Principles and promise of Fabry-Perot resonators at terahertz frequencies

Fabry–Perot resonators have tremendous potential to enhance the sensitivity of spectroscopic systems at terahertz (THz) frequencies. Increasing sensitivity will be of benefit in compensating for the relatively low power of current high resolution continuous wave THz radiation techniques, and to fully express the potential of THz spectroscopy as source power increases. Improved sensitivities, and thus scanning speeds, will allow detailed studies of the complex vibration-rotation-tunneling dynamics that large molecules show at THz wavelengths, and will be especially important in studying more elusive, transient species such as those present in planetary atmospheres and the interstellar medium. Coupling radiation into the cavity presents unique challenges at THz frequencies, however, meaning that the cavity configurations common in neighboring frequency domains cannot simply be translated. Instead, novel constructions are needed. Here we present a resonator design in which wire-grid polarizers serve as the input and output coupling mirrors. Using this configuration, Q-factors of a few times 10^5 are achieved near 0.3 THz. To aid future investigations, the parameter space that limits the quality of the cavity is explored and paths to improved performance highlighted. Lastly, the performance of polarizer cavity-based Fourier transform (FT) THz spectrometers is discussed, in particular those design optimizations that should allow for the construction of THz instrumentation that rivals and eventually surpasses the sensitivities achieved with modern FT-microwave cavity spectrometers

Constraints on the age and dilution of Pacific Exploratory Mission-Tropics biomass burning plumes from the natural radionuclide tracer 210Pb

During the NASA Global Troposphere Experiment Pacific Exploratory Mission-Tropics (PEM-Tropics) airborne sampling campaign we found unexpectedly high concentrations of aerosol-associated 210Pb throughout the free troposphere over the South Pacific. Because of the remoteness of the study region, we expected specific activities to be generally less than 35 μBq m−3 but found an average in the free troposphere of 107 μBq m−3. This average was elevated by a large number of very active (up to 405 μBq m−3) samples that were associated with biomass burning plumes encountered on nearly every PEM-Tropics flight in the southern hemisphere. We use a simple aging and dilution model, which assumes that 222Rn and primary combustion products are pumped into the free troposphere in wet convective systems over fire regions (most likely in Africa), to explain the elevated 210Pb activities. This model reproduces the observed 210Pb activities very well, and predicts the ratios of four hydrocarbon species (emitted by combustion) to CO to better than 20% in most cases. Plume ages calculated by the model depend strongly on the assumed 222Rn activities in the initial plume, but using values plausible for continental boundary layer air yields ages that are consistent with travel times from Africa to the South Pacific calculated with a back trajectory model. The model also shows that despite being easily recognized through the large enhancements of biomass burning tracers, these plumes must have entrained large fractions of the surrounding ambient air during transport

Systematics of the odd-even effect in the resonance ionization of Os and Ti

Measurements of the odd-even effect in the mass spectrometric analysis of Ti and Os isotopes by resonance ionization mass spectrometry have been performed for ΔJ = + 1, 0 and -1 transitions. Under saturating conditions of the ionization and for ΔJ = + 1 transitions odd-even effects are reduced below the 0.5% level. Depending on the polarization state of the laser large odd isotope enrichments are observed for ΔJ = 0 and -1 transitions which can be reduced below the 0.5% level by depolarization of the laser field

