Cavity-enhanced Spectroscopy Research Articles

Cavity-enhanced dual-comb spectroscopy in the molecular fingerprint region using free-running quantum cascade lasers

Cavity-enhanced dual-comb spectroscopy in the molecular fingerprint region using free-running quantum cascade lasers

Parabolic mirror cavity-enhanced Raman spectroscopy for trace gas detection.

A parabolic mirror cavity-enhanced Raman spectroscopy (PM-CERS) method was reported, utilizing a combined optical path of a parabolic mirror and a multi-pass cell. In this setup, the focal point of the parabolic mirror is aligned with the laser convergence center of the multi-pass cell. This method achieved high excitation intensity at the focal point and broadened the collection range of Raman scattering signals, thus significantly improving both the excitation and collection efficiency of Raman signals. Additionally, the structure of the system was simplified through the integrated design of the collection cavity and sample cell. Nitrogen, oxygen, water vapor, and carbon dioxide could be detected in the air within an exposure time of just 0.5 s, achieving the limits of detection at the ppm level. Compared to the conventional multi-pass cell, the signal intensity and signal-to-noise ratio were each enhanced by approximately 5.6-fold, further demonstrating the excellent potential application in trace gas detection.

High-Sensitivity and In Situ Multi-Component Detection of Gases Based on Multiple-Reflection-Cavity-Enhanced Raman Spectroscopy.

Raman spectroscopy with the advantages of the in situ and simultaneous detection of multi-components has been widely used in the identification and quantitative detection of gas. As a type of scattering spectroscopy, the detection sensitivity of Raman spectroscopy is relatively lower, mainly due to the low signal collection efficiency. This paper presents the design and assembly of a multi-channel cavity-enhanced Raman spectroscopy system, optimizing the structure of the sample pool to reduce the loss of the laser and increase the excitation intensity of the Raman signals. Moreover, three channels are used to collect Raman signals to increase the signal collection efficiency for improving the detection sensitivity. The results showed that the limits of detection for the CH4, H2, CO2, O2, and N2 gases were calculated to be 3.1, 34.9, 17.9, 27, and 35.2 ppm, respectively. The established calibration curves showed that the correlation coefficients were all greater than 0.999, indicating an excellent linear correlation and high level of reliability. Meanwhile, under long-time integration detection, the Raman signals of CH4, H2, and CO2 could be clearly distinguished at the concentrations of 10, 10, and 50 ppm, respectively. The results indicated that the designed Raman system possesses broad application prospects in complex field environments.

Cavity-enhanced light-induced thermoelastic spectroscopy for trace-gas sensing

We report a trace gas sensing technique of cavity-enhanced light-induced thermoelastic spectroscopy (CE-LITES) with a Fabry–Pérot (F-P) optical cavity and a high-quality-factor resonant quartz tuning fork (QTF). Pound-Drever-Hall (PDH) locking method is used to lock the laser to the optical cavity. With only a short 9-cm optical cavity (finesse, ∼1283) and a tiny commercially available standard QTF (Q-factor, ∼38910), a CE-LITES sensor for acetylene detection was developed to demonstrate this technique, achieving a minimum detection limit (MDL) of 7.5 parts-per-billion (ppb) for a 216-s integration time and a normalized noise equivalent absorption (NNEA) coefficient of as low as 1.91 × 10−10 cm−1·W·Hz−1/2. The developed technique bears promising potential for sensitive and accurate measurement that is needed for studying trace gas-phase analyte.

