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.

Fano-like Resonance due to Interference with Distant Transitions.

Narrow optical resonances of atoms or molecules have immense significance in various precision measurements, such as testing fundamental physics and the generation of primary frequency standards. In these studies, accurate transition centers derived from fitting the measured spectra are demanded, which critically rely on the knowledge of spectral line profiles. Here, we propose a new mechanism of Fano-like resonance induced by distant discrete levels and experimentally verify it with Doppler-free spectroscopy of vibration-rotational transitions of CO_{2}. The observed spectrum has an asymmetric profile and its amplitude increases quadratically with the probe laser power. Our results facilitate a broad range of topics based on narrow transitions.

Cavity-enhanced saturated absorption spectroscopy of the (30012) - (00001) band of 12C16O2.

The (30012) ← (00001) band of 12C16O2 in the 1.6 µm region is used for satellite observation of carbon dioxide in the Earth's atmosphere. Here, we report a Doppler-free spectroscopy study of this band with comb-locked wavelength-modulated cavity-enhanced absorption spectroscopy. Frequencies of 18 transitions with the rotational quantum numbers up to 42 were determined with sub-kHz accuracy, corresponding to a fractional uncertainty at the 10-12 level. With this precision, we revealed an anomalous decrease of the line shift and an increase of the line broadening for the Lamb dips of CO2 in the low-pressure regime compared to values obtained from Doppler-limited spectra at higher pressures.

Cavity ring-down spectroscopy based on a comb-locked optical parametric oscillator source.

Spectroscopy of molecules in the mid-infrared (MIR) region has important applications in various fields, such as astronomical observation, environmental detection, and fundamental physics. However, compared to that in the near-infrared, precision spectroscopy in the MIR is often limited by the light source and has not shown full potential in sensitivity. Here we report a cavity ring-down spectroscopy system using a tunable narrow-linewidth optical parametric oscillator, which fulfills the requirement of high sensitivity and high precision in the MIR region. The Lamb-dip spectrum of the N2O molecule at 2.7 µm was measured as a demonstration of spectroscopy in the MIR with kilohertz accuracy.

Dispersion-like lineshape observed in cavity-enhanced saturation spectroscopy of HD at 1.4 µm.

Precision measurement of ro-vibrational transitions in the electronic ground state of the hydrogen molecule can be used to test quantum electrodynamics and also to determine the dimensionless proton-to-electron mass ratio. Saturation spectroscopy of the 2-0 overtone transitions of hydrogen deuterium (HD) were measured with three cavity-enhanced spectroscopy methods. With a sensitivity at the 10-13cm-1 level, we revealed a dispersion-like lineshape instead of a conventional Lamb "dip," which explains the significant discrepancy among previous independent measurements. The spectra can be fit well by using the Fano profile. Centers of R(1) and R(3) lines were determined as 217 105 182 111 (19)stat(240)syskHz and 220 704 305 234 (20)stat(240)syskHz, respectively.

Seeded optical parametric oscillator light source for precision spectroscopy.

Precision spectroscopy of fundamental bands of molecules in the mid-infrared (MIR) region is of great interest in applications of trace detection and testing fundamental physics, where high-power and narrow-linewidth MIR lasers are needed. By using a frequency-stabilized near-infrared laser as a seed of the signal light of a continuous-wave optical parametric oscillator, we established a broadly tunable MIR light source that has an output power of several hundred milliwatts and a linewidth of a few tens of kilohertz. The MIR laser frequency drift was reduced to below 1 kHz by using an optical frequency comb to stabilize the frequency of the 1064 nm pumping laser. The performance of the light source was investigated and tested by measuring the saturated absorption spectroscopy of a few molecular transitions at 3.3 µm.

Frequency metrology of molecules in the near-infrared by NICE-OHMS.

