Jiande Han

Electronic spectroscopy and ionization potential of UO2 in the gas phase

The electronic spectroscopy of UO(2) has been examined using multiphoton ionization with mass-selected detection of the UO(2) (+) ions. Supersonic jet cooling was used to reduce the spectral congestion. Twenty-two vibronic bands of neutral UO(2) were observed in the range from 17,400 to 32,000 cm(-1). These bands originated from the U(5fphi(u)7ssigma(g))O(2) X (3)Phi(2u) and (3)Phi(3u) states. The stronger band systems are attributed to metal-centered 7p<--7s transitions. Threshold ionization measurements were used to determine the ionization potentials of UO and UO(2). These were found to be higher than the values obtained previously from electron impact measurements but in agreement with the results of recent theoretical calculations.

Gain and lasing of optically pumped metastable rare gas atoms

Optically pumped alkali vapor lasers are currently being developed in several laboratories. The objective is to construct high-powered lasers that also exhibit excellent beam quality. Considerable progress has been made, but there are technical challenges associated with the reactivity of the metal atoms. Rare gas atoms (Rg) excited to the np(5)(n+1)s (3)P(2) configuration are metastable and have spectral properties that are closely similar to those of the alkali metals. In principle, optically pumped lasers could be constructed using excitation of the np(5)(n+1)p←np(5)(n+1)s transitions. We have demonstrated this potential by observing gain and lasing for optically pumped Ar(*), Kr(*) and Xe(*). Three-level lasing schemes were used, with He or Ar as the collisional energy transfer agent that established the population inversion. These laser systems have the advantage of using inert reagents that are gases at room temperature.

Demonstration of a diode-pumped metastable Ar laser

Pulsed lasing from optically pumped rare gas metastable atoms (Ne, Ar, Kr, and Xe) has been demonstrated previously. The laser relies on a three-level scheme, which involves the (n+1)p[5/2](3) and (n+1)p[1/2](1) states from the np(5)(n+1)p electronic configuration and the metastable (n+1)s[3/2](2) level of the np(5)(n+1)s configuration (Racah notation). Population inversions were achieved using relaxation from ((n+1)p[5/2](3) to (n+1)p[1/2](1) induced by collisions with helium or argon at pressures near 1 atm. Pulsed lasing was easily achieved using the high instantaneous pump intensities provided by a pulsed optical parametric oscillator excitation laser. In the present study we examine the potential for the development of a continuous wave (CW) optically pumped Ar laser. We report lasing of the 4p[1/2](1)→4s[3/2](2) (912.547 nm) transition following CW diode laser excitation of the 4p[5/2](3)←4s[3/2](2) line (811.754 nm). A pulsed discharge was used to generate Ar 4s[3/2](2), and the time-resolved lasing kinetics provide insights concerning the radiative and collisional relaxation processes.

Spectroscopy of the UO2+ cation and the delayed ionization of UO2

Vibronically resolved spectra for the UO+2 cation have been recorded using the pulsed field ionization zero electron kinetic energy (PFI-ZEKE) technique. For the ground state, long progressions in both the bending and symmetric stretch vibrations were observed. Bend and stretch progressions of the first electronically excited state were also observed, and the origin was found at an energy of 2678 cm(-1) above the ground state zero-point level. This observation is consistent with a recent theoretical prediction [Infante et al., J. Chem. Phys. 127, 124308 (2007)]. The ionization energy for UO2, derived from the PFI-ZEKE spectrum, namely, 6.127(1) eV, is in excellent agreement with the value obtained from an earlier photoionization efficiency measurement. Delayed ionization of UO2 in the gas phase has been reported previously [Han et al., J. Chem. Phys. 120, 5155 (2004)]. Here, we extend the characterization of the delayed ionization process by performing a quantitative study of the ionization rate as a function of the energy above the ionization threshold. The ionization rate was found to be 5 x 10(6) s(-1) at threshold, and increased linearly with increasing energy in the range investigated (0-1200 cm(-1)).

Kinetics of optically pumped Ar metastables

Optically pumped lasers that use metastable excited states of Ar have been demonstrated using both pulsed and CW excitation. In terms of Paschen labeling of the states of Ar, the laser system uses excitation of the 2p9-1s5 transition, and lases on the 2p10-1s5 line. Collisional transfer of population from 2p9 to 2p10 is achieved using He as the buffer gas. For the purpose of modeling and developing this laser, rate constants for state-to-state transfer in Ar(2p(i))+Ar/He mixtures are needed. As the 2p10 level can radiate down to 1s4, this lower level also plays a significant role in the laser kinetics. Consequently, rate constants for the relaxation of 1s4 by Ar and He are also required. In the present study we have used pulsed laser excitation techniques to measure rate constants of relevance to the optically pumped metastable Ar laser.

Rotational and vibrational energy transfer in vibrationally excited acetylene at energies near 6560 cm(-1).

