Dissociative Recombination of K and Rb in Diode-Pumped Alkali Lasers: Potential Energy Curves and Atomic Products.

Dissociative recombination (DR) of K and Rb ions is one of the most important processes in K and Rb diode-pumped alkali lasers (DPALs) strongly affecting their power. We report on the calculations of potential energy curves of the K and Rb molecular ions and of the diabatic Σ, Σ, Δ, Δ, Π, Π, Φ, and Φ valence states of K and Rb that provide the routes for DR of the ions. These curves are required for subsequent calculations of DR rate constants.

Analysis of continuous wave diode pumped cesium laser with gas circulation: experimental and theoretical studies.

Analysis of the operation of flowing-gas low power DPALs is crucial for designing high power devices. In particular, the comparison between the measured and calculated temperature rise in the laser cell makes it possible to estimate the contribution of the quenching of the alkali atoms electronic states to the gas heating. Here we report on an experimental and theoretical study of continuous wave flowing-gas Cs DPAL with He and CH buffer gases, flow velocities of 1-4 m/s and pump powers of 30-65 W.

Multi-transverse mode operation of alkali vapor lasers: modeling and comparison with experiments.

In high-power diode pumped alkali lasers with stable resonators the radius of the pump beam is usually larger than that of the fundamental laser mode and thus several high order transverse modes of the resonator can participate in the lasing. A simple optical model of multi-transverse mode operation of alkali vapor lasers is reported. The model is based on calculations of the pump and laser beam intensities in the gain medium, where the laser beam intensity is a linear combination of the azimuthally-symmetric Laguerre-Gaussian modes.

Influence of the pump-to-laser beam overlap on the performance of optically pumped cesium vapor laser.

Experimental and theoretical study of the influence of the pump-to-laser beam overlap, a crucial parameter for optimization of optically pumped alkali atom lasers, is reported for Ti:Sapphire pumped Cs laser. Maximum laser power > 370 mW with an optical-to-optical efficiency of 43% and slope efficiency ~55% was obtained. The dependence of the lasing power on the pump power was found for different pump beam radii at constant laser beam radius.

Flowing-gas diode pumped alkali lasers: theoretical analysis of transonic vs supersonic and subsonic devices.

We examine transonic diode pumped alkali laser (DPAL) devices as a simpler alternative to supersonic devices, suggested by B.D. Barmashenko and S.

Modeling of pulsed K diode pumped alkali laser: Analysis of the experimental results.

A simple optical model of K DPAL, where Gaussian spatial shapes of the pump and laser intensities in any cross section of the beams are assumed, is reported. The model, applied to the recently reported highly efficient static, pulsed K DPAL [Zhdanov et al, Optics Express 22, 17266 (2014)], shows good agreement between the calculated and measured dependence of the laser power on the incident pump power. In particular, the model reproduces the observed threshold pump power, 22 W (corresponding to pump intensity of 4 kW/cm), which is much higher than that predicted by the standard semi-analytical models of the DPAL.

Enhanced sensitivity in H photofragment detection by two-color reduced-Doppler ion imaging.

Two-color reduced-Doppler (TCRD) and one-color velocity map imaging (VMI) were used for probing H atom photofragments resulting from the ~243.1 nm photodissociation of pyrrole. The velocity components of the H photofragments were probed by employing two counterpropagating beams at close and fixed wavelengths of 243.

Vibrational overtone spectroscopy and intramolecular dynamics of C-H stretches in pyrrole.

Room-temperature photoacoustic spectra and jet-cooled action spectra of the regions of the first and second C-H stretch overtones of pyrrole were measured with the goal of gaining new insight on the vibrational patterns and the intramolecular energy flow out of the initially excited vibrational states. The rotational cooling of the action spectra helped in observing hitherto unresolved features, assisting determination of the existing multiple bands and their positions in each region. These bands were analyzed by building vibrational Hamiltonian matrices related to a simplified joint local-mode∕normal-mode (LM∕NM) model, accounting for two types of C-H stretches and their Fermi resonances with the CCH deformation modes.

Revealing the hot bands in the regions of the N-H and C-H stretch fundamentals of pyrrole.

Photoacoustic Raman spectra of gaseous pyrrole in the 3504-3535 and 3068-3152 cm(-1) energetic windows were measured, to obtain new information about the hot bands in the vicinity of the N-H(ν1) and C-H(ν2) stretch fundamentals, respectively. The observed vibrational patterns are characterized by sharp Q-branches, where the strong bands reflect the fundamentals and the weaker ones, as established from their temperature dependence, are hot bands. From the simulation of the observed spectra, the band origins and nondiagonal anharmonicities were determined.

Vibrational dynamics of pyrrole via frequency-domain spectroscopy.

