Direct measurements of DOCO isomers in the kinetics of OD + CO.

Quantitative and mechanistically detailed kinetics of the reaction of hydroxyl radical (OH) with carbon monoxide (CO) have been a longstanding goal of contemporary chemical kinetics. This fundamental prototype reaction plays an important role in atmospheric and combustion chemistry, motivating studies for accurate determination of the reaction rate coefficient and its pressure and temperature dependence at thermal reaction conditions. This intricate dependence can be traced directly to details of the underlying dynamics (formation, isomerization, and dissociation) involving the reactive intermediates cis- and trans-HOCO, which can only be observed transiently. Using time-resolved frequency comb spectroscopy, comprehensive mechanistic elucidation of the kinetics of the isotopic analog deuteroxyl radical (OD) with CO has been realized. By monitoring the concentrations of reactants, intermediates, and products in real time, the branching and isomerization kinetics and absolute yields of all species in the OD + CO reaction are quantified as a function of pressure and collision partner.

Phase-stabilized 100 mW frequency comb near 10 µm.

Long-wavelength mid-infrared (MIR) frequency combs with high power and flexible tunability are highly desired for molecular spectroscopy, including investigation of large molecules such as C60. We present a high power, phase-stabilized frequency comb near 10 µm, generated by a synchronously pumped, singly resonant optical parametric oscillator (OPO) based on AgGaSe2. The OPO can be continuously tuned from 8.4 to 9.5 µm, with a maximum average idler power of 100 mW at the center wavelength of 8.5 µm. Both the repetition rate (f rep) and the carrier-envelope offset frequency (f ceo) of the idler wave are phase-locked to microwave signals referenced to a Cs clock. We describe the detailed design and construction of the frequency comb, and discuss potential applications for precise and sensitive direct frequency comb spectroscopy.

Three-photon absorption in optical parametric oscillators based on OP-GaAs.

We report on, to the best of our knowledge, the first singly resonant (SR), synchronously pumped optical parametric oscillator (OPO) based on orientation-patterned gallium arsenide (OP-GaAs). Together with a doubly resonant (DR) degenerate OPO based on the same OP-GaAs material, the output spectra cover 3 to 6 µm within ∼3 dB of relative power. The DR-OPO has the highest output power reported to date from a femtosecond, synchronously pumped OPO based on OP-GaAs. We observed strong three-photon absorption with a coefficient of 0.35±0.08 cm3/GW2 for our OP-GaAs sample, which limits the output power of these OPOs as mid-IR light sources. We present a detailed study of the three-photon loss on the performance of both the SR- and DR-OPOs, and compare them to those without this loss mechanism.

Continuous probing of cold complex molecules with infrared frequency comb spectroscopy.

For more than half a century, high-resolution infrared spectroscopy has played a crucial role in probing molecular structure and dynamics. Such studies have so far been largely restricted to relatively small and simple systems, because at room temperature even molecules of modest size already occupy many millions of rotational/vibrational states, yielding highly congested spectra that are difficult to assign. Targeting more complex molecules requires methods that can record broadband infrared spectra (that is, spanning multiple vibrational bands) with both high resolution and high sensitivity. However, infrared spectroscopic techniques have hitherto been limited either by narrow bandwidth and long acquisition time, or by low sensitivity and resolution. Cavity-enhanced direct frequency comb spectroscopy (CE-DFCS) combines the inherent broad bandwidth and high resolution of an optical frequency comb with the high detection sensitivity provided by a high-finesse enhancement cavity, but it still suffers from spectral congestion. Here we show that this problem can be overcome by using buffer gas cooling to produce continuous, cold samples of molecules that are then subjected to CE-DFCS. This integration allows us to acquire a rotationally resolved direct absorption spectrum in the C-H stretching region of nitromethane, a model system that challenges our understanding of large-amplitude vibrational motion. We have also used this technique on several large organic molecules that are of fundamental spectroscopic and astrochemical relevance, including naphthalene, adamantane and hexamethylenetetramine. These findings establish the value of our approach for studying much larger and more complex molecules than have been probed so far, enabling complex molecules and their kinetics to be studied with orders-of-magnitude improvements in efficiency, spectral resolution and specificity.

Mid-Infrared Time-Resolved Frequency Comb Spectroscopy of Transient Free Radicals.

We demonstrate time-resolved frequency comb spectroscopy (TRFCS), a new broadband absorption spectroscopy technique for the study of trace free radicals on the microsecond timescale. We apply TRFCS to study the time-resolved, mid-infrared absorption of the deuterated hydroxyformyl radical trans-DOCO, an important short-lived intermediate along the OD + CO reaction path. Directly after photolysis of the chemical precursor acrylic acid-d1, we measure absolute trans-DOCO product concentrations with a sensitivity of 5 × 10(10) cm(-3) and observe its subsequent loss with a time resolution of 25 µs. The multiplexed nature of TRFCS allows us to detect simultaneously the time-dependent concentration of several other photoproducts and thus unravel primary and secondary chemical reaction pathways.