Optimised frequency grids for infrared radiative transfer simulations in cloudy conditions

This paper shows that radiometer channel radiances for cloudy atmospheric conditions can be simulated with an optimised frequency grid derived under clear-sky conditions. A new clear-sky optimised grid is derived for AVHRR channel 5 ð12 m m, 833 cm �1 Þ. For HIRS channel 11 ð7:33 m m, 1364 cm �1 Þ and AVHRR channel 5, radiative transfer simulations using an optimised frequency grid are compared with simulations using a reference grid, where the optimised grid has roughly 100–1000 times less frequencies than the full grid. The root mean square error between the optimised and the reference simulation is found to be less than 0.3 K for both comparisons, with the magnitude of the bias less than 0.03 K. The simulations have been carried out with the radiative transfer model Atmospheric Radiative Transfer Simulator (ARTS), version 2, using a backward Monte Carlo module for the treatment of clouds. With this module, the optimised simulations are more than 10 times faster than the reference simulations. Although the number of photons is the same, the smaller number of frequencies reduces the overhead for preparing the optical properties for each frequency. With deterministic scattering solvers, the relative decrease in runtime would be even more. The results allow for new radiative transfer applications, such as the development of new retrievals, because it becomes much quicker to carry out a large number of simulations. The conclusions are applicable to any downlooking infrared radiometer.

Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2(dppz)]2+ light-switch compound in solution and when bound to DNA

The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this “light-switch” effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280–1450 cm-1, which characterise both the emissive “bright” and the non-emissive “dark” excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the “dark” excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the “bright” state are observed for both L- and D enantiomers of 1 when bound to DNA and that photo-excitation of the complex induces perturbation of the guanine and cytosine carbonyl bands. This perturbation is shown to be stronger for the L enantiomer, demonstrating the different binding site properties of the two enantiomers and the ability of this technique to determine the identity and nature of the binding site of such intercalators.

Daily thin-ice thickness maps from modis thermal infrared imagery

Accurate knowledge of ice-production rates within the marginal ice zones of the Arctic Ocean requires monitoring of the thin-ice distribution within polynyas. The thickness of the ice layer controls the heat loss and hence the new-ice formation. An established thinice algorithm using high-resolution MODIS data allows deriving the ice-thickness distribution within polynyas. The average uncertainty is ±4.7 cm for ice thicknesses below 0.2 m. In this study, the ice-thickness distributions within the Laptev Sea polynya for the two winter seasons 2007/08 and 2008/09 are calculated. Then, a new method is applied to determine a daily MODIS thin-ice product.

Evaluation of a polynya flux model by means of thermal infrared satellite estimates

We test the ability of a two-dimensional flux model to simulate polynya events with narrow open-water zones by comparing model results to ice-thickness and ice-production estimates derived from thermal infrared Moderate Resolution Imaging Spectroradiometer (MODIS) observations in conjunction with an atmospheric dataset. Given a polynya boundary and an atmospheric dataset, the model correctly reproduces the shape of an 11 day long event, using only a few simple conservation laws. Ice production is slightly overestimated by the model, owing to an underestimated ice thickness. We achieved best model results with the consolidation thickness parameterization developed by Biggs and others (2000). Observed regional discrepancies between model and satellite estimates might be a consequence of the missing representation of the dynamic of the thin-ice thickening (e.g. rafting). We conclude that this simplified polynya model is a valuable tool for studying polynya dynamics and estimating associated fluxes of single polynya events.

Long-lived excited-state dynamics of i-motif structures probed by time-resolved infrared spectroscopy

UV-generated excited states of cytosine (C) nucleobases are precursors to mutagenic photoproduct formation. The i-motif formed from C-rich sequences is known to exhibit high yields of long-lived excited states following UV absorption. Here the excited states of several i-motif structures have been characterized following 267 nm laser excitation using time-resolved infrared spectroscopy (TRIR). All structures possess a long-lived excited state of ~300 ps and notably in some cases decays greater than 1 ns are observed. These unusually long-lived lifetimes are attributed to the interdigitated DNA structure which prevents direct base stacking overlap.

The water vapour continuum in near-infrared windows – current understanding and prospects for its inclusion in spectroscopic databases

Spectroscopic catalogues, such as GEISA and HITRAN, do not yet include information on the water vapour continuum that pervades visible, infrared and microwave spectral regions. This is partly because, in some spectral regions, there are rather few laboratory measurements in conditions close to those in the Earth’s atmosphere; hence understanding of the characteristics of the continuum absorption is still emerging. This is particularly so in the near-infrared and visible, where there has been renewed interest and activity in recent years. In this paper we present a critical review focusing on recent laboratory measurements in two near-infrared window regions (centred on 4700 and 6300 cm−1) and include reference to the window centred on 2600 cm−1 where more measurements have been reported. The rather few available measurements, have used Fourier transform spectroscopy (FTS), cavity ring down spectroscopy, optical-feedback – cavity enhanced laser spectroscopy and, in very narrow regions, calorimetric interferometry. These systems have different advantages and disadvantages. Fourier Transform Spectroscopy can measure the continuum across both these and neighbouring windows; by contrast, the cavity laser techniques are limited to fewer wavenumbers, but have a much higher inherent sensitivity. The available results present a diverse view of the characteristics of continuum absorption, with differences in continuum strength exceeding a factor of 10 in the cores of these windows. In individual windows, the temperature dependence of the water vapour self-continuum differs significantly in the few sets of measurements that allow an analysis. The available data also indicate that the temperature dependence differs significantly between different near-infrared windows. These pioneering measurements provide an impetus for further measurements. Improvements and/or extensions in existing techniques would aid progress to a full characterisation of the continuum – as an example, we report pilot measurements of the water vapour self-continuum using a supercontinuum laser source coupled to an FTS. Such improvements, as well as additional measurements and analyses in other laboratories, would enable the inclusion of the water vapour continuum in future spectroscopic databases, and therefore allow for a more reliable forward modelling of the radiative properties of the atmosphere. It would also allow a more confident assessment of different theoretical descriptions of the underlying cause or causes of continuum absorption.