Rotational Cooling Effect on the Rate Constant in the CH3F + Ca+ Reaction at Low Collision Energies.

The rotational cooling effect on the reaction rate constant of the gas-phase ion-polar-molecule reaction CH3F + Ca+ → CH3 + CaF+ was experimentally studied at low collision energies. Fluoromethane molecules showed higher reactivity as the rotational temperature decreased. The experimental rate constants were compared with the capture rate constants which were obtained by the Perturbed Rotational State (PRS) theory assuming the rotational level distribution corresponding to the experimental conditions. The PRS result shows a strong dependence of the capture rate constants on the rotational level distribution in accordance with the experimental findings. However, the PRS capture rate constants deviate from the measurement values as the average collision energy increases especially when the fluoromethane molecules are rotationally cooled far below room temperature. The present paper suggests that the rotational state distribution significantly affects the rate constants of ion-polar-molecule reactions and is one of the important issues to be considered in the study of molecular synthesis in the interstellar medium, where the thermal equilibrium is not necessarily established.

Adaptively Optimized Gas Analysis Model with Deep Learning for Near-Infrared Methane Sensors.

Noise significantly limits the accuracy and stability of retrieving gas concentration with the traditional direct absorption spectroscopy (DAS). Here, we developed an adaptively optimized gas analysis model (AOGAM) composed of a neural sequence filter (NSF) and a neural concentration retriever (NCR) based on deep learning algorithms for extraction of methane absorption information from the noisy transmission spectra and obtaining the corresponding concentrations from the denoised spectra. The model was trained on two data sets, including a computationally generated one and the experimental one. We have applied this model for retrieving methane concentration from its transmission spectra in the near-infrared (NIR) region. The NSF was implemented through an encoder-decoder structure enhanced by the attention mechanism, improving robustness under noisy conditions. Further, the NCR was employed based on a combination of a principal component analysis (PCA) layer, which focuses the algorithm on the most significant spectral components, and a fully connected layer for solving the nonlinear inversion problem of the determination of methane concentration from the denoised spectra without manual computation. Evaluation results show that the proposed NSF outperforms widely used digital filters as well as the state-of-the-art filtering algorithms, improving the signal-to-noise ratio by 7.3 dB, and the concentrations determined with the NCR are more accurate than those determined with the traditional DAS method. With the AOGAM enhancement, the optimized methane sensor features precision and stability in real-time measurements and achieves the minimum detectable column density of 1.40 ppm·m (1σ). The promising results of the present study demonstrate that the combination of deep learning and absorption spectroscopy provides a more effective, accurate, and stable solution for a gas monitoring system.

A study of the translational temperature dependence of the reaction rate constant between CH3CN and Ne+ at low temperatures.

We have measured the translational temperature dependence of the reaction rate constant for CH3CN + Ne+ → products at low temperatures. A cold Ne+ ensemble was embedded in Ca+ Coulomb crystals by a sympathetic laser cooling technique, while cold acetonitrile (CH3CN) molecules were produced by two types of Stark velocity filters to widely change the translational temperatures. The measured reaction rate constant gradually increases with the decrease in the translational temperature of the velocity-selected CH3CN molecules from 60 K down to 2 K, and thereby, a steep increase was observed at temperatures lower than 5 K. A comparison between experimental rate constants and the ion-dipole capture rate constants by the Perturbed Rotational State (PRS) theory was performed. The PRS capture rate constant reproduces well the reaction rate constant at a few kelvin but not for temperatures higher than 5 K. The result indicates that the reaction probability is small compared to typical ion-polar molecule reactions at temperatures above 5 K.

Development of a wavy Stark velocity filter for studying interstellar chemistry.

Cold polar molecules are key to both the understanding of fundamental physics and the characterization of the chemical evolution of interstellar clouds. To facilitate such studies over a wide range of temperatures, we developed a new type of Stark velocity filter for changing the translational and rotational temperatures of velocity-selected polar molecules without changing the output beam position. The translational temperature of guided polar molecules can be significantly varied by exchanging the wavy deflection section with one having a different radius of the curvature and a different deflection angle. Combining in addition a temperature variable gas cell with the wavy Stark velocity filter enables to observe the translational and rotational temperature dependence of the reaction-rate constants of cold ion-polar molecule reactions over the interesting temperature range of 10-100 K.

Single ion fluorescence excited with a single mode of an UV frequency comb.