Gas detection using cavity-enhanced Raman spectroscopy with a bidirectional multi-pass cell and polarization beam-splitting optical path

We demonstrate a substantial enhancement of gas Raman scattering using a bidirectional multi-pass cavity CERS system, which incorporates a polarization beam-splitting optical path. The system design allows the laser light to traverse the multi-pass cavity for four specific trips, satisfying the need for quick detection of various gas components. Our gas detection experiments using multi-pass cavities with different times of reflection indicate that the addition of polarization beam-splitting optical path gives 1.5 to 1.68 times enhancement of Raman signal compared with that of the system without polarization beam-splitting. For the detection of CH4, a limit of detection of 1.66 ppm was achieved with our system using a multi-pass cell with 41 times of reflection and an integration time of 30s. Our proposed design, which integrates a bidirectional multi-pass cavity with polarization beam-splitting optical path, gives an economical multicomponent gas detection system and a valuable tool for guiding the design and precise alignment of these cavities. This system shows significant promise for applications in e.g. human breath and environmental monitoring.

High sensitivity and stability cavity-enhanced photoacoustic spectroscopy with dual-locking scheme

We present a high sensitivity and long-term stability cavity-enhanced photoacoustic spectroscopy (CE-PAS) system with optical cavity and acoustic frequency dual-locking scheme for trace acetylene (C2H2) detection. The first mechanism involves locking the optical wavelength to the cavity resonance by comparing the phase-sensitive component of the reflected light with a reference signal in a feedback loop. The second locking mechanism controls the gas proportion inside the photoacoustic cell to lock the acoustic frequency, suppressing the drift caused by environmental temperature variation. By minimizing amplitude fluctuations through dual-locking, the sensor achieves improved stability with reduced fluctuations from ±10.12 % to ±1.16 %. The linear responsivity and excellent linearity of the sensor are demonstrated over a concentration variation spanning four orders of magnitude. Experimental results showcase a minimum detection limit of 1.2 parts-per-billion (ppb) at an integration time of 400 s, corresponding to a normalized noise equivalent absorption (NNEA) coefficient of 1.37×10−11 cm−1·W· Hz−1/2 for C2H2 detection. Long-term stability is within ±2 % over a 15-day period. The combination of high sensitivity and long-term stability make this CE-PAS sensor suitable for a wide range of applications in environmental monitoring, industrial process control, and gas leak detection.

Cavity-enhanced dual-comb spectroscopy with wide spectral band tuning

Cavity-enhanced dual-comb spectroscopy holds significant research value by combining the high sensitivity of cavity enhancement and dual-comb high resolution and rapid measurement. However, due to the presence of intracavity dispersion, the insufficient coupling between the enhancement cavity and the optical frequency comb restricts the measurement bandwidth of the system, making it unable to provide abundant spectral information of the sample. To overcome this limitation, we propose a cavity-enhanced dual-comb spectroscopy with wide spectral band tuning by a single-point locking tuning scheme, which achieves a tuning capability of over 9 THz at the central wave number of 6400 cm−1. This represents a significant improvement compared to the untuned cavity-enhanced spectrum, increasing the measurable bandwidth by 2.5 times. We verified the capability of the scheme by measuring the rovibrational spectrum of CO2 in various frequency bands within the 6250–6550 cm−1 range. In each tuned frequency band, we achieved an enhancement factor of ∼950, signal-to-noise ratio (SNR > 600) in 30 s, and resolution of 250 MHz. The cavity-enhanced dual-comb spectroscopy with wide spectral band tuning holds promise for potential applications in fields such as trace gas analysis and respiratory diagnostics.

Optical feedback frequency locking: impact of directly reflected field and responding strategies.

The challenges presented by the directly reflected field in optical feedback cavity-enhanced spectroscopy systems serve as substantial obstacles, introducing additional complexity to existing systems and compromising their sensitivity, as the underlying mechanisms of its adverse effects remain not fully understood. This study aims to address this issue by introducing a comprehensive analytical model. Additionally, frequency locking can be achieved by decreasing the feedback rate, the laser's linewidth enhancement factor, and the directly reflected field, and by increasing the refractive index of the gain medium, the length of the laser's resonant cavity, the electric field reflectivity of the laser's output facet, and the resonant field. These parameters can affect the feedback coupling rate pre-factor, and for a resonant cavity with a length of 0.394 m, optical feedback can only be established when the feedback coupling rate pre-factor is less than 1.05 × 109. Through experimental validation, we successfully confirm the effectiveness of the proposed solution in eliminating the detrimental effects of the directly reflected field. Importantly, this suppression is achieved without compromising other aspects of the system's performance. The research findings not only offer the potential to optimize various cavity-enhanced spectroscopy systems that rely on optical feedback but also show promising applications in advancing the development of high-purity spectrum diode lasers utilizing optical feedback from an external high-finesse cavity.

