A.-W. Liu

Ultrasensitive near-infrared cavity ring-down spectrometer for precise line profile measurement

A cavity ring-down (CRD) spectrometer is built with a continuous-wave Ti:sapphire ring laser. Using a pair of R approximately 0.999 95 high-reflective mirrors, the noise-equivalent minimum detectable absorption loss reaches 7 x 10(-11)/cm over the spectral range of 780-830 nm. A thermal-stabilized Fabry-Perot interferometer is applied to calibrate the CRD spectrum with an accuracy of 1 x 10(-4) cm(-1). The quantitative measurement is carried out for the line profile measurements of some overtone absorption lines of C(2)H(2) near 787 nm. Doppler determined line shape has been observed with milli-Torr acetylene gas in the ring-down cavity. The instrumental line width is estimated from the line profile fitting to be <1 x 10(-4) cm(-1). It demonstrates that the CRD spectrometer with extremely high sensitivity is also very suitable for quantitative measurements including precise line profile studies in the near-infrared.

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)).

THE v = 3 ← 0 S(0)-S(3) ELECTRIC QUADRUPOLE TRANSITIONS OF H2 NEAR 0.8 μm

The very weak S(0)-S(3) electric quadrupole transitions of the second overtone band of molecular hydrogen have been recorded in the laboratory by continuous-wave cavity ring-down spectroscopy near 0.8 μm. The ultrahigh sensitivity of the spectrometer (αmin ~ 1 × 10–10 cm–1) allows us to detect the considered transitions at a relatively low sample pressure (50-750 torr). The line positions, intensity, and pressure-shift coefficients are derived from a fit of the line shape using a Galatry profile. Compared with literature values, the relative differences between the experimental and theoretical transition intensities are reduced by one order of magnitude, reaching a value of about 2% mainly dependent of the line-shape function adopted for the profile fitting. The thermal equilibrium relative intensity of the S(1) to S(0) line is determined with an accuracy of 0.4%, which can be used to probe the ortho- to para-H2 concentration ratio. Our measurements confirm the quality of the high-level ab initio calculations, including the relativistic and quantum electrodynamics corrections.

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.

High-resolution spectroscopy of the triple-substituted isotopologue of water molecule D_{\bf 2}^{\bf 18}O: the first triad

The high-resolution Fourier-transform absorption spectrum of the triple-substituted isotopologue of the water molecule, D O is measured in the 1700–9000 cm−1 region. The transitions of the ν1, 2ν2 and ν3 bands are assigned with the help of the high accuracy variational calculations based on an empirical mass-dependent Partridge–Schwenke potential energy surface. The fittings based on an effective Hamiltonian model are also utilized to confirm the assignments. A set of 816 precise ro-vibrational energy levels for the first triad of interacting vibrational states: (0 0 1), (1 0 0) and (0 2 0) is retrieved. With the upper state combination differences, the ground state energy levels are extended to J max = 23 and . These levels can be used to check the quality of the recently available high accuracy ab initio potential energy surface of the water molecule.

Laser-locked, continuously tunable high resolution cavity ring-down spectrometer

A continuous-wave cavity ring-down spectrometer with sub-MHz precision has been built using the sideband of a frequency stabilized laser as the tunable light source. The sideband is produced by passing the carrier laser beam through an electro-optic modulator (EOM) and then selected by a short etalon on resonance. The carrier laser frequency is locked to a longitude mode of a thermo-stabilized Fabry-Perot interferometer (FPI) with a long-term absolute frequency stability of 0.2 MHz (5 × 10(-10)). Broad and precise spectral scanning is accomplished, respectively, by selecting a different longitudinal mode of the FPI and by tuning the radio-frequency driving the EOM. The air broadened water absorption line at 12,321 cm(-1) was studied to test the performance of the spectrometer.

An efficient magneto-optical trap of metastable krypton atoms.

We report a magneto-optical trap of metastable krypton atoms with a trap loading rate of 3×10(11) atoms/s and a trap capture efficiency of 3×10(-5). The system starts with an atomic beam of metastable krypton produced in a liquid-nitrogen cooled, radio-frequency driven discharge. The metastable beam flux emerging from the discharge is 1.5×10(14) atoms/s/sr. The flux in the forward direction is enhanced by a factor of 156 with transverse laser cooling. The atoms are then slowed inside a Zeeman slower before captured by a magneto-optic trap. The trap efficiency can be further improved, possibly to the 10(-2) level, by gas recirculation. Such an atom trap is useful in trace analysis applications where available sample size is limited.

Line Parameters of the 782 nm Band of CO2

The 782 nm band of CO{sub 2}, in a transparent window of Earths atmosphere, was the first CO{sub 2} band observed 80 yr ago in the spectra of Venus. The band is very weak and therefore not saturated by the thick atmosphere of Venus, but its spectral parameters are still very limited due to the difficulty of detecting it in the laboratory. It is the highest overtone (ν{sub 1} + 5ν{sub 3}) of CO{sub 2} given in widely used spectroscopy databases such as HITRAN and GEISA. In the present work, the band is studied using a cavity ring-down spectrometer with ultra-high sensitivity as well as high precision. The positions of 55 lines in the band were determined with an absolute accuracy of 3 × 10{sup –5} cm{sup –1}, two orders of magnitude better than previous studies. The line intensities, self-induced pressure broadening coefficients, and the shift coefficients were also derived from the recorded spectra. The obtained spectral parameters can be applied to model the spectra of the CO{sub 2}-rich atmospheres of planets like Venus and Mars.

CO2 in solid para-hydrogen: spectral splitting and the CO2···(o-H2)n clusters.

Complicated high-resolution spectral structures are often observed for molecules doped in solid molecular hydrogen. The structures can result from miscellaneous effects and are often interpreted differently in references. The spectrum of the ν(3) band of CO(2) in solid para-H(2) presents a model system which exhibits rich spectral structures. With the help of the potential energy simulation of the CO(2) molecule doped in para-hydrogen matrix, and extensive experiments with different CO(2) isotopologues and different ortho-hydrogen concentrations in the matrix, the spectral features observed in p-H(2) matrix are assigned to the CO(2)···(o-H(2))(n) clusters and also to energy level splitting that is due to different alignments of the doped CO(2) molecules in the matrix. The assignments are further supported by the dynamics analysis and also by the spectrum recorded with sample codoped with O(2) which serves as catalyst transferring o-H(2) to p-H(2) in the matrix at 4 K temperature. The observed spectral features of CO(2)/pH(2) can potentially be used as an alternative readout of the temperature and orthohydrogen concentration in the solid para-hydrogen.

Comb-locked cavity ring-down saturation spectroscopy

We present a new method of comb-locked cavity ring-down spectroscopy for the Lamb-dip measurement of molecular ro-vibrational transitions. By locking both the probe laser frequency and a temperature-stabilized high-finesse cavity to an optical frequency comb, we realize saturation spectroscopy of molecules with kilohertz accuracy. The technique is demonstrated by recording the R(9) line in the υ = 3 - 0 overtone band of CO near 1567 nm. The Lamb-dip spectrum of such a weak line (transition rate 0.0075 s-1) is obtained using an input laser power of only 3 mW, and the position is determined to be 191 360 212 770 kHz with an uncertainty of 7 kHz (δν/ν∼3.5×10-11), which is currently limited by our rubidium clock.