The N-H stretch overtones of pyrrole, a key constituent of biologic building blocks, were studied by room temperature photoacoustic and jet-cooled action spectroscopies to unravel their intramolecular dynamics. Contrary to "isolated" states excited with two and three N-H stretch quanta, the one with four quanta shows strong accidental resonances with two other states involving three quanta of N-H stretch and one quantum of C-H stretch. The inhomogeneously reduced features in the action spectra provide the means for getting insight into the intramolecular interactions and the factors controlling energy flow within pyrrole.

Communication: mode-specific photodissociation of vibrationally excited pyrrole.

Laser-based spectroscopies coupled with molecular beam techniques facilitated the monitoring of H fragments released in ultraviolet photodissociation of pre-excited isoenergetic vibrational levels of pyrrole. Most noticeably, there was an order of magnitude larger reactivity for an eigenstate primarily consisting of two quanta of ring deformation than for another with one quantum of symmetric C-H stretch. The dynamics, the intramolecular interactions controlling the energy flow, and the mode-selectivity within a medium-sized, ten atom molecule, is discussed.

Site-dependent photodissociation of vibronically excited CD(3)NH(2) molecules.

The mechanism of H and D atom loss, following ultraviolet photolysis of methylamine-d(3), CD(3)NH(2), has been studied via electronic action and Doppler spectroscopies. The N-H bond is preferentially cleaved and the yield of both H and D photofragments increases gradually, but differently, as higher vibrational states on the first excited electronic state, A, are accessed, leading to some drop in H/D branching ratios. The average translational energies of the H photofragments are somewhat higher than those of D, implying lower energy content left in the internal degrees of freedom of the CD(3)NH than in the CD(2)NH(2) partner fragment.

Ab initio quantum mechanical study of the O((1)D) formation in the photolysis of ozone between 300 and 330 nm.

Spin-allowed production of O((1)D) in the near-UV photolysis of ozone is studied using ab initio potential energy surfaces and quantum mechanics. The O((1)D) quantum yield, reconstructed from the absolute cross sections for eight initial vibrational states in the ground electronic state, is shown to agree with the measurements in a broad range of photolysis wavelengths and temperatures. Relative contributions of one- and two-quantum stretching and bending initial excitations are quantified, with the contribution of the antisymmetric stretch being dominant for lambda < 330 nm.

Quantum tunneling of hydrogen atom in dissociation of photoexcited methylamine.

The probability of hydrogen atom release, following photoexcitation of methylamine, CH(3)NH(2), is found to increase extensively as higher vibrational states on the first excited electronic state are accessed. This behavior is consistent with theoretical calculations, based on the probability of H atom tunneling through an energy barrier on the excited potential energy surface, implying that N-H bond breaking is dominated by quantum tunneling.

Raman spectral signatures as conformational probes of gas phase flexible molecules.

A novel application of ionization-loss stimulated Raman spectroscopy (ILSRS) for monitoring the spectral features of four conformers of a gas phase flexible molecule is reported. The Raman spectral signatures of four conformers of 2-phenylethylamine are well matched by the results of density functional theory calculations, showing bands uniquely identifying the structures. The measurement of spectral signatures by ILSRS in an extended spectral range, with a conventional laser source, is instrumental in facilitating the unraveling of intra- and intermolecular interactions that are significant in biological structure and activity.

Site-dependent photodissociation of vibrationally excited CD3NH2.

The N-H and C-D bond fission in partially deuterated methylamine, CD(3)NH(2), has been investigated using vibrationally mediated photodissociation. Jet-cooled action spectra and Doppler profiles of the H and D photofragments were monitored following approximately 243.1 nm photodissociation of the parent pre-excited to two, three or four N-H stretch quanta.

A new method for determining absorption cross sections out of initially excited vibrational states.

A first experimental demonstration, combining the methods of vibrationally mediated photodissociation (VMP) and ionization-loss stimulated Raman spectroscopy (ILSRS) for measuring cross sections for dissociation of vibrationally excited levels is reported. The action spectrum obtained in the VMP of methylamine exhibits enhancement of the H photofragment yield as a result of initial vibrational excitation and the ILSRS monitors the fraction of molecules being excited. The partial cross sections for H production out of the sampled vibrational states and the extent of mode selectivity were thus determined.

Vibrational overtone spectra of N-H stretches and intramolecular dynamics on the ground and electronically excited states of methylamine.

The vibrational pattern and energy flow in the N-H stretch manifolds and the dissociation dynamics of methylamine (CH(3)NH(2)) were investigated via vibrationally mediated photodissociation. Action spectra and Doppler profiles, reflecting the yield of the ensuing H photofragments, versus near infrared/visible vibrational excitation and UV excitation, respectively, were measured. The jet-cooled action spectra and the simultaneously measured room temperature photoacoustic spectra of the first to third N-H stretching overtones exhibit broad features, somewhat narrower in the former, consisting of barely recognized multiple bands.