Noise-immune cavity enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is extremely sensitive in detecting weak absorption. However, the use of NICE-OHMS for metrology study was also hindered by its sensitivity to influence from various experimental conditions such as the residual amplitude modulation. Here we demonstrate to use NICE-OHMS for precision measurements of Lamb-dip spectra of molecules. After a dedicated investigation of the systematic uncertainties in the NICE-OHMS measurement, the transition frequency of a ro-vibrational line of C2H2 near 789 nm was determined to be 379 639 280 915.3±1.2 kHz (fractional uncertainty 3.2 × 10-12), agreeing well with, but more accurate than, the value determined from previous cavity ring-down spectroscopy measurements. The study indicates the possibility to implement the very sensitive NICE-OHMS method for frequency metrology of molecules, or a molecular clock, in the near-infrared.

Comb-locked cavity ring-down spectroscopy with variable temperature.

Temperature dependence of molecular absorption line shape is important information for spectroscopic studies and applications. In this work, we report a comb-locked cavity ring-down spectrometer employing a cryogenic cooler to perform absorption spectroscopy measurements at temperatures between 40 K and 300 K. As a demonstration, we recorded the spectrum of the R(0) line in the (2-0) band of HD at 46 K. The temperature was also confirmed by the Doppler width of the HD line. Spectra of CH4 near 1.394 µm were also recorded in a wide temperature range of 70-300 K. Lower-state energies of methane lines were analyzed by fitting these spectra, which can be directly compared with the HITRAN and TheoReTS databases. Considerable deviations were observed, indicating the need to investigate the assignments of the methane lines in this region.

Toward a Determination of the Proton-Electron Mass Ratio from the Lamb-Dip Measurement of HD.

Precision spectroscopy of the hydrogen molecule is a test ground of quantum electrodynamics (QED), and it may serve for the determination of fundamental constants. Using a comb-locked cavity ring-down spectrometer, for the first time, we observed the Lamb-dip spectrum of the R(1) line in the overtone of hydrogen deuteride (HD). The line position was determined to be 217 105 182.79±0.03_{stat}±0.08_{syst} MHz (δν/ν=4×10^{-10}), which is the most accurate rovibrational transition ever measured in the ground electronic state of molecular hydrogen. Moreover, from calculations including QED effects up to the order m_{e}α^{6}, we obtained predictions for this R(1) line as well as for the HD dissociation energy, which are less accurate but signaling the importance of the complete treatment of nonadiabatic effects. Provided that the theoretical calculation reaches the same accuracy, the present measurement will lead to a determination of the proton-to-electron mass ratio with a precision of 1.3 parts per billion.

Dissociation Energy of the Hydrogen Molecule at 10

The ionization energy of ortho-H_{2} has been determined to be E_{I}^{o}(H_{2})/(hc)=124 357.238 062(25) cm^{-1} from measurements of the GK(1,1)-X(0,1) interval by Doppler-free, two-photon spectroscopy using a narrow band 179-nm laser source and the ionization energy of the GK(1,1) state by continuous-wave, near-infrared laser spectroscopy. E_{I}^{o}(H_{2}) was used to derive the dissociation energy of H_{2}, D_{0}^{N=1}(H_{2}), at 35 999.582 894(25) cm^{-1} with a precision that is more than one order of magnitude better than all previous results. The new result challenges calculations of this quantity and represents a benchmark value for future relativistic and QED calculations of molecular energies.

Laser Spectroscopy of the Fine-Structure Splitting in the 2

The fine-structure splitting in the 2^{3}P_{J} (J=0, 1, 2) levels of ^{4}He is of great interest for tests of quantum electrodynamics and for the determination of the fine-structure constant α. The 2^{3}P_{0}-2^{3}P_{2} and 2^{3}P_{1}-2^{3}P_{2} intervals are measured by laser spectroscopy of the ^{3}P_{J}-2^{3}S_{1} transitions at 1083 nm in an atomic beam, and are determined to be 31 908 130.98±0.13 kHz and 2 291 177.56±0.19 kHz, respectively. Compared with calculations, which include terms up to α^{5}Ry, the deviation for the α-sensitive interval 2^{3}P_{0}-2^{3}P_{2} is only 0.22 kHz. It opens the window for further improvement of theoretical predictions and an independent determination of the fine-structure constant α with a precision of 2×10^{-9}.

