Time-resolved nsec kinetic methods are used to measure state specific electronic excitation transfer for the near-resonant process: Ca(4s5p /sup 1/P/sub 1/) +Ar /sup k//sub 1/arrow-right-left/sub k//sub -/1 Ca(4s5p /sup 3/P/sub 2,1,0/)+Ar. In stimulated emission experiments it is found that the Ca(4s5p /sup 3/P/sub 2/) level is preferentially populated. The rate constant k/sub 1/ for the specific /sup 3/P/sub 2/ channel is 5.2 +- 0.5 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ sec/sup -1/. These results are discussed in terms of near-resonant spin changing collision mechanisms. Radiative lifetimes for Ca(4s5p /sup 1/P/sub 1/) and Ca(4s5p /sup 3/P/sub 1/) are also determined to be 77 +- 2 nsec and 67 +- 2 nsec, respectively.
Time-resolved nsec kinetic methods are used to measure state specific electronic excitation transfer for the near-resonant process: Ca(4s5p /sup 1/P/sub 1/) +Ar /sup k//sub 1/arrow-right-left/sub k//sub -/1 Ca(4s5p /sup 3/P/sub 2,1,0/)+Ar. In stimulated emission experiments it is found that the Ca(4s5p /sup 3/P/sub 2/) level is preferentially populated. The rate constant k/sub 1/ for the specific /sup 3/P/sub 2/ channel is 5.2 +- 0.5 x 10/sup -11/ cm/sup 3/ molecule/sup -1/ sec/sup -1/. These results are discussed in terms of near-resonant spin changing collision mechanisms. Radiative lifetimes for Ca(4s5p /sup 1/P/sub 1/) and Ca(4s5p /sup 3/P/sub 1/) are also determined to be 77 +- 2 nsec and 67 +- 2 nsec, respectively.
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).
Two separate series of investigations have been carried out on the optically metastable states Ca[4s4p(3PJ)] and Ca[4s3d(1D2)], generated by pulsed dye-laser excitation at λ= 657.3 nm {Ca[4s4p(3P1)]â†� Ca[4s2(1S0)]} and λ= 457.5 nm {Ca[4s3d(1D2)]â†� Ca[4s2(1S0)]}, with particular emphasis on energy pooling. The kinetic behaviour of these two states has been characterised in detail across a wide range of temperature and pressure by time-resolved atomic emission measurements at the resonance wavelengths. In the case of Ca[4s3d(1D2)] these represent the first time-resolved measurements on this atomic state, yielding a mean radiative lifetime for emission to all lower states of τe= 1.71 ± 0.03 ms, in accord with time-of-flight measurements in atomic beams. The measured temperature dependence of the diffusion coefficient D12[Ca(4 1D2)–He], when expressed in the form D12∝Tn, yielded n= 1.77 ± 0.08. Further, the rate constant for the collisional quenching of Ca(4 1D2) by Ca(4 1S0) itself is estimated to be kCa=(4 ± 3)× 10–14 cm3 atom–1 s–1, in sensible accord with similar data for the quenching of Ca(4 3PJ) by the ground-state calcium atom. Energy pooling between Ca(4 3PJ)+ Ca(4 3PJ) is shown to give rise directly to Ca[4s4p(1P1)] and Ca[4s3d(1D2)]. Energy pooling between Ca(4 1D2)+ Ca(4 1D2) is shown to yield 22 electronic states, each of whose kinetic behaviour was characterised quantitatively from the relevant atomic emission profiles, including measurement of relative atomic yields.
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.
