Measurement and calculation of CO (7-0) overtone line intensities.

Intensities of 14 lines in the sixth overtone (7-0) band of carbon monoxide (12C16O) are measured in the visible range between 14 300 and 14 500 cm-1 using a frequency-stabilized cavity ring-down spectrometer. This is the first observation of such a high and weak overtone spectrum of the CO molecule. A theoretical model is constructed and tested based on the use of a high accuracy ab initio dipole moment curve and a semi-empirical potential energy curve. Accurate studies of high overtone transitions provide a challenge to both experiment and theory as the lines are very weak: below 2 × 10-29 cm molecule-1 at 296 K. Agreement between theory and experiment within the experimental uncertainty of a few percent is obtained. However, this agreement is only achieved after issues with the stability of the Davidson correction to the multi-reference configuration interaction calculations are addressed.

Subpromille Measurements and Calculations of CO (3-0) Overtone Line Intensities.

Intensities of lines in the near-infrared second overtone band (3-0) of ^{12}C^{16}O are measured and calculated to an unprecedented degree of precision and accuracy. Agreement between theory and experiment to better than 1‰ is demonstrated by results from two laboratories involving two independent absorption- and dispersion-based cavity-enhanced techniques. Similarly, independent Fourier transform spectroscopy measurements of stronger lines in this band yield mutual agreement and consistency with theory at the 1‰ level. This set of highly accurate intensities can provide an intrinsic reference for reducing biases in future measurements of spectroscopic peak areas.

Line mixing in the oxygen B band head.

We present the results of direct measurements of the line mixing parameters for two pairs of overlapping transitions at the band head of the oxygen B band. Measurements were performed with the frequency-stabilized cavity ring-down spectrometer assisted by an optical frequency comb. The recorded spectra were analyzed with line profiles comprising speed dependence, Dicke narrowing, and line mixing. Incorporation of the line mixing into the model eliminated previous discrepancies for pressure shift and their speed dependence coefficients. First-order line mixing was determined directly from the line shape fitting at relatively low pressure (0.04 atm) together with other line shape parameters and compared with that calculated by Sung et al. [J. Quant. Spectrosc. Radiat. Transfer 235, 232-243 (2019)].

Frequency-based dispersion Lamb-dip spectroscopy in a high finesse optical cavity.

Frequency-based cavity mode-dispersion spectroscopy (CMDS), previously applied for Doppler-limited molecular spectroscopy, is now employed for the first time for saturation spectroscopy. Comparison with two intensity-based, cavity-enhanced absorption spectroscopy techniques, i.e. cavity mode-width spectroscopy (CMWS) and the well-established cavity ring-down spectroscopy (CRDS), shows the predominance of the CMDS. The method enables measurements in broader pressure range and shows high immunity of the Lamb dip position to the incomplete model of saturated cavity mode shape. Frequencies of transitions from the second overtone of CO are determined with standard uncertainty below 500 Hz which corresponds to relative uncertainty below 3 × 10-12. The pressure shift of the Lamb dips, which has not been detected for these transitions in available literature data, is observed.

Ultrahigh finesse cavity-enhanced spectroscopy for accurate tests of quantum electrodynamics for molecules.

We report the most accurate, to the best of our knowledge, measurement of the position of the weak quadrupole S(2) 2-0 line in $ {{\rm D}_2} $D2. The spectra were collected with a frequency-stabilized cavity ringdown spectrometer (FS-CRDS) with an ultrahigh finesse optical cavity ($ {\cal F} = 637 000 $F=637000) and operating in the frequency-agile, rapid scanning spectroscopy (FARS) mode. Despite working in the Doppler-limited regime, we reached 40 kHz of statistical uncertainty and 161 kHz of absolute accuracy, achieving the highest accuracy for homonuclear isotopologues of molecular hydrogen. The accuracy of our measurement corresponds to the fifth significant digit of the leading term in quantum electrodynamics (QED) correction. We observe $ 2.3\sigma $2.3σ discrepancy with the recent theoretical value.

High-accuracy and wide dynamic range frequency-based dispersion spectroscopy in an optical cavity.

