Laser-Induced Breakdown spectroscopy (LIBS) and Laser-Induced Thermal Emission (LITE) emission based laser remote sensing were investigated with the application to the remote measurements of trace chemical species. In particular, UVvisible LIBS and Mid-IR LITE systems were developed and measurements of remote targets and chemical surfaces were studied. The propagation through the atmosphere of the multi-wavelength backscattered LIBS and LITE optical spectrum with atmospheric absorption effects on the returned lidar signal was investigated. An enhanced model of the atmospheric effects on emission-based laser-remote sensing was developed and found to be consistent and in agreement with our experimental results. LITE measurements were performed which involved heating a remote hard target and recording the vibrational band emission spectra produced. Sample heating was carried out using a 1.5W cw-CO2 10.6 μm wavelength laser, and a 9W cw-diode laser operating at 809nm. The emission spectra over the wavelength range of 8 to 14 μm was observed which can be potentially used to detect and identify chemical composition of the target. LITE spectra of DMMP and DIMP (chemical agent simulants), paints, and energetic materials on various substrates were measured for the first time. A LIBS study was carried out with a 1.064 μm Nd:YAG laser (10 ns pulses, 50mJ per pulse) and remote LIBS measurements were performed for aluminum, copper, steel and plastics over the spectral range of 200 – 1000nm. LIBS measurements as a function of range were studied, and compared to a modified lidar equation suitable for emission based lidar remote sensing. A computer simulation model was developed for emission-based LIDAR remote sensing such as LIBS and LITE. This involved the development and modification of atmospheric transmission modeling programs which use the HITRAN, PNNL and other atmospheric spectral databases to model the transmission of the atmosphere over a wide range of wavelengths from the deep-UV near 200 nm to the mid-IR near 14 microns. A comparison of HITRAN simulations with the PNNL database calculated spectra was carried out and used for the first time for improvements of the HITRAN database line intensities. In addition, a Principal Component Analysis (PCA) of the LIBS and LITE lidar return signal as a function of range was performed. This PCA analysis showed, for the first time, the degradation of the chemical selectivity (i.e. identification capability) of the emission lidar system as the range was increased and the effect of atmospheric absorption spectral lines on the propagated LIBS and LITE lidar multi-wavelength spectral signal.

No / Scytonemin-imine, a novel derivative of scytonemin, has been isolated and identified very recently and proposed to serve as a photoprotective biomarker for certain bacteria growing under intense photon flux density. This study predicts theoretically the Raman spectrum of scytonemin-imine by density functional theory calculations and provides comparison of major bands to those of scytonemin, the parent compound for which both the experimentally characterized and theoretically predicted spectra exist in the literature. It is proposed to be an addendum to the collection of our previous work on scytonamin and its derivatives to facilitate recognition of the diagnostic Raman spectral signatures for scytonemin-imine.

No / Raman spectroscopy has been identified as an important first-pass analytical technique for deployment on planetary surfaces as part of a suite of instrumentation in projected remote space exploration missions to detect extant or extinct extraterrestrial life signatures. Aside from the demonstrable advantages of a non-destructive sampling procedure and an ability to record simultaneously the molecular signatures of biological, geobiological and geological components in admixture in the geological record, the interrogation and subsequent interpretation of spectroscopic data from these experiments will be critically dependent upon the recognition of key biomolecular markers indicative of life existing or having once existed in extreme habitats. A comparison made with the characteristic Raman spectral wavenumbers obtained from standards is not acceptable because of shifts that can occur in the presence of other biomolecules and their host mineral matrices. In this paper, we identify the major sources of difficulty experienced in the interpretation of spectroscopic data centring on a key family of biomarker molecules, namely scytonemin and its derivatives; the parent scytonemin has been characterized spectroscopically in cyanobacterial colonies inhabiting some of the most extreme terrestrial environments and, with the support of theoretical calculations, spectra have been predicted for the characterization of several of its derivatives which could occur in novel extraterrestrial environments. This work will form the foundation for the identification of novel biomarkers and for their Raman spectroscopic discrimination, an essential step in the interpretation of potentially complex and hitherto unknown biological radiation protectants based on the scytoneman and scytonin molecular skeletons which may exist in niche geological scenarios in the surface and subsurface of planets and their satellites in our Solar System.