, respectively, with a 1σ multi-instrument spread of up to ±5 %. For HF, the situation is reversed. The two available data sets (HALOE and ACE-FTS) agree well above 100 hPa, with a spread in this region of ±5 to ±10 %, while at altitudes below 100 hPa the HF annual mean state is less well known, with a spread ±30 % and larger. The atmospheric SF6 annual mean states derived from two satellite data sets (MIPAS and ACE-FTS) show only very small differences with a spread of less than ±5 % and often below ±2.5 %. While the overall agreement among the climatological data sets is very good for large parts of the upper troposphere and lower stratosphere (CFCs, SF6) or middle stratosphere (HF), individual discrepancies have been identified. Pronounced deviations between the instrument climatologies exist for particular atmospheric regions which differ from gas to gas. Notable features are differently shaped isopleths in the subtropics, deviations in the vertical gradients in the lower stratosphere and in the meridional gradients in the upper troposphere, and inconsistencies in the seasonal cycle. Additionally, long-term drifts between the instruments have been identified for the CFC-11 and CFC-12 time series. The evaluations as a whole provide guidance on what data sets are the most reliable for applications such as studies of atmospheric transport and variability, model–measurement comparisons and detection of long-term trends. The data sets will be publicly available from the SPARC Data Centre and through PANGAEA (doi:10.1594/PANGAEA.849223).

Electric field gradients in (111)In-doped (Hf/Zr)(3)Al(2) and (Hf/Zr)(4)Al(3) mixed compounds: ab initio calculations, perturbed angular correlation measurements and site preference

The quadrupolar hyperfine interactions of in-diffused (111)In -> (111)Cd probes in polycrystalline isostructural Zr(4)Al(3) and Hf(4)Al(3) samples containing small admixtures of the phases (Zr/Hf)(3)Al(2) were investigated. A strong preference of (111)In solutes for the contaminant (Zr/Hf)(3)Al(2) minority phases was observed. Detailed calculations of the electric field gradient (EFG) at the Cd nucleus using the full-potential augmented plane wave + local orbital formalism allowed us to assign the observed EFG fractions to the various lattice sites in the (Zr/Hf)(3)Al(2) compounds and to understand the preferential site occupation of the minority phases by the (111)In atoms. The effects of the size of the supercell and relaxation around the oversized In and Cd probe atoms were investigated in detail.