Measurement of the Frequency of the 2

The 2 ^{3}S-2 ^{3}P transition of ^{4}He was measured by comb-linked laser spectroscopy using a transverse-cooled atomic beam. The centroid frequency was determined to be 276 736 495 600.0(1.4) kHz, with a fractional uncertainty of 5.1×10^{-12}. This value is not only more accurate but also differs by as much as -49.5 kHz (20σ) from the previous result given by [Cancio Pastor et al., Phys. Rev. Lett. 92, 023001 (2004)PRLTAO0031-900710.1103/PhysRevLett.92.023001; Cancio Pastor et al.Phys. Rev. Lett.97, 139903(E) (2006)10.1103/PhysRevLett.97.139903; Cancio Pastor et al.Phys. Rev. Lett.108, 143001 (2012)10.1103/PhysRevLett.108.143001]. In combination with ongoing theoretical calculations, this work may allow the most accurate determination of the nuclear charge radius of helium.

Heat- and light-induced transformations of Yb trapping sites in an Ar matrix.

The low-lying electronic states of Yb isolated in a solid Ar matrix grown at 4.2 K are characterized through absorption and emission spectroscopy. Yb atoms are found to occupy three distinct thermally stable trapping sites labeled "red," "blue," and "violet" according to the relative positions of the absorption features they produce. Classical simulations of the site structure and relative stability broadly reproduced the experimentally observed matrix-induced frequency shifts and thus identified the red, blue, and violet sites as due to respective single substitutional (ss), tetravacancy (Tv), and hexavacancy (Hv) occupation. Prolonged excitation of the (1)S → (1)P transition was found to transfer the Yb population from hv sites into Tv and ss sites. The process showed reversibility in that annealing to 24 K predominantly transferred the Tv population back into Hv sites. Population kinetics were used to deduce the effective rate parameters for the site transformation processes. Experimental observations indicate that the blue and violet sites lie close in energy, whereas the red one is much less stable. Classical simulations identify the blue site as the most stable one.

CO2 isolated line shapes by classical molecular dynamics simulations: influence of the intermolecular potential and comparison with new measurements.

Room temperature absorption spectra of various transitions of pure CO2 have been measured in a broad pressure range using a tunable diode-laser and a cavity ring-down spectrometer, respectively, in the 1.6 µm and 0.8 µm regions. Their spectral shapes have been calculated by requantized classical molecular dynamics simulations. From the time-dependent auto-correlation function of the molecular dipole, including Doppler and collisional effects, spectral shapes are directly computed without the use of any adjusted parameter. Analysis of the spectra calculated using three different anisotropic intermolecular potentials shows that the shapes of pure CO2 lines, in terms of both the Lorentz widths and non-Voigt effects, slightly depend on the used potential. Comparisons between these ab initio calculations and the measured spectra show satisfactory agreement for all considered transitions (from J = 6 to J = 46). They also show that non-Voigt effects on the shape of CO2 transitions are almost independent of the rotational quantum number of the considered lines.

Normalization of the single atom counting rate in an atom trap.

The single atom counting rate of a rare isotope and the loading rate of another stable isotope with an abundance over 10 orders of magnitude larger are measured in one atom trap. The linear correlation between the measured counting/loading rates is examined to determine the (84)Kr/(82)Kr and (85)Kr/(83)Kr ratios of a Kr gas sample. Experiments show that the relative uncertainty is reduced to 1.3% when the single atom counting rate of (85)Kr is normalized by the measured (83)Kr loading rate. The measurement of the normalized single atom counting rate can be used to determine extremely low (10(-16)-10(-11)) isotope abundance. This normalization method is robust and can also be applied in other atomic systems.

Phonon coupling of water monomers in a solid nitrogen matrix.