A spectroscopic method free from systematic errors is desired for many challenging applications of gas detection. Although existing cavity-enhanced techniques exhibit very high precision, their accuracy strongly depends on propagation of the light amplitude through an optical system and its detection. Here, we demonstrate that the frequency-based molecular dispersion spectroscopy, involving sub-Hz-level precision in frequency measurements of optical cavity resonances, leads to sub-per-mille accuracy and a wide dynamic range, both previously unattainable by any other spectroscopic technique. The method offers great sensitivity of 5×10-11 cm-1, high speed, limited only by the fundamental response time of the cavity, and traceability of both axes of the spectrum to the primary frequency standard. All these features are necessary for convenient realization of comprehensive molecular spectroscopy from Doppler up to collisional regime without changing the spectroscopic method and modification of the experimental setup. Moreover, the presented approach does not require linear, high-bandwidth nor phase-sensitive detectors and can be directly implemented in existing cavity-enhanced spectrometers utilizing either continuous-wave or coherent broadband radiation. We experimentally prove the predominance of frequency-based spectroscopy over intensity-based one. Our results motivate replacement of intensity-based absorption spectroscopy with a pure frequency-based dispersion one in applications where the highest accuracy is required.

Response of an optical cavity to phase-controlled incomplete power switching of nearly resonant incident light.

The response of an optical cavity to incomplete extinction of nearly resonant incident light was experimentally examined. Measurements were performed using a Pound-Drever-Hall-locked frequency-stabilized cavity ring-down spectrometer (CRDS) that allowed the laser frequency detuning from the cavity resonance center to be controlled at Hz-level resolution. It is shown that an insufficient laser light extinction ratio combined with a phase shift and frequency detuning may lead to non-exponential cavity pumping and decay signals. The experimental results can be explained with a simple analytical model. The non-exponential decay can lead to a systematic shift as high as 0.5% in the ring-down time constants, dependent on the laser frequency detuning from the cavity mode center and on the extinction ratio. This can lead to appreciable systematic errors in the absorption coefficients determined with the CRDS technique.

Self-referenced, accurate and sensitive optical frequency comb spectroscopy with a virtually imaged phased array spectrometer.

We present a cavity-enhanced direct optical frequency comb spectroscopy system with a virtually imaged phased array (VIPA) spectrometer and either a dither or a Pound-Drever-Hall (PDH) locking scheme used for stable transmission of the comb through the cavity. A self-referenced scheme for frequency axis calibration is shown along with an analysis of its accuracy. A careful comparison between both locking schemes is performed based on near-IR measurements of the carbon monoxide ν=3←0 band P branch transitions in a gas sample with known composition. The noise-equivalent absorptions (NEA) for the PDH and dither schemes are 9.9×10(-10) cm(-1) and 5.3×10(-9) cm(-1), respectively.

One-dimensional frequency-based spectroscopy.

Recent developments in optical metrology have tremendously improved the precision and accuracy of the horizontal (frequency) axis in measured spectra. However, the vertical (typically absorbance) axis is usually based on intensity measurements that are subject to instrumental errors which limit the spectrum accuracy. Here we report a one-dimensional spectroscopy that uses only the measured frequencies of high-finesse cavity modes to provide complete information about the dispersive properties of the spectrum. Because this technique depends solely on the measurement of frequencies or their differences, it is insensitive to systematic errors in the detection of light intensity and has the potential to become the most accurate of all absorptive and dispersive spectroscopic methods. The experimental results are compared to measurements by two other high-precision cavity-enhanced spectroscopy methods. We expect that the proposed technique will have significant impact in fields such as fundamental physics, gas metrology and environmental remote sensing.

Observations of Dicke narrowing and speed dependence in air-broadened CO2 lineshapes near 2.06 µm.

Frequency-stabilized cavity ring-down spectroscopy was used to study CO2 lineshapes in the (20013) ← (00001) band centered near 2.06 µm. Two rovibrational transitions were chosen for this study to measure non-Voigt collisional effects for air-broadened lines over the pressure range of 7 kPa-28 kPa. Lineshape analysis for both lines revealed evidence of simultaneous Dicke (collisional) narrowing and speed-dependent effects that would introduce biases exceeding 2% in the retrieved air-broadening parameters if not incorporated in the modeling of CO2 lineshapes. Additionally, correlations between velocity- and phase/state changing collisions greatly reduced the observed Dicke narrowing effect. As a result, it was concluded that the most appropriate line profile for modeling CO2 lineshapes near 2.06 µm was the correlated speed-dependent Nelkin-Ghatak profile, which includes all of the physical effects mentioned above and leads to a consistent set of line shape parameters that are linear with gas pressure.

