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Physica Scripta

Quasiresonant Excitation of Lithium 2p–4d and 2p–4s Transitions in Li-Cd Vapor Mixture

Slobodan Milošević, Davorka Azinović, Irena Labazan, Goran Pichler

Published Aug 1, 2000• 1 citation
Publisher

Abstract

We performed quasiresonant laser excitation of Li–Cd vapor mixtures at 460.3 nm (2p–4d) and 497.2 nm (2p–4s). The initial population of the Li(2p) level is caused by three processes: collisional dissociation or photodissociation of the Li 2 (B 1 Π u ) molecules or energy transfer in Li 2 (B 1 Π u ) and Li(2s) collisions. The Li(4d,4s) atoms radiatively decay towards Li(3p), from which collisional population transfer to Cd(5 3 P J ) occurs, followed by three-body reactive collisions which produce the LiCd(2 2 Π ) excimer states

DOI
10.1238/physica.regular.062a00137

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Photoassociation and bound-bound excitation into the 2 2 Π state of LiZn, LiCd, and NaZn molecules

Davorka Azinović, Xinghua Li, Slobodan Milošević +1 more

The photoassociation and bound-bound excitation processes of alkali-metal--group-IIB molecules have been studied for the LiZn, LiCd, and NaZn molecules. We considered two main factors relevant to these processes, namely, the densities of collision complexes and the relevant absorption coefficients. Densities in the vapor mixture were manipulated by preparation of different metal alloys, whereas the free-bound or bound-bound absorption is selected by changing a laser wavelength used for the excitation. The 2${\mathrm{}}^{2}$\ensuremath{\Pi} states were directly excited by the laser wavelength in the spectral range 435--450 nm. The densities of the LiZn, LiCd, and NaZn excimers were estimated from alkali-metal and Zn (Cd) densities using the dissociation equilibrium equation for the corresponding excimers in the ground state. The experimentally observed LiZn excimer band at 477 nm was satisfactory compared with the appropriate theoretical simulation, assuming free-bound excitation of the 2${\mathrm{}}^{2}$\ensuremath{\Pi} state at 438.5 nm. \textcopyright{} 1996 The American Physical Society.

