Two-Dimensional Spectroscopy of Extended Molecular Systems: Applications to Energy Transport and Relaxation in an α-Helix

A simulation study of the coupled dynamics of amide I and amide II vibrations in an α-helix dissolved in water shows that two-dimensional (2D) infrared spectroscopy may be used to disentangle the energy transport along the helix through each of these modes from the energy relaxation between them. Time scales for both types of processes are obtained. Using polarization-dependent 2D spectroscopy is an important ingredient in the method we propose. The method may also be applied to other two-band systems, both in the infrared (collective vibrations) and the visible (excitons) parts of the spectrum.

Calibration of the MSL/ChemCam/LIBS Remote Sensing Composition Instrument

The ChemCam instrument suite on board the 2011 Mars Science Laboratory (MSL) Rover, Curiosity, will provide remote-sensing composition information for rock and soil samples within seven meters of the rover using a laser-induced breakdown spectroscopy (LIBS) system, and will provide context imaging with a resolution of 0.10 mradians using the remote micro-imager (RMI) camera. The high resolution is needed to image the small analysis footprint of the LIBS system, at 0.2-0.6 mm diameter. This fine scale analytical capability will enable remote probing of stratigraphic layers or other small features the size of "blueberries" or smaller. ChemCam is intended for rapid survey analyses within 7 m of the rover, with each measurement taking less than 6 minutes. Repeated laser pulses remove dust coatings and provide depth profiles through weathering layers, allowing detailed investigation of rock varnish features as well as analysis of the underlying pristine rock composition. The LIBS technique uses brief laser pulses greater than 10 MW/square mm to ablate and electrically excite material from the sample of interest. The plasma emits photons with wavelengths characteristic of the elements present in the material, permitting detection and quantification of nearly all elements, including the light elements H, Li, Be, B, C, N, O. ChemCam LIBS projects 14 mJ of 1067 nm photons on target and covers a spectral range of 240-850 nm with resolutions between 0.15 and 0.60 nm FWHM. The Nd:KGW laser is passively cooled and is tuned to provide maximum power output from -10 to 0 C, though it can operate at 20% degraded energy output at room temperature. Preliminary calibrations were carried out on the flight model (FM) in 2008. However, the detectors were replaced in 2009, and final calibrations occurred in April-June, 2010. This presentation describes the LIBS calibration and characterization procedures and results, and details plans for final analyses during rover system thermal testing, planned for early March

Diagenetic origin of nodules in the Sheepbed member, Yellowknife Bay formation, Gale crater, Mars

The Sheepbed member of the Yellowknife Bay formation in Gale crater contains millimeter‐scale nodules that represent an array of morphologies unlike those previously observed in sedimentary deposits on Mars. Three types of nodules have been identified in the Sheepbed member in order of decreasing abundance: solid nodules, hollow nodules, and filled nodules, a variant of hollow nodules whose voids have been filled with sulfate minerals. This study uses Mast Camera (Mastcam) and Mars Hand Lens Imager (MAHLI) images from the Mars Science Laboratory Curiosity rover to determine the size, shape, and spatial distribution of the Sheepbed nodules. The Alpha Particle X‐Ray Spectrometer (APXS) and ChemCam instruments provide geochemical data to help interpret nodule origins. Based on their physical characteristics, spatial distribution, and composition, the nodules are interpreted as concretions formed during early diagenesis. Several hypotheses are considered for hollow nodule formation including origins as primary or secondary voids. The occurrence of concretions interpreted in the Sheepbed mudstone and in several other sedimentary sequences on Mars suggests that active groundwater systems play an important role in the diagenesis of Martian sedimentary rocks. When concretions are formed during early diagenetic cementation, as interpreted for the Sheepbed nodules, they have the potential to create a taphonomic window favorable for the preservation of Martian organics

Diagenetic origin of nodules in the Sheepbed member, Yellowknife Bay formation, Gale crater, Mars

The Sheepbed member of the Yellowknife Bay formation in Gale crater contains millimeter‐scale nodules that represent an array of morphologies unlike those previously observed in sedimentary deposits on Mars. Three types of nodules have been identified in the Sheepbed member in order of decreasing abundance: solid nodules, hollow nodules, and filled nodules, a variant of hollow nodules whose voids have been filled with sulfate minerals. This study uses Mast Camera (Mastcam) and Mars Hand Lens Imager (MAHLI) images from the Mars Science Laboratory Curiosity rover to determine the size, shape, and spatial distribution of the Sheepbed nodules. The Alpha Particle X‐Ray Spectrometer (APXS) and ChemCam instruments provide geochemical data to help interpret nodule origins. Based on their physical characteristics, spatial distribution, and composition, the nodules are interpreted as concretions formed during early diagenesis. Several hypotheses are considered for hollow nodule formation including origins as primary or secondary voids. The occurrence of concretions interpreted in the Sheepbed mudstone and in several other sedimentary sequences on Mars suggests that active groundwater systems play an important role in the diagenesis of Martian sedimentary rocks. When concretions are formed during early diagenetic cementation, as interpreted for the Sheepbed nodules, they have the potential to create a taphonomic window favorable for the preservation of Martian organics

