The cross sections for quenching collisions between excited sodium atoms and ${\mathrm{N}}_{2}$, ${\mathrm{H}}_{2}$, HD, and ${\mathrm{D}}_{2}$ molecules in their electronic ground states have been determined using a delayed-coincidence method. The sodium atoms in mixtures with the gases were excited with 20-nsec pulses of NaD radiation, and the delays between the exciting and fluorescent pulses were measured with a time-to-pulse-height converter. The resulting pulse-height spectra, which were accummulated in a 400-channel kicksorter, yielded the effective lifetimes ${\ensuremath{\tau}}^{\ensuremath{'}}$ of the sodium resonance state, which are shorter than the natural lifetime $\ensuremath{\tau}$ because of the nonradiative decay induced in collisions with the molecules. The cross sections for collisions with ${\mathrm{N}}_{2}$, ${\mathrm{H}}_{2}$, HD, and ${\mathrm{D}}_{2}$, obtained from an analysis of the dependence of ${\ensuremath{\tau}}^{\ensuremath{'}}$ on the gas pressures, are 30.4\ifmmode\pm\else\textpm\fi{}1.2, 16.2\ifmmode\pm\else\textpm\fi{}0.3, 11.6\ifmmode\pm\else\textpm\fi{}0.4, and 9.8\ifmmode\pm\else\textpm\fi{}0.3 ${\mathrm{\AA{}}}^{2}$, respectively.
The cross sections for quenching collisions between excited sodium atoms and N2, H2, HD, and D2 molecules in their electronic ground states have been determined using a delayed-coincidence method. The sodium atoms in mixtures with the gases were excited with 20-nsec pulses of NaD radiation, and the delays between the exciting and fluorescent pulses were measured with a time-to-pulse-height converter. The resulting pulse-height spectra, which were accummulated in a 400-channel kicksorter, yielded the effective lifetimes \ensuremathτ\ensuremath′ of the sodium resonance state, which are shorter than the natural lifetime \ensuremathτ because of the nonradiative decay induced in collisions with the molecules. The cross sections for collisions with N2, H2, HD, and D2, obtained from an analysis of the dependence of \ensuremathτ\ensuremath′ on the gas pressures, are 30.4\ifmmode\pm\else\textpm\fi{}1.2, 16.2\ifmmode\pm\else\textpm\fi{}0.3, 11.6\ifmmode\pm\else\textpm\fi{}0.4, and 9.8\ifmmode\pm\else\textpm\fi{}0.3 A˚2, respectively.
3 2P1/2 ↔ 3 2P3/2 excitation transfer in sodium, induced in inelastic collisions with ground-state N2, H2, HD, and D2 molecules, has been investigated in a series of sensitized fluorescence experiments. Mixtures of sodium vapor at a pressure of 5 × 10−7 Torr, and the gases, were irradiated with each NaD component in turn, and the fluorescence which contained both D components was monitored at right angles to the direction of the exciting beam. Measurements of the relative intensities of the NaD fluorescent components yielded the following collision cross sections for excitation transfer. For Na–N2 collisions: Q12(2P1/2 → P3/2) = 144 Å2, Q21(2P1,2 ← 2P3/2) = 76 Å2 for Na–H2 collisions: Q12 = 80 Å2, Q21 = 42 Å2. For Na–HD collisions: Q12 = 84 Å2, Q21 = 44 Å2. For Na–D2 collisions: Q12 = 98 Å2, Q21 = 52 Å2. The cross sections Q21 exhibit a slight resonance effect between the atomic and molecular rotational transitions.
6 2P1/2 ↔ 6 2P3/2 mixing and 6 2S1/2 ← 6 2P1/2,3/2 quenching in cesium, induced in collisions with ground state N2, H2, HD, and D2 molecules, have been investigated using techniques of sensitized fluorescence. Mixtures of cesium vapor and the gases, in which the cesium vapor pressure was kept very low to avoid multiple scattering, were irradiated with each component of the cesium resonance doublet in turn. The fluorescence which contained both components of the doublet was observed in a direction perpendicular to that of the exciting beam. Measurements of the relative intensities of the fluorescent components yielded the following cross sections for mixing and quenching. For Cs–N2 collisions: Q12(2P1/2 → 2P3/2) = 4.7 Å2, Q21(2P1/2 ← 2P3/2) = 25 Å2, Q10(2S1/2 ← 2P1/2) = 77 Å2, Q20(2S1/2 ← 2P3/2) = 69 Å2. For Cs–H2 collisions: Q12 = 6.7 Å2, Q21 = 44 Å2, Q10 = 7 Å2, Q20 = 5 Å2. For Cs–HD collisions: Q12 = 4.8 Å2, Q21 = 32 Å2, Q10 = 4 Å2, Q20 = 3 Å2. For Cs–D2 collisions: Q12 = 4.2 Å2, Q21 = 28 Å2, Q10 = 8 Å2, Q20 = 7 Å2. The Cs–N2 and Cs–H2 cross sections supersede the values published previously (McGillis and Krause 1967). The cross sections Q21 appear to exhibit resonances with molecular rotational transitions.
52P1/2 ↔ 52P3/2 mixing and 52S1/2 ← 52P1/2, 2P3/2 quenching in rubidium, induced in collisions with ground state H2, HD, D2, N2, CH4, CD4, C2H4, and C2H6 molecules, have been investigated using methods of sensitized fluorescence. The rubidium vapor mixed with each of the gases was excited in turn by each component of the rubidium resonance doublet, and the resulting fluorescence, emitted at right angles to the direction of the exciting light, was resolved into the two fine-structure components whose intensity ratios were measured in relation to the gas pressure using photon counting techniques. The measurements yielded the following cross sections for the mixing and quenching collisions.For H2: Q12(2P1/2 → 2P3/2) = 11 Å2, Q21(2P1/2 ← 2P3/2) = 15 Å2, Q10(2S1/2 ← 2P1/2) = 6 Å2, Q20(2S1/2 ← 2P3/2) = 3 Å2.[Formula: see text]The mixing cross sections agree with theoretical values within an order of magnitude.
