Study of picosecond processes of an intercalated dipyridophenazine Cr(iii) complex bound to defined sequence DNAs using transient absorption and time-resolved infrared methods

Picosecond transient absorption (TA) and time-resolved infrared (TRIR) measurements of rac-[Cr(phen)2(dppz)]3+ (1) intercalated into double-stranded guanine-containing DNA reveal that the excited state is very rapidly quenched. As no evidence was found for the transient electron transfer products, it is proposed that the back electron transfer reaction must be even faster (<3 ps).

First CRDS-measurements of water vapour continuum in the 940nm absorption band

Measurements of near-infrared water vapour continuum using continuous wave cavity ring down spectroscopy (cw- CRDS) have been performed at around 10611.6 and 10685:2 cm1. The continuum absorption coefficients for N2- broadening have been determined for two temperatures and wavenumbers. These results represent the first near-IR continuum laboratory data determined within the complex spectral environment in the 940nm water vapour band and are in reasonable agreement with simulations using the semiempirical CKD formulation.

Evaluation of suitable spectral intervals for near-IR laboratory detection of water vapour continuum absorption

The water vapour continuum absorption is an important component of molecular absorption of radiation in atmosphere. However, uncertainty in knowledge of the value of the continuum absorption at present can achieve 100% in different spectral regions leading to an error in flux calculation up to 3-5 W/m2 global mean. This work uses line-by-line calculations to reveal the best spectral intervals for experimental verification of the CKD water vapour continuum models in the currently least studied near-infrared spectral region. Possible sources of errors in continuum retrieval taken into account in the simulation include the sensitivity of laboratory spectrometers and uncertainties in the spectral line parameters in HITRAN-2004 and Schwenke-Partridge database. It is shown that a number of micro-windows in near-IR can be used at present for laboratory detection of the water vapour continuum with estimated accuracy from 30 to 5%.

Assessment of the consistency of near-infrared water vapor line intensities using high-spectral-resolution ground-based Fourier transform measurements of solar radiation

Calculations of the absorption of solar radiation by atmospheric gases, and water vapor in particular, are dependent on the quality of databases of spectral line parameters. There has been increasing scrutiny of databases such as HITRAN in recent years, but this has mostly been performed on a band-by-band basis. We report nine high-spectral-resolution (0.03 cm(-1)) measurements of the solar radiation reaching the surface in southern England over the wave number range 2000 to 12,500 cm(-1) (0.8 to 5 mm) that allow a unique assessment of the consistency of the spectral line databases over this entire spectral region. The data are assessed in terms of the modeled water vapor column that is required to bring calculations and observations into agreement; for an entirely consistent database, this water vapor column should be constant with frequency. For the HITRAN01 database, the spread in water vapor column is about 11%, with distinct shifts between different spectral regions. The HITRAN04 database is in significantly better agreement (about 5% spread) in the completely updated 3000 to 8000 cm(-1) spectral region, but inconsistencies between individual spectral regions remain: for example, in the 8000 to 9500 cm(-1) spectral region, the results indicate an 18% (+/- 1%) underestimate in line intensities with respect to the 3000 to 8000 cm(-1) region. These measurements also indicate the impact of isotopic fractionation of water vapor in the 2500 to 2900 cm(-1) range, where HDO lines dominate over the lines of the most abundant isotope of H2O.

Vibrational Renner-Teller effects in the infrared spectrum of carbonsuboxide

The infrared spectrum of carbon suboxide has been recorded with a resolution of 0•01cm-1 from 400 to 700 cm-1. The region from 530 to 570 cm-1 shows intense absorption due to the v6(Πu) band system, of which the fundamental band only has been assigned and analysed, giving v6=540•221 cm-1. The region 590 to 660 cm-1 shows weaker absorption due to the v5(Πg) band system appearing in combination with odd quanta of the v7(Πu) fundamental at 18 cm-1. The v5 + v7 band and several hot bands have been assigned and analysed, and the effective v7 bending potential in the v5 state has been deduced. This potential shows a splitting as the large amplitude bending coordinate q7 is displaced due to interaction between v5 and v7 analogous to the Renner-Teller effect in electronic spectroscopy. This splitting is about 4 cm-1 for the classical turning points in q7 and the mean q7 bending potential is closely similar to that in the ground state.

Calibration and use of a cesium-iodide prism in the infrared

With a cesium-iodide prism the long wavelength range of an infrared spectrometer may be extended to 55µ The use of such a prism, the choice of optical system, and the problems of stray radiation are all discussed. Accurate data are assembled for calibration in this region, and sample calibration traces are shown. A simple gas absorption cell is described for use at long wavelengths.

