Model for quantitative tip-enhanced spectroscopy and the extraction of nanoscale-resolved optical constants

Near-field infrared spectroscopy by elastic scattering of light from a probe tip resolves optical contrasts in materials at dramatically sub-wavelength scales across a broad energy range, with the demonstrated capacity for chemical identification at the nanoscale. However, current models of probe-sample near-field interactions still cannot provide a sufficiently quantitatively interpretation of measured near-field contrasts, especially in the case of materials supporting strong surface phonons. We present a model of near-field spectroscopy derived from basic principles and verified by finite-element simulations, demonstrating superb predictive agreement both with tunable quantum cascade laser near-field spectroscopy of SiO$_2$ thin films and with newly presented nanoscale Fourier transform infrared (nanoFTIR) spectroscopy of crystalline SiC. We discuss the role of probe geometry, field retardation, and surface mode dispersion in shaping the measured near-field response. This treatment enables a route to quantitatively determine nano-resolved optical constants, as we demonstrate by inverting newly presented nanoFTIR spectra of an SiO$_2$ thin film into the frequency dependent dielectric function of its mid-infrared optical phonon. Our formalism further enables tip-enhanced spectroscopy as a potent diagnostic tool for quantitative nano-scale spectroscopy.Comment: 19 pages, 9 figure

New Candidate Interstellar Particle in Stardust IS Aerogel Collector: Analysis by STXM and Ptychography

The Stardust Interstellar Preliminary Examination (ISPE) reported in 2014 the discovery of 7 probable contemporary interstellar (IS) particles captured in Stardust IS Collector aerogel and foils. The ISPE reports represented work done over 6 years by more than 60 scientists and >30,000 volunteers, which emphasizes the challenge identifying and analyzing Stardust IS samples was far beyond the primary Stardust cometary collection. We present a new potentially interstellar particle resulting from a continuation of analyses of the IS aerogel collection

Developing V-Xanes Oxybarometry for Probing Materials Formed in Reducing Environments in the Early Solar Disk

Vanadium exhibits four oxidation states (V(sup 2+), V(sup 3+), V(sup 4+) and V(sup 5+)) that have been shown to preferentially partition between melt phases dependent on redox conditions, spanning oxygen fugacity across more than 10 log units. We are developing synchrotron-based x-ray absorption spectroscopy of low-fugacity standards for the determination of V oxidation state in highly reducing conditions relevant to the early solar nebula

Oxygen Buffering in High Pressure Solid Media Assemblies: New Approach Enabling Study of fO2 from IW-4 to IW+4.5

Oxygen fugacity is an intensive parameter that controls some fundamental chemical and physical properties in planetary materials. In terrestrial magmas high fO2 promotes magnetite stability and low fO2 causes Fe-enrichment due to magnetite suppression. In lunar and asteroidal basalts, low fO2 can allow metal to be stable. Experimental studies will therefore be most useful if they are done at a specific and relevant fO2 for the samples under consideration. Control of fO2 in the solid media apparatus (piston cylinder multi-anvil) has relied on either sliding sensors or graphite capsule buffering, which are of limited application to the wide range of fO2 recorded in planetary or astromaterials. Here we describe a new approach that allows fO2 to be specified across a wide range of values relevant to natural samples

Comparison of the Oxidation State of Fe in Comet 81P/Wild 2 and Chondritic-Porous Interplanetary Dust Particles

The fragile structure of chondritic-porous interplanetary dust particles (CP- IDPs) and their minimal parent-body alteration have led researchers to believe these particles originate in comets rather than asteroids where aqueous and thermal alteration have occurred. The solar elemental abundances and atmospheric entry speed of CP-IDPs also suggest a cometary origin. With the return of the Stardust samples from Jupiter-family comet 81P/Wild 2, this hypothesis can be tested. We have measured the Fe oxidation state of 15 CP-IDPs and 194 Stardust fragments using a synchrotron-based x-ray microprobe. We analyzed ~300 nanograms of Wild 2 material - three orders of magnitude more material than other analyses comparing Wild 2 and CP-IDPs. The Fe oxidation state of these two samples of material are >2{\sigma} different: the CP-IDPs are more oxidized than the Wild 2 grains. We conclude that comet Wild 2 contains material that formed at a lower oxygen fugacity than the parent body, or parent bodies, of CP-IDPs. If all Jupiter-family comets are similar, they do not appear to be consistent with the origin of CP-IDPs. However, comets that formed from a different mix of nebular material and are more oxidized than Wild 2 could be the source of CP-IDPs.Comment: Earth and Planetary Science Letters, in pres

On the size and velocity distribution of cosmic dust particles entering the atmosphere

The size and velocity distribution of cosmic dust particles entering the Earth's atmosphere is uncertain. Here we show that the relative concentrations of metal atoms in the upper mesosphere, and the surface accretion rate of cosmic spherules, provide sensitive probes of this distribution. Three cosmic dust models are selected as case studies: two are astronomical models, the first constrained by infrared observations of the Zodiacal Dust Cloud and the second by radar observations of meteor head echoes; the third model is based on measurements made with a spaceborne dust detector. For each model, a Monte Carlo sampling method combined with a chemical ablation model is used to predict the ablation rates of Na, K, Fe, Mg, and Ca above 60 km and cosmic spherule production rate. It appears that a significant fraction of the cosmic dust consists of small (<5 µg) and slow (<15 km s−1) particles

A New View on Interstellar Dust - High Fidelity Studies of Interstellar Dust Analogue Tracks in Stardust Flight Spare Aerogel

In 2000 and 2002 the Stardust Mission exposed aerogel collector panels for a total of about 200 days to the stream of interstellar grains sweeping through the solar system. The material was brought back to Earth in 2006. The goal of this work is the laboratory calibration of the collection process by shooting high speed [5 - 30km/s] interstellar dust (ISD) analogues onto Stardust aerogel flight spares. This enables an investigation into both the morphology of impact tracks as well as any structural and chemical modification of projectile and collector material. First results indicate a different ISD flux than previously assumed for the Stardust collection period

Analysis of "Midnight" Tracks in the Stardust Interstellar Dust Collector: Possible Discovery of a Contemporary Interstellar Dust Grain

In January 2006, the Stardust sample return capsule returned to Earth bearing the first solid samples from a primitive solar system body, Comet 81P/Wild2, and a collector dedicated to the capture and return of contemporary interstellar dust. Both collectors were approximately 0.1m(exp 2) in area and were composed of aerogel tiles (85% of the collecting area) and aluminum foils. The Stardust Interstellar Dust Collector (SIDC) was exposed to the interstellar dust stream for a total exposure factor of 20 m(exp 2) day. The Stardust Interstellar Preliminary Examination (ISPE) is a three-year effort to characterize the collection using nondestructive techniques