CRDS line-shape study of the (7-0) band of CO.

We present the results of the spectral line-shape study of the first measurement of the extremely weak (7-0) band of the 12C16O molecule. Measurements were done with a highly sensitive cavity ring-down spectrometer. Collisional narrowing, analyzed in terms of speed-dependent effects, was observed for the first time for transitions with line intensities below 2⋅10-29 cm/molecule at 296 K. We provide a full set of line-shape parameters of the speed-dependent and regular Voigt profile analysis for 14 transitions from P and R branches. Experimental verification of a strong vibrational dependence of the pressure shifting described by the Hartmann model (Hartmann, 2009) is extended up to the sixth overtone highly sensitive to the model parameter.

Cavity mode-width spectroscopy with widely tunable ultra narrow laser.

We explore a cavity-enhanced spectroscopic technique based on determination of the absorbtion coefficient from direct measurement of spectral width of the mode of the optical cavity filled with absorbing medium. This technique called here the cavity mode-width spectroscopy (CMWS) is complementary to the cavity ring-down spectroscopy (CRDS). While both these techniques use information on interaction time of the light with the cavity to determine absorption coefficient, the CMWS does not require to measure very fast signals at high absorption conditions. Instead the CMWS method require a very narrow line width laser with precise frequency control. As an example a spectral line shape of P7 Q6 O2 line from the B-band was measured with use of an ultra narrow laser system based on two phase-locked external cavity diode lasers (ECDL) having tunability of ± 20 GHz at wavelength range of 687 to 693 nm.

Pressure and temperature dependencies of air-perturbed O2 B-band line shapes.

The air-broadened lines from the oxygen B band were measured for the first time in controlled laboratory conditions with a high signal-to-noise ratio using frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) referenced to the optical frequency comb. Spectra measured at various pressures and temperatures were analyzed with an advanced line-shape model, considering the speed-dependence of collisional broadening and shift, and the effect of velocity-changing collisions. The temperature dependence of collisional broadening and shift is determined, whereas no significant temperature dependence of speed-dependent parameters and Dicke narrowing was observed. In addition, we have demonstrated that reasonable estimation of temperature dependence for pressure broadening is possible even from measurements done in single temperature where the speed dependence of pressure broadening was determined. New spectroscopic data improve the accuracy of the air-broadened oxygen B-band spectra description by an order of magnitude.

Cryogenic mirror position actuator for spectroscopic applications.

We demonstrate a mirror position actuator that operates in a wide temperature range from room temperature to a deep cryogenic regime (10 K). We use a Michelson interferometer to measure the actuator tuning range (and piezoelectric efficiency) in the full temperature range. We demonstrate an unprecedented range of tunability of the mirror position in the cryogenic regime (over 22 µm at 10 K). The capability of controlling the mirror position in the range from few to few tens of microns is crucial for cavity-enhanced molecular spectroscopy techniques, especially in the important mid-infrared spectral regime where the length of an optical cavity has to be tunable in a range larger than the laser wavelength. The piezoelectric actuator offering this range of tunability in the cryogenic conditions, on the one hand, will enable development of optical cavities operating at low temperatures that are crucial for spectroscopy of large molecules whose dense spectra are difficult to resolve at room temperature. On the other hand, this will enable us to increase the accuracy of the measurement of simple molecules aimed at fundamental studies.

Dual-comb cavity ring-down spectroscopy.