The kinetics of Ca(4 3PJ), Sr(5 3PJ) and Sr(6 3S1) have been studied by time-resolved emission following pulsed dye-laser excitation. Ground-state calcium atoms, Ca[4s2(1S0)], in the presence of Sr[5s2(1S0)], were optically excited to the first electronically excited state, Ca[4s4p(3P1)], by means of a dye-laser operating at λ= 657.3 nm [Ca(4 3P1)â†� Ca(4 1S0)]. Following rapid Boltzmann equilibration within the Ca(43PJ) manifold, fast, near-resonant energy transfer took place with Sr(5 1S0) to yield Sr(5 3PJ), together with energy pooling to yield Sr(6 3S1). The following transitions were monitored in the time-resolved mode using pre-trigger photomultiplier gating and boxcar integration with repetitive pulsing on a slow-flow system, kinetically equivalent to a static system: Ca(4 3P1)→ Ca(4 1S0)+hν(λ= 657.3 nm), Sr(5 3P1)→ Sr(5 1S0)+hν(λ= 689.3 nm) and Sr(6 3S1)→ Sr(5 3P0)+hν(λ= 679.1 nm). Detailed measurements of the time dependence of the emission profiles at λ= 657.3 and 689.3 nm demonstrated the rapid establishment of the equilibrium Ca(4 3PJ)+ Sr(5 1S0)⇌ Ca(4 1S0)+ Sr(5 3PJ) and its sustenance throughout kinetic decays. A further comparison of the first-order decay coefficients for the decays of Ca(4 3PJ) and Sr(5 3PJ) with those for Sr(6 3S1) demonstrated energy pooling between Ca(4 3PJ)+ Sr(5 3PJ) and Sr(5 3PJ)+ Sr(5 3PJ). Finally, the measured first-order decay coefficients, k′, for Ca(4 3PJ) and Sr(5 3PJ) in chemical equilibrium with one another are seperated quantitatively into their component parts of spontaneous emission, diffusion, the equilibrium constant connecting the 3PJ states and collisional quenching rate constants. Rate constants for quenching of Ca(4 3PJ) and Sr(5 3PJ) by Kr, Xe, H2 and D2 derived from earlier measurements on the individual atoms are found to be quantitatively consistent with the decay profiles under equilibrium conditions.
In a crossed beam atomic energy transfer experiment, relative cross sections are measured between initial and final magnetic substates of atomic orbitals in a three vector correlation experiment. A pulsed laser beam prepares Ca(4s5p 1P1) in a single magnetic sublevel ‖j1mi〉 with respect to the laser polarization vector. Subsequent collision with He at a well-defined relative velocity yields Ca(4s5p 3P2). The near-resonant Ca(4s5p 3P2) is probed by a second polarized pulsed laser, revealing its magnetic sublevel ‖j2mf〉 distribution with respect to the probe laser polarization vector. The experiment is analyzed in the collision frame where the direction of the initial relative velocity vector serves as the quantization axis. In this frame, the initial and final Ca states are characterized by substates ‖j1m1〉 and ‖j2m2〉, respectively. Fourteen collision frame cross sections are needed to describe the energy transfer completely. Eight of these cross sections are real and positive (conventional type—describing population transfer) and six are complex (coherence type—containing phase information). By symmetry, only 15 unique parameters for the real and imaginary parts of the cross sections are required, nine of which are obtained here using linear polarizations and collinear laser beams. Possible cases for circularly polarized light are also tabulated; measurement of these cases would provide several more parameters. For initial parallel preparation of the 1P1 p orbital with respect to the relative velocity (m1=0), the final 3P2 state is highly aligned in the m2=±1 and m2=±2 sublevels. Initial preparation of the p orbital perpendicular to the relative velocity vector (m1=±1) produces an aligned 3P2 state with greater population in the m2=0 and m2=±1 sublevels compared to the m2=±2 sublevels. Using the coherence information and symmetry, orientation cross sections are obtained into the m2=±1 sublevels (i.e., m preserving 1→1 and m-changing 1→−1) and are nearly identical. Preparation of the Ca p orbital perpendicular to the initial relative velocity enhances the state-specific collisional transfer of 1P1→3P2 by a factor of 2.2±0.2 over initial parallel preparation.
We have studied Superfluorescence (SF) under highly unfavorable conditions of rapid collisional and radiative distribution in a Doppler broadened medium. Nanosecond SF pulses at 5.5 {mu} were generated from a 50 cm column of calcium vapor buffered with argon by optically pumping the Ca (4s{sup 2} {sup 1}S{sub 0} - 4s4p{sup 1}P{sub 1} - 3d4s{sup 1}D{sub 2}) Raman Amplifier scheme. Power broadening due to an intense 13 nsec pump pulse precludes the evolution of SF for essentially this duration. As a result, the scaling laws which govern the properties of SF in a transversely excited system are shown to apply in our situation in which the conditions resemble swept excitation.