Optical frequency combs have revolutionized the measurement of optical frequencies and improved the precision of spectroscopic experiments. Besides their importance as a frequency-measuring ruler, the frequency combs themselves can excite target transitions (direct frequency comb spectroscopy). The direct frequency comb spectroscopy may extend the optical frequency metrology into spectral regions unreachable by continuous wave lasers. In high precision spectroscopy, atoms/ions/molecules trapped in place have been often used as a target to minimize systematic effects. Here, we demonstrate direct frequency comb spectroscopy of single 25Mg ions confined in a Paul trap, at deep-UV wavelengths. Only one mode out of about 20,000 can be resonant at a time. Even then we can detect the induced fluorescence with a spatially resolving single photon camera, allowing us to determine the absolute transition frequency. The demonstration shows that the direct frequency comb spectroscopy is an important tool for frequency metrology for shorter wavelengths where continuous wave lasers are unavailable.Frequency combs are useful tools in high precision measurement including atomic transitions and atomic clocks. Here the authors demonstrate direct frequency comb spectroscopy to shorter wavelengths by probing a transition frequency in a trapped Mg+ ion using a single mode of a UV frequency comb.

Near infrared frequency comb vernier spectrometer for broadband trace gas detection.

We present a femtosecond frequency comb vernier spectrometer in the near infrared with a femtosecond Er doped fiber laser, a scanning high-finesse cavity and an InGaAs camera. By utilizing the properties of a frequency comb and a scanning high-finesse cavity such a spectrometer provides broad spectral bandwidth, high spectral resolution, and high detection sensitivity on a short time scale. We achieved an absorption sensitivity of ~8 × 10(-8) cm(-1)Hz(-1/2), corresponding to a detection limit of ~70 ppbv for acetylene, with a resolution of ~1.1 GHz in single images taken in 0.5 seconds and covering a frequency range of ~5 THz. Such measurements have broad applications for sensing greenhouse gases in this fingerprint near infrared region with a simple apparatus.

Femtosecond electron-lattice thermalization dynamics in a gold film probed by pulsed surface plasmon resonance.

The dynamics of electronic excitations and their relaxation in a gold film is studied on the femtosecond time scale with a pump-probe technique. For the pump beam we use pulses with wavelengths centered at 800 nm, 400 nm or both. The surface plasmon resonance (SPR) in Kretschmann's configuration is used as a sensitive and fast-response probe of the dynamics of the dielectric properties of the gold film. The quantity that is monitored is the intensity of the reflected light at an incidence angle close to the SPR. With changes of the dielectric properties induced by the pump beam and during subsequent relaxation, the amount of the reflected light of the probe beam, sent with a variable delay, also changes, thus providing information on the temporal characteristics of the thermalization process. Special features of SPR probing with short pulses are also accounted for in this work. The thermalization of the electronic subsystem and energy transfer to the lattice are discussed in connection with the two-temperature relaxation model that takes into account temperature dependences of the electronic heat capacity and the electron-phonon coupling.

High-power mid-infrared frequency comb source based on a femtosecond Er:fiber oscillator.

We report on a high-power mid-infrared (MIR) frequency comb source based on a femtosecond (fs) Er:fiber oscillator with a stabilized repetition rate of 250 MHz. The MIR frequency comb is produced through difference frequency generation in a periodically poled MgO-doped lithium niobate crystal. The output power is about 120 mW, with a pulse duration of about 80 fs and spectrum coverage from 2.9 to 3.6 µm, and the single comb mode power is larger than 0.3 µW over the range of 700 nm. The coherence properties of the produced high-power broadband MIR frequency comb are maintained, which was verified by heterodyne measurements. As the first application, the spectrum of a ~200 ppm methane-air mixture in a short 20 cm glass cell at ambient atmospheric pressure and temperature was measured.

Krypton separation from ambient air for application in collinear fast beam laser spectroscopy.

A portable apparatus for the separation of krypton from environmental air samples was tested. The apparatus is based on the cryogenic trapping of gases at liquid nitrogen temperature followed by controlled releases at higher temperatures. The setup consists of a liquid nitrogen trap for the removal of H(2)O and CO(2), followed by charcoal-filled coils that sequentially collect and release krypton and other gases providing four stages of gas chromatography to achieve separation and purification of krypton from mainly N(2), O(2), and Ar. Residual reactive gases remaining after the final stage of chromatography are removed with a hot Ti sponge getter. A thermal conductivity detector is used to monitor the characteristic elution times of the various components of condensed gases in the traps during step-wise warming of the traps from liquid nitrogen temperatures to 0 °C, and then to 100 °C. This allows optimizing the switching times of the valves between the stages of gas chromatography so that mainly krypton is selected and loaded to the next stage while exhausting the other gases using a He carrier. A krypton separation efficiency of ~80 % was determined using a quadrupole mass spectrometer.