Collisional energy transfer kinetics of vibrationally excited acetylene has been examined for states with internal energies near 6560 cm(-1). Total population removal rate constants were determined for selected rotational levels of the (1,0,1,0(0),0(0)) and (0,1,1,2(0),0(0)) states. Values in the range of (10-18) × 10(-10) cm(3) s(-1) were obtained. Measurements of state-to-state rotational energy transfer rate constants were also carried out for these states. The rotational energy transfer kinetics was found to be consistent with simple energy gap models for the transfer probabilities. Vibrational transfer out of the (0,1,1,2(0),0(0)) state accounted for no more than 16% of the total removal process. Transfer from (1,0,1,0(0),0(0)) to the u-symmetry (0,2,0,3(1),1(-1)), (0,1,1,2(0),0(0)), and (1,1,0,1(1),1(-1)) states was observed. Applying the principle of detailed balance to these data indicated that vibrational transfer to (1,0,1,0(0),0(0)) accounted for ~0.1% of the population loss from (0,2,0,3(1),1(-1)) or (0,1,1,2(0),0(0)), and 3% of the loss from (1,1,0,1(1),1(-1)). Relative rotational transfer probabilities were obtained for transfer to the g-symmetry (1,1,0,2(0),0(0))∕(0,0,2,0(0),0(0)) dyad. These results are related to recent studies of optically pumped acetylene lasers.

Theoretical investigations of alkali metal: rare gas interaction potentials

Alkali vapor lasers pumped by diode lasers are currently being investigated in several laboratories. One problem with this type of device is the poor matching of the broad linewidth of the pump source with the narrow absorption lines of the alkali atoms. A possible means for overcoming this difficulty is to use far-wing line broadening effects that are associated with alkali - metal rare gas interactions. This concept has recently been demonstrated for optical excitation of Cs-Ar dimers and collision pairs. Accurate data concerning the upper and lower state potential energy curves of M-Rg pairs are needed to evaluate the scaling possibilities for alkali metal rare gas dimer lasers. In addition to determining the details of the dimer absorption spectra, knowledge of the ground state potential also permits calculation of the number density of dimer pairs that will contribute to the absorption at a specific wavelength. In the present study we have used theoretical potential energy curves to predict equilibrium constants for the M + Rg ↔ MRg systems with M=Rb and Cs, and Rg=Ar, Kr and Xe. Excited state potential energy curves have been calculated for CsAr, and these data have been used to investigate the ability of first-principles calculations to predict the spectral properties of the Cs-Ar dimer.

I* kinetics of relevance to discharge-driven COIL systems

Singlet oxygen generators for COIL devices that utilize electrical or microwave discharge excitation are currently being investigated. A unique characteristic of these types of generators is that they deliver relatively high yields of O atoms. Dissociation of I2 will be facilitated by reaction with O atoms. However, a potential complication is that quenching of I* by O may be rapid. In recent studies using discharged oxygen to excite I* it was found that addition of NO2 to the output of the generator improved the yield of I*. In an attempt to understand the mechanism of the enhancement we have investigated the quenching of I* by O(3P) and NO2.

Kinetics of an optically pumped metastable Ar laser

In recent studies, an optically pumped Ar*/He laser has been demonstrated using the Ar 4p[1/2]1→4s[3/2]2 transition at 912.55 nm. Time-resolved data for this system, recorded using CW laser excitation and pulsed discharge production of Ar* 4p[3/2]2, yielded laser output pulses that were of unexpectedly short duration. It was speculated that radiative relaxation from the upper laser level to the 4s[3/2]1 state (607 cm-1 above 4s[3/2]2) caused termination of the laser pulse. In the present study this hypothesis has been tested by observing the energy transfer kinetics of the 4s[3/2]2 and 4s[3/2]1 states in Ar/He gas mixtures. Following pulsed laser excitation out of 4s[3/2]2, population recovery was observed on a μs time scale. Energy transfer from 4s[3/2]1 to 4s[3/2]2, induced by collisions with He, was characterized. The rate constant was found to be (1.0±0.5)x10-13 cm3 s-1. These observations confirmed that radiative transfer to 4s[3/2]1 was responsible for the short duration laser pulses. Modeling of a fully CW optically pumped Ar* laser shows that radiative transfer to 4s[3/2]1 reduces the number density of the Ar* atoms involved in lasing, but is otherwise benign.

Spectroscopy, dissociation dynamics, and potential energy surfaces for CN(A)−Ar

The A (2)Pi-X (2)Sigma(+) band system of CN-Ar has been examined using fluorescence depletion and action spectroscopy techniques. Eight vibronic bands of the complex were observed in association with the monomer 3-0 transition. Pump-probe measurements were used to characterize CN(A (2)Pi(32),nu=3) fragments from direct photodissociation of CN(A (2)Pi,nu=3)-Ar and CN(X (2)Sigma(+),nu=7) fragments from CN(A (2)Pi,nu=3)-Ar predissociation. The latter showed a marked preference for population of positive parity diatomic rotational levels. Bound state calculations were used to assign the A-X bands and to obtain fitted potential energy surfaces for the A state. The average potential obtained from fitting had a well depth of D(e)=137.8 cm(-1). High-level ab initio calculations were used to obtain equilibrium Jacobi coordinates of theta(e)=94 degrees and R(e)=7.25 bohr. The near-symmetric character of the fitted potential energy surface was consistent with the symmetry preference observed in the predissociation dynamics.