The infrared absorption spectra of the H2O, HDO, and D2O monomers isolated in solid N2 have been recorded at various temperatures between 4 and 30 K. A study of the absorption features of the ν1, ν2, and ν3 vibrational modes for each monomer shows their optical line shapes to be strongly temperature dependent. For all three modes, a decrease in the absorption amplitude and a proportional broadening of the linewidth was observed with increasing temperature, while the integrated absorbance remained constant. These observations were explained in terms of phonon coupling, by which high frequency intramolecular modes decay by exciting matrix phonons. Fits of the linewidth for the lowest frequency ν2 vibrational mode to the predicted vibrational relaxation rate in a solid medium gave average phonon mode frequencies consistent with the Debye frequency for solid N2.

The 4ν(CH) overtone of 12C2H2: sub-MHz precision spectrum reveals perturbations.

The third CH stretching vibration overtone (4ν(CH)) of the acetylene molecule has been a prototype for intra-molecular dynamics studies. Using a sensitive cavity ring-down spectrometer calibrated with precise atomic transitions, the absolute line frequencies of 50 lines of this band have been determined with sub-MHz accuracy, or relatively 2 × 10(-9). The accuracy is also confirmed by the combination differences between the transitions sharing the same upper level. The improved accuracy, two orders of magnitude better than previous studies, allows us to reveal finer ro-vibrational couplings. Fitting of the rotational energies indicates that the J-dependent interactions take place after J > 7. The precise line positions present useful confinements to the models of the intra-molecular interactions of the acetylene molecule.

Cavity ring-down spectroscopy of Doppler-broadened absorption line with sub-MHz absolute frequency accuracy.

A continuous-wave cavity ring-down spectrometer has been built for precise determination of absolute frequencies of Doppler-broadened absorption lines. Using a thermo-stabilized Fabry-Pérot interferometer and Rb frequency references at the 780 nm and 795 nm, 0.1 - 0.6 MHz absolute frequency accuracy has been achieved in the 775-800 nm region. A water absorption line at 12579 cm(-1) is studied to test the performance of the spectrometer. The line position at zero-pressure limit is determined with an uncertainty of 0.3 MHz (relative accuracy of 0.8 × 10(-9)).

Electronic spectroscopy of ytterbium in a neon matrix.

The low-lying electronic states of Yb isolated in a solid Ne matrix are characterized through absorption and emission spectroscopy. The absorption spectra of matrix isolated Yb while pumped into its triplet states have been recorded for the first time and the 6s6p (3)P(J) → 5d6s (3)D(1, 2) transition frequencies obtained. Under matrix conditions, the structure of these states is found to be qualitatively the same as in the free atom, but the intersystem crossing rate is observed to be several orders of magnitude greater. A proposed explanation for this is curve crossings between the bound potential energy surface correlated to the 6s6p (1)P(1) state and the potential energy surfaces correlated to the 5d6s (3)D(1, 2) states in isolation. The potentials of the Yb·Ne dimer in its lowest electronic states are computed ab initio and used in a pairwise cluster model to explicitly demonstrate these curve crossings.

Application of cavity ring-down spectroscopy to the Boltzmann constant determination.

The Boltzmann constant can be optically determined by measuring the Doppler width of an absorption line of molecules at gas phase. We propose to apply a near infrared cavity ring-down (CRD) spectrometer for this purpose. The superior sensitivity of CRD spectroscopy and the good performance of the near-ir lasers can provide ppm (part-per-million) accuracy which will be competitive to present most accurate result obtained from the speed of sound in argon measurement. The possible influence to the uncertainty of the determined Doppler width from different causes are investigated, which includes the signal-to-noise level, laser frequency stability, detecting nonlinearity, and pressure broadening effect. The analysis shows that the CRD spectroscopy has some remarkable advantages over the direct absorption method proposed before. The design of the experimental setup is presented and the measurement of C2H2 line near 0.8 µm at room temperature has been carried out as a test of the instrument.