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Transitions of the quadruplet-t(2) state in pink ruby and development of measuring techniques for short lifetimes/

Patrick N. Everett

Published Jan 1, 1969• 0 citations
OpenAlex

Abstract

At the time this investigation was undertaken the published experimental evidence indicated that the lifetime 1 4 of the T 2 state in pink ruby was approximately 5 0 ns. 4 Observation of fluorescence from the T 2 state had been reported but no details of the emission had been published.In this investigation it was demonstrated by direct 4 measurements that the T 2 state lifetime is less than 2 ns at temperatures between 2° K and 3 0 0° K.No fluorescent 4 emission from the T 2 state was observed although extremely high excitation powers and sensitive detection equipment were used.It was demonstrated that the nonradiative 4 2 transitions T 2 -► E occur with a frequency which is greater by a factor of at least 3 x 10^ than that of the fluorescent 4 4 4 4 Tj A 2 transitions.If the T 2 -* ■ A 2 transitions are considered to be purely electronic, it is shown that the 4 lxfetime of the T 2 state must be less than 45 p s .In the more likely event that the transitions are vibrationally assisted it is shown that the lifetime must be less than 3.5 p s .The author is indebted to the members of his doc toral committee who have been extremely generous with their time and facilities.Without such generosity the project could never have been completed.Professor C. Kikuchi was co-chairman of the committee

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At the time this investigation was undertaken the published experimental evidence indicated that the lifetime 1 4 of the T 2 state in pink ruby was approximately 5 0 ns. 4 Observation of fluorescence from the T 2 state had been reported but no details of the emission had been published.In this investigation it was demonstrated by direct 4 measurements that the T 2 state lifetime is less than 2 ns at temperatures between 2° K and 3 0 0° K.No fluorescent 4 emission from the T 2 state was observed although extremely high excitation powers and sensitive detection equipment were used.It was demonstrated that the nonradiative 4 2 transitions T 2 -► E occur with a frequency which is greater by a factor of at least 3 x 10^ than that of the fluorescent 4 4 4 4 Tj A 2 transitions.If the T 2 -* ■ A 2 transitions are considered to be purely electronic, it is shown that the 4 lxfetime of the T 2 state must be less than 45 p s .In the more likely event that the transitions are vibrationally assisted it is shown that the lifetime must be less than 3.5 p s .The author is indebted to the members of his doc toral committee who have been extremely generous with their time and facilities.Without such generosity the project could never have been completed.Professor C. Kikuchi was co-chairman of the committee
Optical absorption cross sections and the fluorescent quantum efficiency in ruby have been determined. This data has been used to correlate calculations with the analysis of the preceding paper. Stimulated emission from ruby under pulsed excitation has been studied in some detail; the observations are found to depend strongly on the perfection of the particular crystal under study. A peak power output of approximately 5 kw, total output energy of near 1 joule, beam collimation of less than ${10}^{\ensuremath{-}2}$ rad, and a spectral width of individual components in the output radiation of about 6\ifmmode\times\else\texttimes\fi{}${10}^{\ensuremath{-}4}$A at 6943 A have been measured. It is suggested that mode instabilities due to temperature shifts and a time-varying magnetic field are contributing to an oscillatory behavior of the output pulse.
Several experiments on optically excited ruby are described. First, absorption transitions initiated from the metastable states,t\min{2}\max{3}2Eandt\min{2}\max{3}2T1, are investigated in the photon energy range from 5500 to 45 000 cm-1. The absorption spectrum of these excited states is determined in both\pi-and σ-polarizations and assignments for the observed absorption bands are achieved. Obtained results are compared with other experiments reported in the literature. Next, emission properties of pink ruby are studied in the region near theRlines. The emission spectrum is determined point by point by means of intense flash excitation. The observed weak bands are ascribed to theR'and phonon assistedRtransitions. Laser actions in these bands are discussed and experimental results on phonon terminated laser amplification are presented. An experiment using a giant pulse as an excitation source reveals that the transition time fromt\min{2}\max{3}2Etot\min{2}\max{3}2T1is shorter than a fraction of 1μs at room temperature.
The unique optical properties of the ruby crystal that make it effective as a lasing medium were measured using a simple optical setup.Ruby's absorption of visible light was shown to be strongest at 420 and 550 nm, corresponding to its physical appearance as transparent pink.While the ruby crystal was illuminated with a 532 nm green laser, the R-line fluorescence peaked at 693.5 ± 1.1 nm.Finally, the fluorescence lifetime of ruby was measured by pulsing the laser with a signal generator and capturing the decaying fluorescence on a digital oscilloscope using a photodiode.An exponential decay time-constant of 3.6 ± 0.1 ms was obtained, corresponding to the fluorescence lifetime.
We have measured the radiative lifetimes of ns, np and nd Rydberg states of rubidium in the range 28 < n < 45. To enable long-lived states to be measured, our experiment uses slow-moving Rb atoms in a magneto-optical trap (MOT). Two experimental techniques have been adopted to reduce random and systematic errors. First, a narrow-bandwidth pulsed laser is used to excite the target Rydberg state, resulting in minimal shot-to-shot variation in the initial state population. Second, we monitor the target state population as a function of time delay from the laser pulse using a short-duration, millimetre-wave pulse that is resonant with a one- or two-photon transition. We then selectively field ionize the monitor state, and detect the resulting electrons with a micro-channel plate. This signal is an accurate mirror of the target state population, and is uncontaminated by contributions from other states which are populated by black body radiation. Our results are generally consistent with other recent experimental results obtained using a less sensitive method, and are also in excellent agreement with theory.
We have measured the radiative efficiency (ratio of RRR-line photons to the total number of photons emitted) and absorption cross sections for the RRR lines of dilute ruby, as a function of polarization and temperature between 20 and 373\ifmmode^\circ\else\textdegree\fi{}K. We have also measured the fluorescent lifetime from 20 to 373\ifmmode^\circ\else\textdegree\fi{}K in optically thin crystals, and from 20 to 273\ifmmode^\circ\else\textdegree\fi{}K in optically thick crystals. The difference between the reciprocal lifetimes in thin and thick crystals is directly comparable (via the Einstein relations) with the integrated absorption in the RRR lines. This comparison shows that for the RRR lines at 20 and 77\ifmmode^\circ\else\textdegree\fi{}K detailed balance holds to well within the experimental error of 5%, a precision never to our knowledge previously approached in solids. An upper limit of 0.002 ${\mathrm{cm}}^{\ensuremath{-}1}$ was placed on any Stokes shift of the R1{R}_{1}R1​ line, confirming that it is a no-phonon line. Comparison of $\ensuremath{\sigma}$ and $\ensuremath{\alpha}$ spectra confirms that the RRR lines and their vibronic satellites are predominately electric-dipole in character. The radiative efficiency of the RRR lines is strongly polarization dependent, a result which differs from that of previous workers. Its temperature dependence agrees well with that calculated from the observed vibronic spectrum at 77\ifmmode^\circ\else\textdegree\fi{}K. The integrated absorption in the RRR lines increases by about 20% between 20 and 373\ifmmode^\circ\else\textdegree\fi{}K. The absorption in the vibronic satellites on the high-frequency side of the RRR lines appears to be weaker than the corresponding emission on the low-frequency side. The temperature variation of the lifetime agrees well with that calculated from the absorption and radiative efficiency, but about 10% of the decay at 77\ifmmode^\circ\else\textdegree\fi{}K and 30% at 373\ifmmode^\circ\else\textdegree\fi{}K is either nonradiative or by emission at wavelengths outside the range of observation. The implications of our results for laser work are discussed.