Precision Measurement of Vibrational Quanta in Tritium Hydride.

Saturated absorption measurements of transitions in the (2-0) band of radioactive tritium hydride are performed with the ultrasensitive noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy intracavity absorption technique in the range 1460-1510nm. The hyperfine structure of rovibrational transitions of tritium hydride, in contrast to that of hydrogen deuteride, exhibits a single isolated hyperfine component, allowing for the accurate determination of hyperfineless rovibrational transition frequencies, resulting in R(0)=203 396 426 692(22) kHz and R(1)=205 380 033 644(21) kHz. This corresponds to an accuracy 3 orders of magnitude better than previous measurements in tritiated hydrogen molecules. Observation of an isolated component in P(1) with reversed signal amplitude contradicts models for line shapes in hydrogen deuteride based on crossover resonances.

Cavity-enhanced photoacoustic dual-comb spectroscopy

Photoacoustic dual-comb spectroscopy (DCS), converting spectral information in the optical frequency domain to the audio frequency domain via multi-heterodyne beating, enables background-free spectral measurements with high resolution and broad bandwidth. However, the detection sensitivity remains limited due to the low power of individual comb lines and the lack of broadband acoustic resonators. Here, we develop cavity-enhanced photoacoustic DCS, which overcomes these limitations by using a high-finesse optical cavity for the power amplification of dual-frequency combs and a broadband acoustic resonator with a flat-top frequency response. We demonstrate high-resolution spectroscopic measurements of trace amounts of C2H2, NH3 and CO in the entire telecommunications C-band. The method shows a minimum detection limit of 0.6 ppb C2H2 at the measurement time of 100 s, corresponding to the noise equivalent absorption coefficient of 7 × 10−10 cm−1. The proposed cavity-enhanced photoacoustic DCS may open new avenues for ultrasensitive, high-resolution, and multi-species gas detection with widespread applications.

Impact of pH on Gas-Particle Partitioning of Semi-Volatile Organics in Multicomponent Aerosol.

The partitioning of semivolatile organic compounds (SVOCs) between the condensed and gas phases can have significant implications for the properties of aerosol particles. In addition to affecting size and composition, this partitioning can alter radiative properties and impact cloud activation processes. We present measurements and model predictions on how activity and pH influence the evaporation of SVOCs from particles to the gas phase, specifically investigating aqueous inorganic particles containing dicarboxylic acids (DCAs). The aerosols are studied at the single-particle level by using optical trapping and cavity-enhanced Raman spectroscopy. Optical resonances in the spectra enable precise size tracking, while vibrational bands allow real-time monitoring of pH. Results are compared to a Maxwell-type model that accounts for volatile and nonvolatile solutes in aqueous droplets that are held at a constant relative humidity. The aerosol inorganic-organic mixture functional group activity coefficients thermodynamic model and Debye-Hückel theory are both used to calculate the activities of the species present in the droplet. For DCAs, we find that the evaporation rate is highly sensitive to the particle pH. For acidity changes of approximately 1.5 pH units, we observe a shift from a volatile system to one that is completely nonvolatile. We also observe that the pH itself is not constant during evaporation; it increases as DCAs evaporate, slowing the rate of evaporation until it eventually ceases. Whether a DCA evaporates or remains a stable component of the droplet is determined by the difference between the lowest pKa of the DCA and the pH of the droplet.