Remote gas detection and quantitative analysis from infrared emission spectra obtained by Fourier transform infrared spectroscopy

Techniques for obtaining quantitative values of the temperatures and concentrations of remote hot gaseous effluents from their measured passive emission spectra have been examined in laboratory experiments. The high sensitivity of the spectrometer in the vicinity of the 2397 cm-1 band head region of CO2 has allowed the gas temperature to be calculated from the relative intensity of the observed rotational lines. The spatial distribution of the CO2 in a methane flame has been reconstructed tomographically using a matrix inversion technique. The spectrometer has been calibrated against a black body source at different temperatures and a self absorption correction has been applied to the data avoiding the need to measure the transmission directly. Reconstruction artifacts have been reduced by applying a smoothing routine to the inversion matrix.

Temperature dependent high-resolution infrared photoabsorption cross-sections of trifluoromethyl sulphur pentafluoride

Absolute infrared photoabsorption cross-sections have been measured over the range 600-1500 cm(-1) for the powerful greenhouse gas SF5CF3 at high resolution (0.03 cm(-1)) and at temperatures between 203 and 298 K. Our data indicate that the integrated absorption intensity shows a weak negative dependence on temperature. It is concluded therefore that previous calculations of radiative forcings and global warming potentials based on room-temperature data are reasonable estimates for the atmosphere, but may be low by a few percent. (C) 2002 Elsevier Science B.V. All rights reserved.

The temperature-dependent spectral properties of filter substrate materials in the far-infrared (6-40 mu m)

This paper presents the experimental results on the low temperature absorption and dispersion properties for a variety of frequently used infrared filter substrate materials. Index of refraction (n) and transmission spectra are presented for a range of temperatures 300-50 K for the Group IV materials silicon (Si) and germanium (Ge), and Group II-VI materials zinc selenide (ZnSe), zinc sulphide (ZnS) and cadmium telluride (CdTe). (C) 2003 Elsevier B.V. All rights reserved.

Theoretical investigation of infrared spectra and pocket dynamics of photodissociated carbonmonoxy myoglobin

Molecular dynamics simulations of the photodissociated state of carbonmonoxy myoglobin (MbCO) are presented using a fluctuating charge model for CO. A new three-point charge model is fitted to high-level ab initio calculations of the dipole and quadrupole moment functions taken from the literature. The infrared spectrum of the CO molecule in the heme pocket is calculated using the dipole moment time autocorrelation function and shows good agreement with experiment. In particular, the new model reproduces the experimentally observed splitting of the CO absorption spectrum. The splitting of 3–7 cm−1 (compared to the experimental value of 10 cm−1) can be directly attributed to the two possible orientations of CO within the docking site at the edge of the distal heme pocket (the B states), as previously suggested on the basis of experimental femtosecond time-resolved infrared studies. Further information on the time evolution of the position and orientation of the CO molecule is obtained and analyzed. The calculated difference in the free energy between the two possible orientations (Fe···CO and Fe···OC) is 0.3 kcal mol−1 and agrees well with the experimentally estimated value of 0.29 kcal mol−1. A comparison of the new fluctuating charge model with an established fixed charge model reveals some differences that may be critical for the correct prediction of the infrared spectrum and energy barriers. The photodissociation of CO from the myoglobin mutant L29F using the new model shows rapid escape of CO from the distal heme pocket, in good agreement with recent experimental data. The effect of the protein environment on the multipole moments of the CO ligand is investigated and taken into account in a refined model. Molecular dynamics simulations with this refined model are in agreement with the calculations based on the gas-phase model. However, it is demonstrated that even small changes in the electrostatics of CO alter the details of the dynamics.