Cavity ring-down spectroscopy is a ubiquitous optical method used to study light-matter interactions with high resolution, sensitivity and accuracy. However, it has never been performed with the multiplexing advantages of direct frequency comb spectroscopy without significantly compromising spectral resolution. We present dual-comb cavity ring-down spectroscopy (DC-CRDS) based on the parallel heterodyne detection of ring-down signals with a local oscillator comb to yield absorption and dispersion spectra. These spectra are obtained from widths and positions of cavity modes. We present two approaches which leverage the dynamic cavity response to coherently or randomly driven changes in the amplitude or frequency of the probe field. Both techniques yield accurate spectra of methane-an important greenhouse gas and breath biomarker. When combined with broadband frequency combs, the high sensitivity, spectral resolution and accuracy of our DC-CRDS technique shows promise for applications like studies of the structure and dynamics of large molecules, multispecies trace gas detection and isotopic composition.

The air-broadened, near-infrared CO2 line shape in the spectrally isolated regime: evidence of simultaneous Dicke narrowing and speed dependence.

Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was employed to measure air-broadened CO(2) line shape parameters for transitions near 1.6 µm over a pressure range of 6.7-33 kPa. The high sensitivity of FS-CRDS allowed for the first measurements in this wavelength range of air-broadened line shape parameters on samples with CO(2) mixing ratios near those of the atmosphere. The measured air-broadening parameters show several percent deviations (0.9%-2.7%) from values found in the HITRAN 2008 database. Spectra were fit with a variety of models including the Voigt, Galatry, Nelkin-Ghatak, and speed-dependent Nelkin-Ghatak line profiles. Clear evidence of line narrowing was observed, which if unaccounted for can lead to several percent biases. Furthermore, it was observed that only the speed-dependent Nelkin-Ghatak line profile was able to model the spectra to within the instrumental noise level because of the concurrent effects of collisional narrowing and speed dependence of collisional broadening and shifting.

Broadband Optical Cavity Mode Measurements at Hz-Level Precision With a Comb-Based VIPA Spectrometer.

Optical frequency comb spectrometers open up new avenues of investigation into molecular structure and dynamics thanks to their accuracy, sensitivity and broadband, high-speed operation. We combine broadband direct frequency comb spectroscopy with a dispersive spectrometer providing single-spectrum acquisition time of a few tens of milliseconds and high spectral resolution. We interleave a few tens of such comb-resolved spectra to obtain profiles of 14-kHz wide cavity resonances and determine their positions with precision of a few hertz. To the best of our knowledge, these are the most precise and highest resolution spectral measurements performed with a broadband spectrometer, either comb-based or non-comb-based. This result pushes the limits of broadband comb-based spectroscopy to Hz-level regime. As a demonstration of these capabilities, we perform simultaneous cavity-enhanced measurements of molecular absorption and dispersion, deriving the gas spectra from cavity mode widths and positions. Such approach is particularly important for gas metrology and was made possible by the Hz-level resolution of the system. The presented method should be especially applicable to monitoring of chemical kinetics in, for example, plasma discharges or measurements of narrow resonances in cold atoms and molecules.

Note: Reliable, robust measurement system for trace moisture in gas at parts-per-trillion levels using cavity ring-down spectroscopy.

We report a simple, robust cavity ring-down spectroscopy system to reliably measure trace moisture in gases at parts-per-trillion (ppt) levels. The performance of the system was evaluated on the basis of experiments performed in a manner traceable to the International System of Units. The obtained result was in good agreement with the primary trace-moisture standard at 12 nmol/mol (12 ppb) in N2 in amount-of-substance fraction. Measurement capability of residual moisture in high-purity dry N2 at ∼130 pmol/mol (130 ppt) was demonstrated, and background noise of 5.3 × 10(-12) cm(-1) was attained, corresponding to a minimum detectable H2O of 5 pmol/mol (5 ppt).

Absolute measurement of the 1S0 - 3P0 clock transition in neutral 88Sr over the 330 km-long stabilized fibre optic link.

We report a stability below 7 × 10(-17) of two independent optical lattice clocks operating with bosonic (88)Sr isotope. The value (429 228 066 418 008.3(1.9)(syst) (0.9)(stat) Hz) of the absolute frequency of the (1)S(0) - (3)P(0) transition was measured with an optical frequency comb referenced to the local representation of the UTC by the 330 km-long stabilized fibre optical link. The result was verified by series of measurements on two independent optical lattice clocks and agrees with recommendation of Bureau International des Poids et Mesures.