Physical Review A•Mar 1, 1996•8 citations
We performed quasiresonant laser excitation of Li–Cd vapor mixtures at 460.3 nm (2p–4d) and 497.2 nm (2p–4s). The initial population of the Li(2p) level is caused by three processes: collisional dissociation or photodissociation of the Li 2 (B 1 Π u ) molecules or energy transfer in Li 2 (B 1 Π u ) and Li(2s) collisions. The Li(4d,4s) atoms radiatively decay towards Li(3p), from which collisional population transfer to Cd(5 3 P J ) occurs, followed by three-body reactive collisions which produce the LiCd(2 2 Π ) excimer states
Using the resonance 2s-2p excitation of the Li atom in a lithium-cadmium vapour mixture we observed cadmium atoms excited to very high energy levels such as 6s 3 S 1 , 5d 3 D J and 6p 1 P 1 . As the main excitation process we propose radiative collisions between excited lithium and ground state cadmium atoms followed by an energy-pooling collision between Cd( 3 P J ) atoms. The temporal evolution of intensities of selected lithium and cadmium atomic lines is simulated using a system of rate equations. We estimated the rate coefficient for the radiative collision Li(2p) + Cd(5 1 S 0 ) + h ν 670.8 nm + Δ E →Li(2s) + Cd(5 3 P 0 ), to be 6×10 -10 cm 3 s -1 at T = 965 K.
Using resonance excitation of the lithium 2p atomic level in a lithium-cadmium vapor mixture we observed cadmium atomic transitions from very high levels. Time dependent fluorescence intensity from various lithium and cadmium atomic levels is measured. Solving a system of 11 rate equations simulates the time evolutions of corresponding atom densities in the lithium and cadmium atomic energy levels. From the best fit we estimate rate coefficient for radiative collision Li(2p)+Cd(51S0)+hν670.8 forming Li(2s)+Cd(53P0).
Using resonance excitation of the lithium 2p atomic level in a lithium-cadmium vapor mixture we observed cadmium atomic transitions from very high levels. Time dependent fluorescence intensity from various lithium and cadmium atomic levels is measured. Solving a system of 11 rate equations simulates the time evolutions of corresponding atom densities in the lithium and cadmium atomic energy levels. From the best fit we estimate rate coefficient for radiative collision Li(2p)+Cd(51S0)+hν670.8 forming Li(2s)+Cd(53P0).
The population and deactivation processes of the first excited 2S and 2D levels of alkali atoms have not been the focus of extensive attention to date, since these levels do not have dipole transitions to the 2S ground state, and the only radiative transitions to the 2p resonance level lie in the IR ( 1-3 fLm). We have demonstrated that in the case of potassium it is possible to populate the 32D and 52S levels in socalled optical collisions by laser excitation of the vapor and also by excitation energy transfer (EET) from the laser-excited Kidimers. 1 The lines of the corresponding 4D--->5P (1.529/1.475 f.lm and 6S ---> 5P (1.367/1.324 f.lm) transitions have also been identified in the laser-induced fluorescence of rubidium vapor,2 although the population mechanism of the levels is not examined in the present study. This st~dy will focus on determining the processes that result in the population of the Rb 42D and 62S levels and to determining the rate constants of these1'rocesses. The spectrum of the LGN-402 argon laser-induced fluorescence of Rb vapors was recorded in the IR by cooled Ge photo diodes selected for IR sensitivity and configured along the outlet slit of an MDR-3 monochromator. The synchronous detection method was employed. A FEU-79 photomultiplier was used in the visible range. Details on the experimental setup can be found in Ref. 3. The Rb vapor was excited by various argon laser lines (514.5-476.5 nm), although the 5l4.5-nm line was of primary interest. The C 1 ITu state of the RB2 dimer is not populated by this laser line; its predissociation efficiently populates the 52P resonance levels4 (see Fig. 1). Moreover the 5l4.5-nm laser line is closer in energy to the Rb 5S--->4D quadrupole transition (M= 75 cm-I). In the experiment at an atomic concentration [Rb] _1016 cm-3 the fluorescence lines from the 62S level (2.5 eV) were weaker by a factor of 50 compared to the lines from the 42D level (2.4 eV). A transition to the shorterwavelength laser excitation lines causes a certain increase in the population efficiency of the 4D level, although it also results in a more rapid growth of the population of the 5P resonance level due to the predissociation of Rb2 (C 1IT u ). I. In pure Rb vapors I) the line intensity of the 4D---> 5P transition has a linear relation to the laser excitation power ,(514.5 nm andp 5X 1016 cm-3 can be attributed to the onset of collisional quenching of the RB 4D state ('Trad =90 nsec). 5 So-called opticaJ.collisions lead to the population of the 4D level in these conditions (Aexc = 514.5 nm and no Na impurities)
The photoassociation and bound-bound excitation processes of alkali-metal--group-IIB molecules have been studied for the LiZn, LiCd, and NaZn molecules. We considered two main factors relevant to these processes, namely, the densities of collision complexes and the relevant absorption coefficients. Densities in the vapor mixture were manipulated by preparation of different metal alloys, whereas the free-bound or bound-bound absorption is selected by changing a laser wavelength used for the excitation. The 22{\mathrm{}}^{2}2\ensuremath{\Pi} states were directly excited by the laser wavelength in the spectral range 435--450 nm. The densities of the LiZn, LiCd, and NaZn excimers were estimated from alkali-metal and Zn (Cd) densities using the dissociation equilibrium equation for the corresponding excimers in the ground state. The experimentally observed LiZn excimer band at 477 nm was satisfactory compared with the appropriate theoretical simulation, assuming free-bound excitation of the 22{\mathrm{}}^{2}2\ensuremath{\Pi} state at 438.5 nm. \textcopyright{} 1996 The American Physical Society.