Bryce Bjork

Mid-infrared virtually imaged phased array spectrometer for rapid and broadband trace gas detection

We present and characterize a two-dimensional (2D) imaging spectrometer based on a virtually imaged phased array (VIPA) disperser for rapid, high-resolution molecular detection using mid-infrared (MIR) frequency combs at 3.1 and 3.8 μm. We demonstrate detection of CH4 at 3.1 μm with >3750 resolution elements spanning >80 nm with ~600 MHz resolution in a <10 μs acquisition time. In addition to broadband detection, we also demonstrate rapid, time-resolved single-image detection by capturing dynamic concentration changes of CH4 at a rate of ~375 frames per second. Changes in absorption above the noise floor of 5×10(-4) are readily detected on the millisecond time scale, leading to important future applications such as real-time monitoring of trace gas concentrations and detection of reactive intermediates.

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.

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.

Direct frequency comb measurement of OD + CO → DOCO kinetics

Combing through CO oxidation kinetics Carbon monoxide reacts with OH radicals to produce CO2. This process is central to combustion and atmospheric oxidation chemistry. The reaction sequence is widely assumed to involve the intermediacy of a HOCO adduct that has eluded direct monitoring under thermal conditions. Bjork et al. successfully observed the formation of the deuterated analog of this intermediate, DOCO, while simultaneously monitoring OD by using a multifrequency infrared comb. The results confirm the termolecular nature of the formation mechanism and its sensitivity to the ambient bath gas. Science, this issue p. 444 A broadband frequency comb tracks the kinetics of a previously elusive intermediate in the oxidation of carbon monoxide to carbon dioxide The kinetics of the hydroxyl radical (OH) + carbon monoxide (CO) reaction, which is fundamental to both atmospheric and combustion chemistry, are complex because of the formation of the hydrocarboxyl radical (HOCO) intermediate. Despite extensive studies of this reaction, HOCO has not been observed under thermal reaction conditions. Exploiting the sensitive, broadband, and high-resolution capabilities of time-resolved cavity-enhanced direct frequency comb spectroscopy, we observed deuteroxyl radical (OD) + CO reaction kinetics and detected stabilized trans-DOCO, the deuterated analog of trans-HOCO. By simultaneously measuring the time-dependent concentrations of the trans-DOCO and OD species, we observed unambiguous low-pressure termolecular dependence of the reaction rate coefficients for N2 and CO bath gases. These results confirm the HOCO formation mechanism and quantify its yield.

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.

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

Frequency comb spectroscopy captures real-time dynamics of cis- and trans-DOCO isomers produced from the OD + CO reaction. 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.

Spectral analyses of trans- and cis-DOCO transients via comb spectroscopy

ABSTRACT We use time-resolved direct frequency comb spectroscopy in the mid-infrared to obtain high-resolution rovibrational spectra of products produced from the OD + CO reaction. In this work, we present spectral analyses for isotopologues of the transient DOCO radicals from this reaction in the OD stretch region. The analyses were performed with the aid of two different theoretical approaches based on both perturbation theory and variational calculations used for prediction of rovibrational spectra of polyatomic molecules. We discuss the advantages and challenges of our current approach for studying spectroscopy and dynamics of transient molecules. GRAPHICAL ABSTRACT

Mid-infrared crystalline mirrors with ultralow optical losses

Substrate-transferred crystalline coatings are a groundbreaking new concept for the fabrication of ultralow-loss mirrors. The low defect density single-crystal nature of these semiconductor supermirrors enables the lowest mechanical losses and hence unmatched Brownian noise performance [1], which currently limits the stability of precision optical interferometers. Another outstanding feature of these coatings is the wide spectral coverage of the GaAs/AlGaAs material platform. Limited by interband absorption at short wavelengths and the reststrahlenband at long wavelengths [2], crystalline coatings can be employed as low-loss multilayers from approximately 900 nm up to 5 μm and beyond. Excellent optical performance has been demonstrated in the near-infrared with excess optical losses (scatter + absorption) as low as 3 parts per million (ppm) [3], enabling cavity finesse values up to 360, 000 at 1.55 μm at room temperature and as high as 400, 000 at cryogenic temperatures for the same wavelength. Our first attempts at applying crystalline coatings in the mid-infrared has resulted in mirrors with excess optical losses (scatter + absorption) of 159 and 242 ppm at 3.3 and 3.7 μm, respectively. Remarkably, these results are already on par with current state-of-the-art amorphous mirror coatings, with the first use of mid-infrared crystalline mirrors in a cavity-enhanced spectroscopy setup enabling a detailed investigation of the reaction kinetics of the deuterated hydroxyl molecule, OD, and carbon monoxide, CO [4]. Absorption measurements based on photothermal common-path interferometry (PCI) [5] reveal that the optical losses are largely dominated by optical scatter. Via, PCI, we have confirmed absorption losses below 10 ppm at 3.7 μm, showing the enormous potential of GaAs/AlGaAs Bragg mirrors at mid-infrared wavelengths. An optimized fabrication process, which is currently under development, can efficiently suppress optical scatter due to accumulated growth defects on the surface. Ultimately, we foresee excess losses significantly less than 50 ppm in the mid-infrared spectral region.

Mid-infrared crystalline supermirrors with ultralow optical absorption (Conference Presentation)

Substrate-transferred crystalline coatings are a groundbreaking new concept for the fabrication of ultralow-loss mirrors. The single-crystal lattice structure of these substrate-transferred GaAs/AlGaAs Bragg mirrors exhibits the lowest mechanical losses and hence unmatched Brownian noise performance, which nowadays limits the stability of precision optical interferometers. Another outstanding feature of these coatings is the wide spectral coverage of the GaAs/AlGaAs material platform. Limited by interband absorption at short wavelengths and the reststrahlen band at long wavelengths, crystalline coatings can be employed as low-loss multilayers from approximately 900 nm up to 5 μm and beyond. Excellent optical performance has been demonstrated in the near-infrared with excess optical losses (scatter + absorption) as low as 3 parts per million (ppm), enabling cavity finesse values up to 360,000 at 1.55 μm. Our first attempts at applying crystalline coatings in the mid-infrared has resulted in mirrors with excess optical losses of 159 and 242 ppm at 3.3 and 3.7 μm, respectively. Remarkably, these results are already on par with current state-of-the-art amorphous mirror coatings. Absorption measurements based on photothermal common-path interferometry (PCI) reveal that the optical losses are largely dominated by optical scatter. Via, PCI, we have confirmed absorption losses below 10 ppm at 3.7 μm, showing the enormous potential of GaAs/AlGaAs Bragg mirrors at mid-infrared wavelengths. An optimized fabrication process, which is currently under development, can efficiently suppress optical scatter due to accumulated growth defects on the surface. Ultimately, we foresee excess losses significantly less than 50 ppm in the mid-infrared spectral region.

Advancements in substrate-transferred crystalline coatings

We outline recent advances in high-performance substrate-transferred crystalline coatings with key results being the demonstration of sub-ppm absorption in the near infrared, as well as preliminary loss measurements in the mid-IR from 3-4 μm.