Optical and radiometric models of the NOMAD instrument part I: the UVIS channel.

The NOMAD instrument has been designed to best fulfil the science objectives of the ExoMars Trace Gas Orbiter mission that will be launched in 2016. The instrument is a combination of three channels that cover the UV, visible and IR spectral ranges and can perform solar occultation, nadir and limb observations. In this series of two papers, we present the optical models representing the three channels of the instrument and use them to determine signal to noise levels for different observation modes and Martian conditions. In this first part, we focus on the UVIS channel, which will sound the Martian atmosphere using nadir and solar occultation viewing modes, covering the 200-650nm spectral range. High SNR levels (>1000) can easily be reached for wavelengths higher than 300nm both in solar occultation and nadir modes when considering binning. Below 300nm SNR are lower primarily because of the lower signal and the impact of atmospheric absorption.

NOMAD spectrometer on the ExoMars trace gas orbiter mission: part 1--design, manufacturing and testing of the infrared channels.

NOMAD is a spectrometer suite on board ESA's ExoMars trace gas orbiter due for launch in January 2016. NOMAD consists of two infrared channels and one ultraviolet and visible channel allowing the instrument to perform observations quasi-constantly, by taking nadir measurements at dayside and nightside, and during solar occultations. In this paper, the design, manufacturing, and testing of the two infrared channels are described. We focus upon the optical working principle in these channels, where an echelle grating, used as a diffractive element, is combined with an acousto-optical tunable filter, used as a diffraction order sorter.

Infrared spectra of the complexes of trifluoroethene with dimethyl ether, acetone, and oxirane: a cryosolution study.

Infrared spectra of solutions of trifluoroethene and dimethyl ether, acetone, or oxirane in liquid krypton and liquid argon have been studied. For each Lewis base the formation of a 1:1 complex with the Lewis acid was observed. The C-H stretching of trifluoroethene being perturbed by a strong Fermi resonance, the complexes with trifuloroethene-d were also investigated and showed that in each case the hydrogen bond between the acid and base is of the traditional, red-shifting type. The structures of the complexes were investigated using ab initio calculations. These indicate that with dimethyl ether and acetone two different isomeres can be formed, but with a single one detected in the solution in each case. The Fermi resonance in the complex with unlabeled trifluoroethene is discussed using data derived form ab initio potential and dipole hypersurface calculations. The complexation enthalpies of the complexes were obtained from temperature dependent studies of the solutions and are discussed in relation to the ab initio complexation energies and Monte Carlo free energy perturbation calculations of solvent effects.

Stabilities of the C-H...O bonded complexes of the haloforms HCClnF3-n (n = 0-3) with dimethyl ether, oxirane, and acetone: an experimental and theoretical study.

Complexation enthalpies of the complexes of the haloforms HCCl(n)F(3-)(n) (n = 0-3) with dimethyl ether, oxirane, and acetone have been determined in liquid krypton and/or liquid argon using infrared spectroscopy. The same quantities were derived starting from ab initio complexation energies, calculated at the MP2=FULL/aug-cc-VTZ level, and by correcting these energies for thermodynamic and solvent contributions. The two sets of data are compared and discussed.

A cryosolution infrared study of the complexes of fluoroform with ammonia and pyridine: Evidence for a C-H...N pseudo blue-shifting hydrogen bond.

Mid-infrared spectra of mixed solutions in liquid xenon containing fluoroform and either ammonia or pyridine have been investigated at temperatures between 173 and 213 K. For both Lewis bases, a new band is found in the CH stretching region at a frequency approximately 5 cm(-1) higher than that of monomer fluoroform, which is assigned to a complex between fluoroform and the Lewis base. A detailed analysis of the nu1/2nu(4) Fermi resonance in the proton donor shows that the blue shifts observed for the complexes are not caused by a strengthening of the CH bond during the complexation, but are due to the changes in the Fermi resonance interactions. Information on the nu1/2nu(4) Fermi resonance was also obtained for the complexes of fluoroform with dimethyl ether and trimethyl amine.

Blue shifting hydrogen bonding in the complexes of chlorofluoro haloforms with acetone-d(6) and oxirane-d(4).

Mixtures of haloforms of the type HCClnF3-n (n = 0-3) with oxirane-d4 and acetone-d6 have been studied in liquid krypton, using infrared spectroscopy. Analysis of the spectra shows that a small fraction of the monomers is transformed into 1:1 complexes in which the haloform C-H bond is hydrogen bonded to the oxygen atom of the base. For all complexes, the haloform CH stretch is blue shifted, with the shift increasing from chloroform to fluoroform, while the ratio of the infrared intensities of the C-H stretching bands of complexed and free C-H bonds changes from a value well over 50 for the chloroform to a value near 0.1 for the fluoroform complexes. These observations have been corroborated by ab initio calculations using CP-corrected gradient techniques.

Improper or classical hydrogen bonding? A comparative cryosolutions infrared study of the complexes of HCClF(2), HCCl(2)F, and HCCl(3) with dimethyl ether.

Complexes of haloforms of the type HCCl(n)F(3-)(n) (n = 1-3) with dimethyl ether have been studied in liquid argon and liquid krypton, using infrared spectroscopy. For the haloform C[bond]H stretching mode, the complexation causes blue shifts of 10.6 and 4.8 cm(-1) for HCClF(2) and HCCl(2)F, respectively, while for HCCl(3) a red shift of 8.3 cm(-1) is observed. The ratio of the band areas of the haloform C[bond]H stretching in complex and monomer was determined to be 0.86(4) for HCClF(2), 33(3) for HCCl(2)F, and 56(3) for HCCl(3). These observations, combined with those for the HCF(3) complex with the same ether (J. Am. Chem. Soc. 2001, 123, 12290), have been analyzed using ab initio calculations at the MP2[double bond]FC/6-31G(d) level, and using some recent models for improper hydrogen bonding. Ab initio calculations on the haloforms embedded in a homogeneous electric field to model the influence of the ether suggest that the complexation shift of the haloform C[bond]H stretching is largely explained by the electric field effect induced by the electron donor in the proton donor. The model calculations also show that the electric field effect accounts for the observed intensity changes of the haloform C[bond]H stretches.