Rovibrational spectroscopy and intramolecular dynamics of 1,2-trans-d(2)-ethene in the first C-H stretch overtone region.

The first overtone region of the C-H stretching vibration of 1,2-trans-d(2)-ethene (HDC=CDH) was monitored via jet-cooled action spectroscopy and room temperature photoacoustic spectroscopy. The spectra include a strong band, which we assigned as the nu(1)+nu(9) C-H stretch vibration, and five additional bands related to transitions to coupled states. The spectral features were modeled in terms of a six-state deperturbation analysis, revealing the energies of the zero-order states and the relatively strong couplings between the initially excited nu(1)+nu(9) state and the doorway states.

Mode-dependent enhancement of photodissociation and photoionization in a seven atom molecule.

We report the first experimental demonstration of vibrational mode-dependent enhancement in photodissociation and photoionization of a seven atom molecule, methylamine (CH(3)NH(2)). The fundamental C-H stretches and the overtones or combinations of CH(3) bends were prepared via stimulated Raman excitation (SRE) prior to their 243.135 nm one-photon dissociation or two-photon ionization.

Vibrationally mediated photodissociation of ethene isotopic variants preexcited to the fourth C-H stretch overtone.

H and D photofragments produced via vibrationally mediated photodissociation of jet-cooled normal ethene (C2H4), 1,2-trans-d2-ethene (HDCCDH), and 1,1-d2-ethene (CH2CD2), initially excited to the fourth C-H stretch overtone region, were studied for the first time. H and D vibrational action spectra and Doppler profiles were measured. The action spectra include partially resolved features due to rotational cooling, while the monitored room temperature photoacoustic spectra exhibit only a very broad feature in each species.

Low level laser irradiation stimulates osteogenic phenotype of mesenchymal stem cells seeded on a three-dimensional biomatrix.

Mesenchymal stem cells (MSCs) seeded on three-dimensional (3D) coralline (Porites lutea) biomatrices were irradiated with low-level laser irradiation (LLLI). The consequent phenotype modulation and development of MSCs towards ossified tissue was studied in this combined 3D biomatrix/LLLI system and in a control group, which was similarly grown, but was not treated by LLLI. The irradiated and non irradiated MSC were tested at 1-7, 10, 14, 21, 28 days of culturing via analysis of cellular distribution on matrices (trypan blue), calcium incorporation to newly formed tissue (alizarin red), bone nodule formation (von Kossa), fat aggregates formation (oil red O), alkaline phosphatase (ALP) activity, scanning electron microscopy (SEM) and electron dispersive spectrometry (EDS).

Overtone spectroscopy of C-H ethyl stretches of 1-butyne.

Room-temperature photoacoustic (PA) spectra and jet-cooled action spectra of the first to third overtone regions of the ethyl C-H stretches in vapor phase 1-butyne, CH3CH2C[Triple Bond]C-H, were measured. Both the PA and action spectra exhibit a complex multiple peak structure being better resolved and more pronounced in the latter, due to inhomogeneous structure reduction. The observed manifolds were analyzed in terms of a simplified joint local-/normal-mode (LM/NM) model accounting for two types of C-H stretches (methyl and methylene) and for Fermi resonances between stretches and deformations.

Evidence for new bands in the 3nu1 and 4nu1 regions of propyne.

Vibrationally mediated photodissociation and room-temperature photoacoustic (PA) spectroscopy have been used for obtaining action (monitoring the yield of H photofragments) and absorption spectra of the second (3nu(1)) and third (4nu(1)) C-H acetylenic stretches overtone regions in propyne. The band contours appearing in these regions seem mostly regular even though they are perturbed, as expressed by the origin shifts in different K components, splitting of the K structure, and splitting due to resonances between neighboring states. Symmetric rotor simulations of the band contours of the PA and action spectra allowed extraction of the molecular parameters and rough estimates for the homogeneous broadening arising from energy flow to the bath vibrational states.

Determining the vibrational pattern via overtone cold spectra: C-H methyl stretches of propyne.

Vibrationally mediated photodissociation and photoacoustic (PA) spectroscopy were employed for studying the intramolecular dynamics of propyne initially excited to the first through fourth overtone of methyl C-H stretching modes. Room-temperature PA and jet-cooled action spectra, monitoring the absorption of the parent and the yield of the ensuing H photofragments, respectively, were obtained. The PA spectra exhibit mainly broad features, while the action spectra, due to inhomogeneous structure reduction, expose multiple peaks of recognizable shapes in the differing overtone manifolds.