Time ruby laser

An interferometric method was first used by Porter and Topp [1, 92] to perfonn a time-resolved absorption experiment with a -switched ruby laser in the 1960s. The nonlinear crystal in the autocorrelation apparatus shown in figure B2.T2 is replaced by an absorbing sample, and then tlie transmission of the variably delayed pulse of light is measured as a fiinction of the delay This approach is known today as a pump-probe experiment the first pulse to arrive at the sample transfers (pumps) molecules to an excited energy level and the delayed pulse probes the population (and, possibly, the coherence) so prepared as a fiinction of time. 

Capellos and Suryanarayanan (Ref 28) described a ruby laser nanosecond flash photolysis system to study the chemical reactivity of electrically excited state of aromatic nitrocompds. The system was capable of recording absorption spectra of transient species with half-lives in the range of 20 nanoseconds (20 x lO sec) to 1 millisecond (1 O 3sec). Kinetic data pertaining to the lifetime of electronically excited states could be recorded by following the transient absorption as a function of time. Preliminary data on the spectroscopic and kinetic behavior of 1,4-dinitronaphthalene triplet excited state were obtained with this equipment... 

The first laser Raman spectra were inherently time-resolved (although no dynamical processes were actually studied) by virtue of the pulsed excitation source (ruby laser) and the simultaneous detection of all Raman frequencies by photographic spectroscopy. The advent of the scanning double monochromator, while a great advance for c.w. spectroscopy, spelled the temporary end of time resolution in Raman spectroscopy. The time-resolved techniques began to be revitalized in 1968 when Bridoux and Delhaye (16) adapted television detectors (analogous to, but faster, more convenient, and more sensitive than, photographic film) to Raman spectroscopy. The advent of the resonance Raman effect provided the sensitivity required to detect the Raman spectra of intrinsically dilute, short-lived chemical species. The development of time-resolved resonance Raman (TR ) techniques (17) in our laboratories and by others (18) has led to the routine TR observation of nanosecond-lived transients (19) and isolated observations of picosecond-timescale events by TR (20-22). A specific example of a TR study will be discussed in a later section. 

In his article mainly mode-locked tunable dye lasers are discussed. Giant pulse ruby lasers (3 nsec pulse halfwidth) have been successfully used to probe electron densities as a function of time in a rapidly expanding plasma 22). The electron lifetime in the conduction band can be determined with nanosecond semiconductor lasers. By absorption of the laser pulse the electrons in the semiconductor probe are excited into the conduction band, resulting in a definite conductivity. The mean lifetime is obtained by measuring the decrease of conductivity with time 26). 

Using as the background continuum the short-lived spontaneous fluorescence of rhodamine B or 6 G, McLaren and Stoicheff 233) developed this method further to obtain inverse Raman spectra over the range of frequency shifts 300-3500 cm" in liquids and solids in a time of 40 nsec The stimulating monochromatic radiation at 6940 A is provided by a giant-pulse ruby laser. A small part of the main laser beam is frequency-doubled in a KDP-crystal and serves to excite the rhodamine fluorescence, thus ensuring simultaneous irradiation of the sample by both beams. 

Because of the relatively large dispersion from the electrons compared with the almost constant refractivity of the neutrals and the negligible contribution of the ions, it is possible, with simultaneous measurements at two different wavelength, to determine independent values of the density of electrons and of the nonelectronic components in the plasma 274). Alcock and Ramsden 275) used the light from a giant-pulse ruby laser and its second harmonic generated in an ADP-crystal (ammonium dihydrogen phosphate) to probe a pulsed plasma and its time-dependent density in a Mach-Zehnder interferometer. 

In the laser photolysis experiments the aromatic compound (4-10" M) and the nucleophile (0 04 M ) in acetonitrile-water (1 1) were irradiated with the frequency doubled pulse (100 mj, 6 ns, 347 nm) of a ruby laser. Only time-dependent absorption changes were measured (double pulsed xenon flash lamp with 10 /is continuous output as light source) absorption spectra were constructed from these measurements at 12 or 25 nm intervals. 

CW operation of a ruby laser was achieved in early 1962 for the first time, at Bell Telephone Laboratories (Ref 1, p 14). Gas phase lasers had previously operated continuously, but these deliver only 3 milliwatts (Ref 2, p 16) as against 1 watt from solid-state CW lasers. Bell scientists revealed five new... 

Plotted curves illustrating this relation, Fig. 5, resemble very much the curves of Fig. 3. Consequently, one cannot infer from a measured intensity or energy saturation curve reliable values of molecular data without additional information, as for instance an independent measurement of ksr Another possibility is a measurement of the temporal characteristics of the bleaching as demonstrated in an experiment by Hercher et al. 14>. These authors bleached a thoroughly degassed solution of metal-free phthalocyanine in 1-chloronaphthalene by a ruby laser pulse (694.3 nm) of about 59 nsec pulse width. At the same time they measured the absorption at 632.8 nm using a He-Ne-laser, and the result of this measurement is shown in Fig. 6. It clearly demonstrates that the sample was almost completely bleached even before the laser pulse reached its maximum intensity, and that almost all of the molecules were stored in the triplet state because the transmission did not decrease with the fall of the laser intensity for at least 100 nsec. A small residual absorption indicates triplet-triplet absorption. 

Fig. 8. Laser intensity S and dye population density difference between ground state and excited state, mo—mi, versus time for a typical example of a Q-switched ruby laser. (From Ref. D)...