Laser-induced isotopic selectivity in the resonance ionization of Os

Isotope selective effects in resonance ionization mass spectrometry (RIMS) pose a potentially serious limitation to the application of this technique to the precise and reproducible measurement of isotope ratios. In order to identify some of the underlying causes of isotope selectivity in RIMS and to establish procedures for minimizing these effects, we investigated laser-induced isotope selectivity in the resonance ionization of Os. A single-color, one-photon resonant ionization scheme was used for several different transitions to produce Os photoions from a thermal atomization source. Variations in Os isotope ratios were studied as a function of laser parameters such as wavelength, bandwidth, power and polarization state. Isotope selectivity is strongly dependent on laser power and wavelength, even when the bandwidth of the laser radiation is much larger than the optical isotope shift. Variations in the ^(190)Os/^(188)Os ratio of ≈20% for a detuning of 0.8 cm^(−1) were observed on a transition with a small oscillator strength. Large even—odd isotope selectivity with a 13% depletion of ^(189)Os was observed on a ΔJ = +1 transition at low laser intensity; the odd mass Os isotopes are systematically depleted. For ΔJ = −1 and 0 transitions the isotope selectivity was reduced by polarization scrambling and for strongly saturating conditions. A technique employing the wavelength dependence of even—even isotope selectivity as an internal wavelength standard was developed to permit accurate and reproducible wavelength adjustment of the laser radiation. This technique provides control over laser-induced isotope selectivity for single-color ionization and enabled us to obtain reproducible measurements of ^(192)Os/^(188)Os and ^(189)Os/^(190)Os ratios in the saturation regime for a ΔJ = +1 transition with a precision of better than 0.5%. The application of this wavelength-tuning procedure should significantly improve the quality of RIMS isotope ratio data for many elements

Systematics of isotope ratio measurements with resonant laser photoionization sources

Sources of laser-induced even-even and odd-even isotopic selectivity in the resonance ionization mass spectroscopy of Os and Ti have been investigated experimentally for various types of transitions. A set of conditions with regard to laser bandwidth and frequency tuning, polarization state and intensity was obtained for which isotopic selectivity is either absent or reduced below the 2 % level

Search for interstellar methoxyacetonitrile and cyanoethanol: insights into coupling of cyano- to methanol and ammonia chemistry

As part of an effort to study gas-grain chemical models in star-forming regions as they relate to molecules containing cyanide (–C≡N) groups, we present here a search for the molecules 2-cyanoethanol (OHCH_2CH_2CN) and methoxyacetonitrile (CH_3OCH_2CN) in the galactic center region SgrB2. These species are structural isomers of each other and are targeted to investigate the cross-coupling of pathways emanating from the photolysis products of methanol and ammonia with pathways involving cyano-containing molecules. Methanol and ammonia ices are two of the main repositories of the elements C, O, and N in cold clouds and understanding their link to cyanide chemistry could give important insights into prebiotic molecular evolution. Neither species was positively detected, but the upper limits we determined allow comparison to the general patterns gleaned from chemical models. Our results indicate the need for an expansion of the model networks to better deal with cyanochemistry, in particular with respect to pathways including products of methanol photolysis. In addition to these results, the two main observational routes for detecting new interstellar molecules are discussed. One route is by decreasing detection limits at millimeter wavelength through spatial filtering with interferometric studies at the Atacama Large Millimeter Array (ALMA), and the second is by searching for intense torsional states at THz frequencies using the Herschel Space Observatory. 2-cyanoethanol and methoxyacetonitrile would both be good test beds for exploring the capabilities of ALMA and Herschel in the study of complex interstellar chemistry

Excitation of methyl cyanide in the hot core of Orion

The excitation of CH_3CN in the hot core of Orion is examined using high-sensitivity observational data at 1.3 mm. Observed line fluxes are analyzed by means of multilevel statistical equilibrium (SE) calculations which incorporate current theoretical values of the collisional excitation rates. The analysis is applied to both optically thin models of the hot core region and models with significant optical depths. Trapping is found to play a critical role in the excitation of CH_3CN. An optically thin analysis yields a kinetic temperature of 275 K and a cloud density of 2 x 10^6 cm^(-3). Unequal column densities are deduced in this case for the two symmetry species: N_A = 1.4 x 10^(14) cm^(-2) and N_E = 2.0 x 10^(14) cm^(-2). The deduced cloud density and temperature are lowered to 1.5 x 10^6 cm^(-3) and 240 K. The model with trapping is favored because of the agreement with measured sizes of the hot core source and the more plausible N_A/N_E ratio. Analysis of radiative excitation in the hot core indicates it is unlikely to significantly affect the ground vibrational state populations of CH_3CN. It most likely is significant for excitation of the V_8 band