Ultrafast charge separation in a photoreactive rhenium-appended porphyrin assembly monitored by picosecond transient infrared spectroscopy

Rhenium(bipyridine)(tricarbonyl)(picoline) units have been linked covalently to tetraphenylmetalloporphyrins of magnesium and zinc via an amide bond between the bipyridine and one phenyl substituent of the porphyrin. The resulting complexes, abbreviated as [Re(CO)(3)(Pic)Bpy-MgTPP][OTf] and [Re(CO)(3)(Pic)Bpy-ZnTPP][OTf], exhibit no signs of electronic interaction between the Re(CO)(3)(bpy) units and the metalloporphyrin units in their ground states. However, emission spectroscopy reveals solvent-dependent quenching of porphyrin emission on irradiation into the long-wavelength absorption bands localized on the porphyrin. The characteristics of the excited states have been probed by picosecond time-resolved absorption (TRVIS) spectroscopy and time-resolved infrared (TRIR) spectroscopy in nitrile solvents. The presence of the charge-separated state involving electron transfer from MgTPP or ZnTPP to Re(bpy) is signaled in the TRIR spectra by a low-frequency shift in the nu(CO) bands of the Re(CO)(3) moiety similar to that observed by spectroelectrochemical reduction. Long-wavelength excitation of [Re(CO)(3)(Pic)Bpy-MTPP][OTf] results in characteristic TRVIS spectra of the S-1 state of the porphyrin that decay with a time constant of 17 ps (M = Mg) or 24 ps (M = Zn). The IR bands of the CS state appear on a time scale of less than 1 ps (Mg) or ca. 5 ps (Zn) and decay giving way to a vibrationally excited (i.e., hot) ground state via back electron transfer. The IR bands of the precursors recover with a time constant of 35 ps (Mg) or 55 ps (Zn). The short lifetimes of the charge-transfer states carry implications for the mechanism of reaction in the presence of triethylamine.

Infrared filters for space-flight focal plane array applications

Infrared filters and coatings have been employed on many sensing radiometer instruments to measure the thermal emission profiles and concentrations of certian chemical constituents found in planetary atmospheres. The High Resolution Dynamics Limb Sounder ( HIRDLS) is an example of the most recent developments in limb-viewing radiometry by employing a cooled focal plane detector array to provide simultaneous multi-channel monitoring of emission from gas and aerosols over an altitude range between 8 - 70 km. The use of spectrally selective cooled detectors in focal plane arrays has simplified the optical layout of radiometers, greatly reducing the number of components in the optical train. this has inevitably led to increased demands for the enviromnetal durability of the focal plane filters because of the need to cut sub-millimeter sizes, whilst maintaining an optimal spectral performance. Additionally the remaining refractive optical elements require antireflection coatings which must cover the entire spectral range of the focal plane array channels, in this case 6 to 18µm, with a minimum of reflection and absorption. This paper describes the optical layout and spectral design requirements for filteriong in the HIRDLS instrument, and reports progress on the manufacturing and testing of the sub-millimetre sized cooled filters. We also report on the spectral and environmental performance of prototype wideband antireflection coatings which satisfy the requirements above.

High-performance infrared filters for the HIRDLS 21-channel focal plane detector array

The High Resolution Dynamics Limb Sounder is described, with particular reference to the atmospheric measurements to be made and the rationale behind the measurement strategy. The demands this strategy places on the filters to be used in the instrument and the designs to which this leads to are described. A second set of filters at an intermediate image plane to reduce "Ghost Imaging" is discussed together with their required spectral properties. A method of combining the spectral characteristics of the primary and secondary filters in each channel are combined together with the spectral response of the detectors and other optical elements to obtain the system spectral response weighted appropriately for the Planck function and atmospheric limb absorption. This method is used to demonstrate whether the out-of-band spectral blocking requirement for a channel is being met and an example calculation is demonstrated showing how the blocking is built up for a representative channel. Finally, the techniques used to produce filters of the necessary sub-millimetre sizes together with the testing methods and procedures used to assess the environmental durability and establish space flight quality are discussed.

Design and disposition of infrared optical multilayer coatings for the Improved Stratospheric and Mesospheric Sounder (ISAMS)

The Improved Stratospheric and Mesospheric Sounder (ISAMS) is designed to measure the Earths middle atmosphere in the range of 4.6 to 16.6 micorns. This paper considers all the coated optical elements in two radiometric test channels. (Analysis of the spectral response will be presented as a seperate paper at this symposium, see Sheppard et al). Comparisons between the compued spectral performance and measurements from actual coatings will be discussed: These will include substrate absorption simulations. The results of environmental testing (durability and stability) are included, together with details of coating deposition and monitoring conditions.

Measurement of infrared multilayer filters at temperatures down to 4 deg K

Measurement is reported at 4 deg K (and blocked transmission below 10-5) of PbTe/ZnS thin-film filters deposited on Ge substrates. The reduced carrier-absorption which is obtained by cooling these PbTe films is found to accord with simple theory. Advantage for various high-performance multilayers by cooling is significant at the longer wavelengths, and has been verified.