Low-Temperature Cavity-Enhanced Spectroscopy with a Diode Laser: Vibration–Rotation Absorption of CO (3ν) at 80 K and CH3C≡C–H (2ν1) at 165 K

A rotational resolution cavity-enhanced absorption spectroscopy (CEAS) technique is presented for infrared (IR) absorption studies at temperatures between 77 and 300 K. The cavity consists of an aluminum tube with two highly reflecting near-IR mirrors at each end. The cavity is attached to the cold head of a liquid nitrogen cryostat inside a vacuum chamber. In this way, all the cavity components are the temperature of the cold head. The spectra are obtained with a tunable diode laser and lock-in detection. The laser is modulated with an electro-optic modulator and coupled to the optical cavity. To illustrate the use of the technique, the vibrational–rotational overtone transitions (υ = 0→3) of carbon monoxide at 295 and 80 K and the acetylenic C–H (υ = 0→2) bond of CH3C≡C–H at 293 and 165 K are obtained. Temperatures are obtained with a Boltzmann distribution calculation that involves rotational intensities and energies from the spectra. Spectroscopic constants agree with previous determinations using other methods. An average of signals over the entire range of the absorption produces a rotational intensity distribution with some deviations. The calculated temperature based on the Boltzmann distribution is in very good agreement with the temperature measured with a silicon temperature sensor attached to the cell. Comparison with other experimental approaches to CEAS and the importance of the technique for applications in astrochemistry are discussed.

Pulsed CW laser for long-term spectroscopic measurements at high power in deep-UV.

We present a novel technique for in-vacuum cavity-enhanced UV spectroscopy that allows nearly continuous measurements over several days, minimizing mirror degradation caused by high-power UV radiation. Our method relies on pulsing of the cavity's internal power, which increases the UV intensity to maximum only for short periods when the studied atom is within the cavity mode volume while keeping the average power low to prevent mirror degradation. Additionally, this method significantly decreases laser-induced background on charged particle detectors. The described 244 nm laser system is designed for 1S-2S two-photon CW spectroscopy of muonium in the Mu-MASS project. It was tested to provide intracavity powers above 20 W, requiring maintenance only a few times a day. The pulsing technique demonstrates minimal impact on the radiation frequency, with no observed shifts exceeding 15 kHz. Our approach represents a promising new technique for high-precision spectroscopy of atoms in harsh UV environments and demonstrates the feasibility of CW spectroscopy of muonium.

Mid-infrared swept cavity-enhanced photoacoustic spectroscopy using a quartz tuning fork

We report the development of swept cavity-enhanced photoacoustic spectroscopy using a quartz tuning fork for ultra-sensitive and high-resolution molecular spectroscopy. By using a quantum cascade laser (QCL) as the mid-infrared light source, a dual-feedback Pound–Drever–Hall locking method is proposed to lock the QCL frequency to a continuously swept optical cavity. By placing an off-beam quartz-enhanced photoacoustic spectroscopy module in a 48-mm Fabry–Pérot cavity, we are able to achieve ultra-sensitive gas detection based on the doubly resonant photoacoustic effect. As a proof-of-concept, we use a distributed feedback QCL to exploit the CO line at 2190.02 cm−1, where the cavity-locked QCL is scanned over a spectral range of 10 GHz with a spectral resolution of ∼3 MHz. With the incident laser power of 7.3 mW, the optical cavity (finesse 1931) builds up the intracavity power beyond 3 W. Our photoacoustic spectrometer achieves the minimum detection limit of 375 part-per-trillion (ppt) at the averaging time of 150 s and the normalized noise equivalent absorption coefficient of 1.27 × 10−9 Wcm−1 Hz−1/2.