The SuperCam Instrument Suite on the Mars 2020 Rover: Science Objectives and Mast-Unit Description

On the NASA 2020 rover mission to Jezero crater, the remote determination of the texture, mineralogy and chemistry of rocks is essential to quickly and thoroughly characterize an area and to optimize the selection of samples for return to Earth. As part of the Perseverance payload, SuperCam is a suite of five techniques that provide critical and complementary observations via Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), visible and near-infrared spectroscopy (VISIR), high-resolution color imaging (RMI), and acoustic recording (MIC). SuperCam operates at remote distances, primarily 2-7 m, while providing data at sub-mm to mm scales. We report on SuperCam's science objectives in the context of the Mars 2020 mission goals and ways the different techniques can address these questions. The instrument is made up of three separate subsystems: the Mast Unit is designed and built in France; the Body Unit is provided by the United States; the calibration target holder is contributed by Spain, and the targets themselves by the entire science team. This publication focuses on the design, development, and tests of the Mast Unit; companion papers describe the other units. The goal of this work is to provide an understanding of the technical choices made, the constraints that were imposed, and ultimately the validated performance of the flight model as it leaves Earth, and it will serve as the foundation for Mars operations and future processing of the data.In France was provided by the Centre National d'Etudes Spatiales (CNES). Human resources were provided in part by the Centre National de la Recherche Scientifique (CNRS) and universities. Funding was provided in the US by NASA's Mars Exploration Program. Some funding of data analyses at Los Alamos National Laboratory (LANL) was provided by laboratory-directed research and development funds

Aqueous alteration processes in Jezero crater, Mars—implications for organic geochemistry

The Perseverance rover landed in Jezero crater, Mars, in February 2021. We used the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument to perform deep-ultraviolet Raman and fluorescence spectroscopy of three rocks within the crater. We identify evidence for two distinct ancient aqueous environments at different times. Reactions with liquid water formed carbonates in an olivine-rich igneous rock. A sulfate-perchlorate mixture is present in the rocks, which probably formed by later modifications of the rocks by brine. Fluorescence signatures consistent with aromatic organic compounds occur throughout these rocks and are preserved in minerals related to both aqueous environments

Soil Diversity and Hydration as Observed by ChemCam at Gale Crater, Mars

Abstract: The ChemCam instrument, which provides insight into martian soil chemistry at the submillimeter scale, identified two principal soil types along the Curiosity rover traverse: a fine-grained mafic type and a locally derived, coarse-grained felsic type. The mafic soil component is representative of widespread martian soils and is similar in composition to the martian dust. It possesses a ubiquitous hydrogen signature in ChemCam spectra, corresponding to the hydration of the amorphous phases found in the soil by the CheMin instrument. This hydration likely accounts for an important fraction of the global hydration of the surface seen by previous orbital measurements. ChemCam analyses did not reveal any significant exchange of water vapor between the regolith and the atmosphere. These observations provide constraints on the nature of the amorphous phases and their hydration.Keywords: Water, Allophane, Chemistry, X-ray spectrometer, Surface, Instrument suite, Chemical composition, Emission spectrometer data, Hydrous minerals, Martian Regolit

Volatile and Organic Compositions of Sedimentary Rocks in Yellowknife Bay, Gale crater, Mars

H₂O, CO₂, SO₂, O₂, H₂, H₂S, HCl, chlorinated hydrocarbons, NO and other trace gases were evolved during pyrolysis of two mudstone samples acquired by the Curiosity rover at Yellowknife Bay within Gale crater, Mars. H₂O/OH-bearing phases included 2:1 phyllosilicate(s), bassanite, akaganeite, and amorphous materials. Thermal decomposition of carbonates and combustion of organic materials are candidate sources for the CO₂. Concurrent evolution of O₂ and chlorinated hydrocarbons suggest the presence of oxychlorine phase(s). Sulfides are likely sources for S-bearing species. Higher abundances of chlorinated hydrocarbons in the mudstone compared with Rocknest windblown materials previously analyzed by Curiosity suggest that indigenous martian or meteoritic organic C sources may be preserved in the mudstone; however, the C source for the chlorinated hydrocarbons is not definitively of martian origin