Excitation transfer between the 62P21 and 62P23 resonance states in cesium, induced by Cs-N2 and Cs-H2 collisions, was observed in the first experiment of its kind, in which techniques of sensitized fluorescence are used to investigate collisional mixing between resonance states of alkali atoms in mixtures with molecular gases. The cesium-vapor-gas system, in which the cesium vapor pressure was low enough to avoid radiation trapping, was irradiated with a single component of the resonance doublet. The fluorescent light, which contained both components of the doublet, was monitored at right angles to the direction of excitation. Measurements of relative intensities of the fluorescent components yielded the following cross sections for excitation transfer and for quenching of resonance radiation. For Cs-N2 collisions: ${Q}_{12}(^{2}P_{\frac{1}{2}}\ensuremath{\rightarrow}^{2}P_{\frac{3}{2}})=3.6$ A˚2, ${Q}_{21}(^{2}P_{\frac{1}{2}}\ensuremath{\leftarrow}^{2}P_{\frac{3}{2}})=16.2$ A˚2, ${Q}_{10}(^{2}S_{\frac{1}{2}}\ensuremath{\leftarrow}^{2}P_{\frac{1}{2}})=55.2$ A˚2, ${Q}_{20}(^{2}S_{\frac{1}{2}}\ensuremath{\leftarrow}^{2}P_{\frac{3}{2}})=63.5$ A˚2. For Cs-H2 collisions: Q12=6.7A˚2, Q21=29.6A˚2, Q10=11.7A˚2, Q20=6.7A˚2. The large sizes of the excitation-transfer cross sections, which are comparable to the corresponding Cs-Cs cross sections, are attributed to resonances with transitions in the molecules.
The met h o d of delayed coincidences for measu r i n g lifetimes of excited states has been used to investigate imprisonment of radiation in potassium vapor and to measure quenching cross sections in mixtures of potassium w ith diatomic gases and sodium wi t h noble gases.The me thod has also been u s e d to investigate the possibility that a longlived molec u l a r complex might be formed in inelastic collisions between 2 potassium and xenon, which lead to excitation transfer between the P potassium states.The alkali metal atoms were excited w i t h short pulses of resonance radiation, and the delays between the exciting and fluores cent pulses were m e a s u r e d w i t h a time-to-amplitude converter.At 10 3 pure potassium densities below 10 atoms/cm , the m e a s u r e d lifetimes approach the constant values of 27.8 + 0 .8 and 27.6 + 0 .8 nsec, 2 2 corresponding to the m e a n lifetimes of the 4 ^^2 anc* ^ ^3 / 2 s t a t e s > respectively.At higher densities, the apparent lifetimes are in satisfactory agreement w i t h the predictions of H o l s t e i n 's theory.The decrease in the apparent lifetimes, u p o n addition of diatomic gases to the potassium vapor, yielded cross sections for quenching collisions w it h N^, H^, HD and D^, which equal 34.0 + 2 .0 X2, 9.4 + 1.3 X2, 11.9 + 1.5 X2 and 8 .0 + 2 .0 X2, respectively.Addition of the noble gases He, Ne, Kr, Ar and Xe to sodium vapor did not lead to any measurable change in the decay rates for the sodium states within the iii
Excitation transfer between the 62P fine-structure substates in rubidium, induced in inelastic collisions with ground-state molecules, has been studied using techniques of sensitized fluorescence. Rubidium vapor in mixtures with various molecular gases was irradiated with each component of the 2P rubidium doublet in turn, and measurements of sensitized-to-resonance fluorescent intensity ratios yielded the following mixing cross sections Q12(2P1/2 → 2P3/2) and Q21(2P1/2 ← 2P3/2), as well as effective quenching cross sections Q1X(2P1/2 → 2XJ″) and Q2X(2P3/2 → 2XJ″). For collisions with H2: Q12(2P1/2 → 2P3/2) = (41 ± 5) Å2; Q21(2P1/2 ← 2P3/2) = (26 ± 3) Å2; Q1X(2P1/2 → 2XJ″) = (36 ± 9) Å2; Q2X(2P3/2 → 2XJ″) = (31 ± 8) Å2. For HD: Q12 = (42 ± 5) Å2; Q21 = (27 ± 4) Å2; Q1X = (47 ± 13) Å2; Q2X = (38 ± 10) Å2. For D2: Q12 = (42 ± 5) Å2; Q21 = (27 ± 4) Å2; Q1X = (28 ± 8) Å2; Q2X = (21 ± 7) Å2. For N2: Q12 = (107 ± 15) Å2; Q21 = (70 ± 10) Å2; Q1X = (128 ± 44) Å2; Q2X = (126 ± 33) Å2. For CH4: Q12 = (38 ± 6) Å2; Q21 = (24 ± 3) Å2; Q1X = (129 ± 41) Å2; Q2X = (114 ± 37) Å2. For CD4: Q12 = (52 ± 7) Å2; Q21 = (34 ± 5) Å2; Q1X = (82 ± 30) Å2; Q2X = (76 ± 22) Å2. An analysis of these results suggests the possibility of resonances with various molecular rotational and vibrational transitions.