Carrier-envelope offset frequency measurement by means of an external optical resonator

A general-purpose method based on the implementation of the asymmetric Pound–Drever–Hall (PDH) technique is proposed to measure the carrier-envelope offset (CEO) frequency of a mode-locked laser using an external optical cavity. By analyzing the synchronously demodulated signal of the spectrally filtered cavity reflection when the optical resonator is locked to the mode-locked laser, a discriminating signal depending on the relative frequency offset between the mode-locked and optical cavity comb-like spectra is obtained. For a given geometry and group delay dispersion (GDD) of the cavity parameters (i.e., a known cavity mode offset), this signal can be used to retrieve the laser CEO. This approach turns out to be advantageous in terms of setup complexity with respect to other well-known techniques that rely on non-linear frequency generation, such as f–2f interferometers. In addition, this method can be used to precisely determine the laser–cavity spectral coupling, which is an important topic in cavity-enhanced spectroscopy and non-linear optics applications. After the theoretical description of the generalized asymmetric PDH signal, an experimental validation of the proposed method is reported using an Er-doped fiber frequency comb source centered at 1,550 nm, with a repetition rate of 250 MHz, locked to a linear optical cavity with a 1 GHz free spectral range. The theoretical effect of the GDD is confirmed experimentally using different cavity configurations. Moreover, the comparison with the CEO frequency values measured using an f–2f interferometer demonstrates the feasibility of the proposed method.

Cavity-Enhanced Raman Spectroscopy for Detection of Trace Gaseous Impurities in Hydrogen for Fuel Cells

Gaseous impurities contained in hydrogen (H2) profoundly affect the performance of hydrogen proton-exchange membrane fuel cells. We demonstrate the utility of cavity-enhanced Raman spectroscopy as a unique approach for detection of gaseous impurities. A dense-pattern multipass cavity which is composed of four spherical mirrors placed in a Z-shaped configuration is used to enhance the Raman signal by extending the laser-gas interaction length. A total of 85 spots are identified on the 2-inch-diameter front (or rear) mirror, which indicates that 510 beams exist in the cavity. Detection limits of the impurity gases, including oxygen (O2), nitrogen (N2), carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), ammonia (NH3), and hydrogen sulfide (H2S), reach sub-ppm- and ppb-levels at a total pressure of 0.1 and 2.5 MPa, respectively. This satisfies the detection requirements according to the maximum allowable concentration for these gases. Our cavity-enhanced Raman spectroscopy (CERS) apparatus can simultaneously measure multiple gases with high sensitivity and selectivity with no sample destruction. It has excellent application prospects in gaseous impurity analysis for the quality assessment of gaseous energy.

Multiple Gas Detection by Cavity-Enhanced Raman Spectroscopy with Sub-ppm Sensitivity.

Accurate and sensitive detection of multicomponent trace gases below the parts-per-million (ppm) level is needed in a variety of medical, industrial, and environmental applications. Raman spectroscopy can identify multiple molecules in the sample simultaneously and has excellent potential for fast diagnosis of various samples, but applications are often limited by its sensitivity. In this contribution, we report the development of a cavity-enhanced Raman spectroscopy instrument using a narrow-line width 532 nm laser locked with a high-finesse cavity through a Pound-Drever-Hall locking servo, which allows continuous measurement in a broad spectral range. An intracavity laser power of up to 1 kW was achieved with an incident laser power of about 240 mW, resulting in a significant enhancement of the Raman signal in the range of 200-5000 cm-1 and a sub-ppm sensitivity for various molecules. The technique is applied in the detection of different samples, including ambient air, natural gas, and reference gas of sulfur hexafluoride, demonstrating its capability for the quantitative measurement of various trace components.

Rapid Enantiomeric Excess Measurements of Enantioisotopomers by Molecular Rotational Resonance Spectroscopy.

