We report an application of laser spectroscopy techniques to a study of collision-induced interactions in atomic excited states. Due to pulsed dye laser excitation a considerable selective population of highly excited states of ccsium is obtained. Collision-induced transfer of excitation energy between the excited states results in modifications in time and spectral characteristics of observed atomic fluorescence. Quantitative information on the efficiency of collisional processes can be obtained from the measurements of time constants of the time-resolved fluorescence signals and/or from those of the integrated intensities of the fluorescence lines. Both possibilities are used in the present work. Perturbation of nD (n=8-14) and nS (n=1O-15) states of cesium in collisions with noble-gas atoms is investigated. The cross sections for the transfer of excitation between fine-structure substates of the nD states (J mixing) and for the nS-(n-4)F intermultiplet transfer are obtained.
We present a kinetic study of the low-lying electronically excited state of atomic calcium, Ca[4s4p(3PJ)], 1.885 eV above the 4s2(1S0) ground state. Ca(4 3P1) was generated by dye-laser pulsed excitation at λ= 657.3 nm of calcium vapour [Ca(4 3P1)â†� Ca(4 1S0)] at elevated temperatures (1000 K), in equilibrium with solid calcium, in a slow-flow system, kinetically equivalent to a static system. Following rapid Boltzmann equilibration within Ca(4 3PJ) through collisions, the forbidden time-resolved atomic resonance fluorescence at the same wavelength was monitored using boxcar integration. The decay of Ca(4 3PJ) in the presence of all the noble gases, He, Ne, Ar, Kr and Xe, was studied, yielding measurements of relative diffusion coefficients. Extrapolation of the diffusional component of the decay in each noble gas to infinite pressure yields an independent value of the mean radiative lifetime for Ca(4 3P1)→ Ca(4 1S0)+hν(λ= 657.3 nm), the average of which from the measurements in all the noble gases yields τe= 0.34 ± 0.02 ms (error 2σ). This result is compared with values reported from previous measurements, particularly atomic beams and time-resolved measurements. The kinetic analysis also gives rise to data for the collisional quenching of Ca(4 3PJ), which is found to be insignificant for most of the noble gases [kHe,Ne,Ar,Kr⩽ 4 × 10–15 cm3 molecule–1 s–1(1000 K)], in contrast to measurements from earlier work using phase-shift techniques. Xenon, however, exhibited measurable rates of collisional quenching of Ca(4 3PJ) characterised by kXe= 2.4 ± 0.3 × 10–14 cm3 molecule–1 s–1(1000 K). The time-resolved emission technique is further applied to the study of the removal of Ca(4 3PJ) by added gases, for which we report (errors 1σ)kN2=(8.9 ± 0.9)× 10–13 cm3 molecule–1 s–1(1000 K), kH2=(6.0 ± 0.6)× 10–14 cm3 molecule–1 s–1(1000 K), kD2=(2.7 ± 0.3)× 10–14 cm3 molecule–1 s–1(1000 K).
Inert-gas-induced collisional transfer between the first four excited states of Sr has been measured by determining excited-state densities following pulsed laser excitation of the 5
1P state. We observe 5
1P collisional transfer exclusively to the 4
3D state, with (\ensuremath{\sim}800 K) rate coefficients ranging from 0.24 to 2.0\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}11}$
cm3 ${\mathrm{s}}^{\mathrm{\ensuremath{-}}1}$ for the various gases. We also measure 4
1D2 transfer primarily to the 4
3D state, with rate coefficients of 0.65 to 6.8\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}11}$
cm3 ${\mathrm{s}}^{\mathrm{\ensuremath{-}}1}$. The 4
3D state radiative lifetime is observed to be 2.9\ifmmode\pm\else\textpm\fi{}0.2 \ensuremath{\mu}s, collisional mixing between the 4
3Dj fine-structure levels is essentially gas kinetic (k\ensuremath{\sim}5\ifmmode\times\else\texttimes\fi{}${10}^{\mathrm{\ensuremath{-}}10}$
cm3 ${\mathrm{s}}^{\mathrm{\ensuremath{-}}1}$), and k${10}^{\mathrm{\ensuremath{-}}13}$
cm3 ${\mathrm{s}}^{\mathrm{\ensuremath{-}}1}$ for 4
3D\ensuremath{\rightarrow}5
3P collisional transfer.
The role of some intermediate states, e.g. 4s5p 3 P, 3d4p( 1 D, 3 F) of Ca I in the collisional excitation of the 4p 2 P 3/2,1/2 states of Ca II (located at 74720.35 and 74497.46 cm -1 above the ground state of Ca I) following pulsed-laser pumping of the 4s4p 3 P 1 state of Ca I (E ex =15210.063 cm -1 ), is investigated. A 'pump' and 'probe' technique is employed together with the study of fluorescent emission. The 'probe' laser selectively prepares a substantially higher population of a specific intermediate state in Ca I and the increase in the fluorescent intensity of the 4p 2 P 3/2 - 4s 2 S 1/2 transition of Ca II is read as the relative strength of the particular collision channel utilizing that intermediate state. It is found that the 3d4p 1 D 2 state has the strongest influence.