A major advance in the investigation of the intramolecular dynamics of spin equilibria was the development of the Raman laser temperature-jump technique (43). This uses the power of a laser to heat a solution within the time of the laser pulse width. If the relaxation time of the spin equilibrium is longer than this pulse width the dynamics of the equilibrium can be observed spectroscopically. At the time of its development only two lasers had sufficient power to cause an adequate temperature rise, the ruby laser at 694 nm and the neodymium laser at 1060 nm. Neither of these wavelengths is absorbed by solvents. Various methods were used in attempts to absorb the laser power, with partial success for microsecond relaxation times. 

Barker later described some work that involved apparatus like that shown in Figure 28.11. Light was supplied to a continuously renewed mercury pool electrode by a Q-switched, frequency-doubled ruby laser with a pulse width of — 15 ns. The electrode was set initially at any desired potential by a simple polarizing circuit, the response of which was slow enough that the electrode s reaction to the flash could be monitored as a coulostatic transient, AE (measured with respect to the initial potential) versus time. The difference in charge with respect to the initial condition is straightforwardly related to AE,... 

Kurtz and Giordmaine 79> were the first to observe stimulated Raman scattering at the polariton associated with the TO phonon at 630 cm-1 which was shifted to 497 cm-1 for 0° scattering excited with a Q-switched ruby laser. The corresponding phonon was also observed in this experiment. This can be explained by backward (180°) stimulated Raman scattering reflected from the laser resonator mirrors as confirmed by measurements of relative time of arrival at the spectrometer. 

Three important papers, published at about the same time in 1966, demonstrated very dramatically the usefulness of lasers in the measurement of molecular energy transfer. The first of these, by DeMartini and Ducuing [137], reports a study of vibrational relaxation in normal H2 using stimulated Raman scattering. The experimental arrangement is shown in Figure 3.16. Radiation from a -switched ruby laser was focused onto a pressure cell of H2 gas at room temperature to produce about IO16 vibrationally excited H2 molecules in a period of about 20 nsec. This excess population distribution... 

The first optical laser, the ruby laser, was built in 1960 by Theodore Maiman. Since that time lasers have had a profound impact on many areas of science and indeed on our everyday lives. The monochromaticity, coherence, high-intensity, and widely variable pulse-duration properties of lasers have led to dramatic improvements in optical measurements of all kinds and have proven especially valuable in spectroscopic studies in chemistry and physics. Because of their robustness and high power outputs, solid-state lasers are the workhorse devices in most of these applications, either as primary sources or, via nonlinear crystals or dye media, as frequency-shifted sources. In this experiment the 1064-mn near-infrared output from a solid-state Nd YAG laser will be frequency doubled to 532 nm to serve as a fast optical pump of a raby crystal. Ruby consists of a dilute solution of chromium 3 ions in a sapphire (AI2O3) lattice and is representative of many metal ion-doped solids that are useful as solid-state lasers, phosphors, and other luminescing materials. The radiative and nonradiative relaxation processes in such systems are important in determining their emission efficiencies, and these decay paths for the electronically excited Cr ion will be examined in this experiment. 

The hole drift mobility was determined with the aid of the time-of-ftight method (TOF) [8] in conjunction with a frequency doubled ruby laser (A k= 347 nm, flash length 20 ns). 

Secondary-ion mass spectrometry (SIMS) of a thin layer of nucleic acid bases deposited on a silver foil under bombardment with Ar ions at 3 kV gives intense pseudomolecular ions [M H] but practically no simple bond cleavage fragments. Another new technique is that of (pulsed) laser induced desorption (LD). When applied to nucleotide bases such as cytosine or adenine (266 nm, quadruplet neodymium laser or 347 nm, ruby laser) the technique has good detection limits, particularly for ions with a short lifetime (up to 100 nsec). The technique makes use of a time-of-flight instrument and is utilized in both modes, positive (PI) and negative ions (NI). Both bases exhibit an intense [BH]" ion. These results are similar to those obtained by Cf plasma desorption (PD). 

Our present experimental arrangement for kinetic laser saturation spectroscopy with a g-switched ruby laser has been described in detail previously where it has been shown that the amplitude and temporal profile of the probe laser pulses contain the picosecond time history of the /i-level... 

A SisGes superlattice (the lower indices designate the number of atomic monolayers in a SL period) containing 360 periods with an entire thickness of 500 mn was grown by MBE at 500°C on a (001) Si substrate on top of a thin (50 nm) relaxed Sio.4Geo.6 buffer. The layer sequence terminated with a 10 run thick Si cap. The wafer was irradiated by single 80 ns pulses of a ruby laser upon normal incidence. The experimental setup for the time resolved reflectivity (TRR)... 

St -> Sn Spectra.—A description has been given of a method for recording ultrafast absorption spectra using a passively mode-locked ruby laser with a ruby amplifier, a pulsed flashlamp probe source, and streak-camera detection for ps time resolution. Results for the dye 3,3 -diethylthiatricarbocyanine in methanol were reported.2870 These results can be compared with those obtained by an alternative method 29711 which permits nm spectral resolution and ps time resolution over the entire visible region, and which was first used on the Sx -> Sn absorption of 3,3 -diethyloxadicarbocyanine iodide, and which has recently been used to record the Si - Sn absorption spectra of bis-(4-dimethylaminodithio-benzil) nickel(n), and of SnIV, Pd11, and Cu" porphyrins.298 The use of time-resolved Si - Sn, Ti - Tn absorption and emission spectroscopy to assist in the selection of laser dyes has been illustrated with respect to anthracene and its derivatives.299 Si - Sn Spectra of coronene, 1 2-benzanthracene, l 12-benz-perylene, 1,2,3,4-dibenzanthracene, and benzo[6]chrysene in poly(methyl methacrylate) and toluene have been reported, the method of detection being modulation spectrophotometry, for which it is claimed that species of lifetime down to... 

---