Recent work in drug discovery has shown that selectively deuterated small molecules can improve the safety and efficacy for active pharmaceutical ingredients. The advantages derive from changes in metabolism resulting from the kinetic isotope effect when deuterium is substituted for a hydrogen atom at a structural position where rate limiting C-H bond breaking occurs. This application has pushed the development of precision deuteration strategies in synthetic chemistry that can install deuterium atoms with high regioselectivity and with stereocontrol. Copper-catalyzed alkene transfer hydrodeuteration chemistry has recently been shown to have high stereoselectivity for deuteration at the metabolically important benzyl C-H position. In this case, stereocontrol results in the creation of enantioisotopomers-molecules that are chiral solely by virtue of the deuterium substitution-and chiral analysis techniques are needed to assess the reaction selectivity. It was recently shown that chiral tag molecular rotational resonance (MRR) spectroscopy provides a routine way to measure the enantiomeric excess and establish the absolute configuration of enantioisotopomers. High-throughput implementations of chiral tag MRR spectroscopy are needed to support optimization of the chemical synthesis. A measurement methodology for high-throughput chiral analysis is demonstrated in this work. The high-throughput ee measurements are performed using cavity-enhanced MRR spectroscopy, which reduces measurement times and sample consumption by more than an order-of-magnitude compared to the previous enantioisotopomer analysis using a broadband MRR spectrometer. It is also shown that transitions for monitoring the enantiomers can be selected from a broadband rotational spectrum without the need for spectroscopic analysis. The general applicability of chiral tag MRR spectroscopy is illustrated by performing chiral analysis on six enantioisotopomer reaction products using a single molecule as the tag for chiral discrimination.

High-precision cavity-enhanced spectroscopy for studying the H2-Ar collisions and interactions.

Information about molecular collisions is encoded in the shapes of collision-perturbed molecular resonances. This connection between molecular interactions and line shapes is most clearly seen in simple systems, such as the molecular hydrogen perturbed by a noble gas atom. We study the H2-Ar system by means of highly accurate absorption spectroscopy and ab initio calculations. On the one hand, we use the cavity-ring-down-spectroscopy technique to record the shapes of the S(1) 3-0 line of molecular hydrogen perturbed by argon. On the other hand, we simulate the shapes of this line using ab initio quantum-scattering calculations performed on our accurate H2-Ar potential energy surface (PES). In order to validate the PES and the methodology of quantum-scattering calculations separately from the model of velocity-changing collisions, we measured the spectra in experimental conditions in which the influence of the latter is relatively minor. In these conditions, our theoretical collision-perturbed line shapes reproduce the raw experimental spectra at the percent level. However, the collisional shift, δ0, differs from the experimental value by 20%. Compared to other line-shape parameters, collisional shift displays much higher sensitivity to various technical aspects of the computational methodology. We identify the contributors to this large error and find the inaccuracies of the PES to be the dominant factor. With regard to the quantum scattering methodology, we demonstrate that treating the centrifugal distortion in a simple, approximate manner is sufficient to obtain the percent-level accuracy of collisional spectra.

Evidence for Topological Magnon-Phonon Hybridization in a 2D Antiferromagnet down to the Monolayer Limit.

Topological phonons and magnons potentially enable low-loss, quantum coherent, and chiral transport of information and energy at the atomic scale. Van der Waals magnetic materials are promising to realize such states due to their recently discovered strong interactions among the electronic, spin, and lattice degrees of freedom. Here, we report the first observation of coherent hybridization of magnons and phonons in monolayer antiferromagnet FePSe3 by cavity-enhanced magneto-Raman spectroscopy. The robust magnon-phonon cooperativity in the 2D limit occurs even in zero magnetic field, which enables nontrivial band inversion between longitudinal and transverse optical phonons caused by the strong coupling with magnons. The spin and lattice symmetry theoretically guarantee magnetic-field-controlled topological phase transition, verified by nonzero Chern numbers calculated from the coupled spin-lattice model. The 2D topological magnon-phonon hybridization potentially offers a new route toward quantum phononics and magnonics with an ultrasmall footprint.