Two-photon fluorescence of Coumarin 30 excited by optimally shaped pulses.

We optimized the two-photon fluorescence (TPF) of a Coumarin 30 dye by using a feedback-controlled femtosecond pulse shaping technique. For optimization we implemented an evolutionary algorithm with a liquid crystal phase-only pulse shaper in a folded 4f setup. The optimization procedure applied to the second harmonic generation, and TPF noticeably improved the output signals and demonstrated good convergence. In addition, signal ratios involving TPF and second harmonic generation (SHG) were successfully optimized. The correlation between TPF and SHG was studied, and it was found to decrease when the pulse shape was close to the optimum. These experimental results are of interest for potential applications of coherent control to complex molecular systems as well as in biomedical imaging.

Impedance spectroscopy of alpha-beta tubulin heterodimer suspensions.

Impedance spectroscopy is a technique that reveals information, such as macromolecular charges and related properties about protein suspensions and other materials. Here we report on impedance measurements over the frequency range of 1 Hz to 1 MHz of alpha-beta tubulin heterodimers suspended in a buffer. These and other polyelectrolyte suspensions show enormous dielectric responses at low frequencies, due both to the motion of charges suspended in the medium and to an electrical double layer that forms at each electrode-medium interface. We propose an equivalent circuit model to minimize electrode polarization effects and extract the intrinsic response of the bulk medium. At megaHertz frequencies, the conductivity increases with concentration below the critical concentration of approximately 1 mg/ml for microtubule polymerization, above which the conductivity decreases. This suggests that such measurements can be used to monitor the dynamics of microtubule polymerization. Finally, we obtain the net charge number per tubulin dimer of /Z/ = 306 in the saline buffer, which, if maintained as the dimers polymerized, would yield a linear charge density of 3.8 e/angstroms for the assembled microtubules. These results are potentially important for fundamental electrostatic processes in biomolecules and suggest the possibility of developing future bioelectronic applications.

A frequency comb in the extreme ultraviolet.

Since 1998, the interaction of precision spectroscopy and ultrafast laser science has led to several notable accomplishments. Femtosecond laser optical frequency 'combs' (evenly spaced spectral lines) have revolutionized the measurement of optical frequencies and enabled optical atomic clocks. The same comb techniques have been used to control the waveform of ultrafast laser pulses, which permitted the generation of single attosecond pulses, and have been used in a recently demonstrated 'oscilloscope' for light waves. Here we demonstrate intra-cavity high harmonic generation in the extreme ultraviolet, which promises to lead to another joint frontier of precision spectroscopy and ultrafast science. We have generated coherent extreme ultraviolet radiation at a repetition frequency of more than 100 MHz, a 1,000-fold improvement over previous experiments. At such a repetition rate, the mode spacing of the frequency comb, which is expected to survive the high harmonic generation process, is large enough for high resolution spectroscopy. Additionally, there may be many other applications of such a quasi-continuous compact and coherent extreme ultraviolet source, including extreme ultraviolet holography, microscopy, nanolithography and X-ray atomic clocks.

Effect of varying electric potential on surface-plasmon resonance sensing.

The high sensitivity of surface-plasmon resonance (SPR) sensors allows measurements of small variations in surface potentials to be made. We studied the changes of the SPR angle when an oscillating electric potential was applied to a gold film on which surface plasmons were excited. The shifts of the SPR resonance angle were observed for various aqueous solutions as an adjacent medium. A model that takes into account the redistribution of charges at the double layer near the metal-liquid interface as well as the oxidation of the gold film was developed. It was found that a change in the electronic density at voltages below the oxidation potential and, in addition, the oxidation of the gold surface above this potential are the main mechanisms that account for the observed dependences. It was shown that relatively slow oxidation-reduction processes can explain the observed hysteresis effect. Application of these techniques to studies of dielectric properties and conformational changes of polar biomolecules, such as tubulin, are discussed.