12CO2 transition frequencies with kHz-accuracy by saturation spectroscopy in the 1.99-2.09 µm region.

Saturation spectroscopy has been used to determine the absolute frequencies of 107 ro-vibrational transitions of the two strongest 12CO2 bands of the 2 µm region. The considered 20012-00001 and 20013-00001 bands are of importance for the CO2 monitoring in our atmosphere. Lamb dips were measured using a cavity ring-down spectrometer linked to an optical frequency comb referenced to a GPS-disciplined Rb oscillator or to an ultra-stable optical frequency. The comb-coherence transfer (CCT) technique was applied to obtain a RF tunable narrow-line comb-disciplined laser source using an external cavity diode laser and a simple electro-optic modulator. This setup allows obtaining transition frequency measurements with kHz-level accuracy. The resulting accurate values of the energy levels of the 20012 and 20013 vibrational states are reproduced with a (1σ)-rms of about 1 kHz using the standard polynomial model. The two upper vibrational states appear thus to be highly isolated except for a local perturbation of the 20012 state leading to an energy shift of 15 kHz at J = 43. A recommended list of 145 transition frequencies with kHz accuracy is obtained providing secondary frequency standards across the 1.99-2.09 µm range. The reported frequencies will be valuable to constrain the zero-pressure frequencies of the considered transitions in 12CO2 retrieval from atmospheric spectra.

Long time scale dynamics of vibrationally excited (HBr)n clusters.

We investigated the photodissociation dynamics of vibrationally excited HBr molecules and clusters. The species were generated in a molecular beam and excited with an IR laser to a v = 1 vibrational state. A subsequent ultraviolet (UV)-pulse with 243 nm radiation photolysed the molecules to yield H-fragments, which were resonantly ionized by the same UV-pulse (2 + 1 REMPI) and detected in a velocity map imaging (VMI) experiment. We performed action spectroscopy to distinguish between two expansion regimes: (i) expansion leading to isolated HBr molecules and (ii) generation of large (HBr)n clusters. Photodissociation of isolated HBr ( v = 1) molecules in particular J ro-vibrational states yielded faster H-fragments (by approximately 0.3 eV) with respect to the photodissociation of the ground state HBr ( v = 0). On the contrary, the IR excitation of molecules in (HBr) n clusters enhanced the yield of the H-fragments UV-photodissociated from the ground-state HBr ( v = 0) molecules. Our findings show that these molecules are photodissociated within clusters, and they are not free molecules evaporated from clusters after the IR excitation. Nanosecond IR-UV pump-probe experiments show that the IR-excitation enhances the H-fragment UV-photodissociation yield up to ∼100 ns after the IR excitation. After these long IR-UV delays, excitation of HBr molecules in clusters does not originate from the IR-excitation but from the UV-photodissociation and subsequent caging of HBr molecules in v > 0 states. We show that even after ∼100 ns the IR-excited larger (HBr) n clusters do not decay to individual molecules, and the excitation is still present in some form within these clusters enhancing their UV-photodissociation.

Imaging of rotational wave-function in photodissociation of rovibrationally excited HCl molecules.

We demonstrate a visualization of quantum mechanical phenomena with the velocity map imaging (VMI) technique, combining vibrationally mediated photodissociation (VMP) of a simple diatomic HCl with the VMI of its H-photofragments. Free HCl molecules were excited by a pump infrared (IR) laser pulse to particular rotational J levels of the v = 2 vibrational state, and subsequently a probe ultraviolet laser photodissociated the molecule at a fixed wavelength of 243.07 nm where also the H-fragments were ionized. The molecule was aligned by the IR excitation with respect to the IR laser polarization, and this alignment was reflected in the angular distribution of the H-photofragments. In particular, the highest degree of molecular alignment was achieved for the J=1←0 transition, which exclusively led to the population of a single rotational state with M = 0. The obtained images were analyzed for further details of the VMP dynamics, and different J states were studied as well. Additionally, we investigated the dynamic evolution of the excited states by changing the pump-probe laser pulse delay; the corresponding images reflected dephasing due to a coupling between the molecular angular momentum and nuclear spin. Our measurements confirmed previous observation using the time-of-flight technique by Sofikitis et al. [J. Chem. Phys. 127, 144307 (2007)]. We observed a partial recovery of the originally excited state after 60 ns in agreement with the previous observation.

A simple photoacoustic detector for highly corrosive gases.

In this work, we present a new design of a cantilever-type photoacoustic (PA) detector with high chemical resistance to be used for a broad range of gaseous samples including highly corrosive gasses. A thin mica cantilever used to sense the PA pressure is the only part that comes into direct contact with the sample gas as its deflection is sensed by a probe laser from outside of the gas cell. The design of the detector is simple, compact, and affordable. It can be constructed without any special fabrication procedure in laboratories equipped with a standard mechanical and electronic workshop. The detector has been tested and its performance evaluated in combination with commercially available pulsed IR tunable optical parametric oscillator and amplifier delivering 2-10 mJ of energy per pulse sampling highly corrosive HCl and HBr gasses. The ro-vibration PA spectrum of the first overtone (ν = 0 → ν = 2) of HCl molecules in the range from 5315 to 5855 cm-1 is presented.

Velocity map imaging of HBr photodissociation in large rare gas clusters.

We have implemented the velocity map imaging technique to study clustering in the pulsed supersonic expansions of hydrogen bromide in helium, argon, and xenon. The expansions are characterized by direct imaging of the beam velocity distributions. We have investigated the cluster generation by means of UV photodissociation and photoionization of HBr molecules. Two distinct features appear in the hydrogen atom photofragment images in the clustering regime: (i) photofragments with near zero kinetic energies and (ii) "hot" photofragments originating from vibrationally excited HBr molecules. The origin of both features is attributed to the fragment caging by the cluster. We discuss the nature of the formed clusters based on the change of the photofragment images with the expansion parameters and on the photoionization mass spectra and conclude that single HBr molecule encompassed with rare gas "snowball" is consistent with the experimental observations.

Absolute frequency stabilization of an injection-seeded optical parametric oscillator.

A method is described that provides absolute frequency stabilization and calibration of the signal and idler waves generated by an injection-seeded optical parametric oscillator (OPO). The method makes use of a He-Ne stabilized transfer cavity (TC) to control the frequencies of the cw sources used to seed both the pump laser and OPO cavity. The TC serves as a stable calibration source for the signal and idler waves by providing marker fringes as the seed laser is scanned. Additionally, an acoustic-optic modulator (AOM) is used to shift the OPO seed laser's frequency before locking it onto the TC. The sidebands of the AOM are tunable over more than one free spectral range of the TC, thereby permitting stabilization of the signal and idler waves at any frequency. A ±25-MHz residual error in the absolute frequency stabilities of the pump, signal, and idler waves is experimentally demonstrated, which is roughly 30% of the 160-MHz near-transform-limited linewidths of the signal and idler pulses.