In 1928 Chandrasekhara Raman reported a process in which a material would simultaneously absorb one photon and emit another. The energies of the two photons differed by an amount corresponding to the energy difference between two quantum-mechanical levels of the medium. Raman scattering, as the phenomenon came to be known, provided a tool for the spectroscopic investigation of energy levels not accessible by the usual absorption and emission techniques. For the first thirty-five years Raman scattering was a laborious and exotic technique, important more for the quantum-mechanical principles it illustrated than for its practical applications.
In 1928 Chandrasekhara Raman reported a process in which a material would simultaneously absorb one photon and emit another. The energies of the two photons differed by an amount corresponding to the energy difference between two quantum-mechanical levels of the medium. Raman scattering, as the phenomenon came to be known, provided a tool for the spectroscopic investigation of energy levels not accessible by the usual absorption and emission techniques. For the first thirty-five years Raman scattering was a laborious and exotic technique, important more for the quantum-mechanical principles it illustrated than for its practical applications.
After the sequence of introductory chapters that collected the necessary tools, we are now ready to discuss complete experiments. The first type of experiment we consider is the creation and detection of order in multilevel atoms through coherent Raman processes. The atoms that we use to study these processes are rare earth ions in a crystal matrix. Enclosing them in a crystal allows long interaction times, but also makes it necessary to consider their interaction with neighbouring atoms. Overview Raman processes Introduction In the preceding chapters, we mentioned several types of Raman processes. Their common feature is a resonant change of the energy of the photons that interact with the material system. The energy of the scattered photons may be lower (Stokes process) or higher (anti-Stokes) than that of the incident photons. The energy difference is transferred to the material system, where it must match an energy level separation. The photon energy itself, however, does not have to match exactly a transition frequency of the medium. This is commonly expressed by the statement that the Raman scattering proceeds through a virtual state, represented by the dashed line in Figure 7.1. The presence of a real state of the atom, indicated by the full line, nevertheless increases the coupling efficiency, as discussed in Chapter 3. The earlier sections on three-level effects and optical anisotropy dealt with the mathematical formalism of Raman processes, using generic level systems to describe them.
Raman scattering is a two-photon process [1]. As illustrated in Fig. la, an incident photon is annihilated and a new photon of a different frequency is created. This implies that the scattering is inelastic, and the medium is left in a different energy state. When the scattered photon is lower in energy, or frequency, it is said to be Stokes shifted. The shift in frequency of the Stokes photon is related to a characteristic frequency of the medium. This is illustrated in Fig. 2a. Calling this characteristic material excitation frequency ω)v, the Stokes frequency is then ωs = ΩL — ωv, where ωL is the incident laser frequency. Thus, Raman (Stokes) scattering results in an excitation from the ground state of the medium to an excited state mediated by a two-photon inelastic scattering. The internal material excitation can involve the creation of an excited electronic state, an excited vibrational-rotational state, a lattice vibration, a spin flip in semiconductors, or electron waves in plasmas [2]. The phenomenon occurs in gases, liquids, solids, and plasmas.
The traditional Raman process alluded to in Chap. 13 is a three-state sequence of transitions in which radiative excitation (induced by a pump field) is followed by spontaneous emission that produces a final state differing from the initial state [Her50b] [Sho90, § 17.5]. When the final state of the sequence is more energetic than the initial state the resulting emission line (to the red of the pump wavelength) is known as a Stokes spectral line. The difference between the pump frequency and the Stokes frequency, the Raman frequency , defines the excitation energy of the final state relative to the initial state. When, instead, the final state has lower energy than the initial state, as can occur when the initial quantum state is already excited, then the emission is an anti-Stokes line, at a bluer wavelength than the pump field. The overall Raman scattering is a two-photon process. Typically Raman spectroscopy deals with molecules; the two-photon transitions are then between vibrational-rotational states, through electronically excited intermediate states, that are characterized in part by vibrational quantum number v and rotational angular momentum quantum numbers J, M . From any given excited electronic state there are many fluorescing transitions, corresponding to various vibrational and rotational quantum numbers of the final state. The wavelengths of the various Stokes and anti-Stokes lines (i.e. the Raman frequencies) characterize the particular molecular species, and so they have provided a valuable diagnostic tool for spectroscopists.
Light gets scattered when it encounters an obstacle or inhomogeneity even on a microscopic scale. A well-known example is the blue color of the sky, resulting from Rayleigh scattering of light by molecules in the air. Such redirection of energy can be used to amplify signals by taking power from a “pump” wave co-propagating with the signal in an appropriate optical medium. An example of this is provided by Raman scattering. Having said that, it is important to realize that scattering does not always occur when light interacts with a material [1]. In some cases, photons get absorbed in the medium, and their energy is eventually dissipated as heat. In other cases, the absorbed light may be re-emitted after a relatively short time delay in the form of a less energetic photon [2], a process known as fluorescence. If fluorescence takes place after a considerable delay, the same process is called phosphorescence [3]. For a photon to get absorbed by a material, its energy must correspond to the energy required by the atoms or molecules of that material to make a transition from one energy level to a higher energy level. In contrast, the scattering of photons from a material can take place without such a requirement. However, if the energy of the incident photon is close to an allowed energy transition, significant enhancement of scattering can occur.
This chapter discusses scattering. As mentioned already, optics is primarily photons interacting with electrons, atoms, and molecules. If the energy of the photon matches the difference in energy between two levels of excitation, then the photon vanishes, its energy converted into other forms. However, if the photon's energy does not find a match among the differences in possible energy states, a new photon will quickly be emitted. The new photon is usually the same energy—and thus the same wavelength—as the old one, making it appear as if the original photon bounced, which is why this nonabsorptive interaction is known as “scattering.” When the energy of the new photon matches that of the old one, the scattering is known as elastic. When the energy of the new photon is lower, the scattering is known as inelastic. All the observed phenomena of scattering—refraction, reflection, structural colors, turbidity, and more—are based on these few principles.
Technological progress in commercializing ultrafast lasers and detectors has allowed realization of cooperative processes on an ultrashort time scale, which demand a re-evaluation of the conventional cooperative phenomena with a new insight. Ultrafast cooperative phenomena in coherently prepared media and various applications of superfluorescence and coherent Raman scattering are studied in this dissertation. In particular, a simple theoretical testimony on analogy between a cooperative emission and coherent Raman scattering is presented by offering an opportunity to perform parallel research on these two processes from a unified point of view.\n\nOn one hand, the superfluorescent pulse with a time duration of a few tens of picoseconds (ps) from alkali metal vapor is observed for the first time, even though cooperative phenomena in atomic vapor have been extensively studied for more than five decades. A dense rubidium vapor pumped by ultrashort (100 femtosecond, fs) pulses allows a realization of the ultrafast superfluorescence while a time-resolved study of superfluorescence is accomplished by using a streak camera with 2 ps time resolution. Experimental research on quantum nature of cooperative emissions has been “frozen” over the years (three decades) possibly because of the technical difficulties. Quantum fluctuations of superfluorescence development are explored experimentally by taking advantage of the ultra fast streak camera. Presumable applications of the superfluorescent pulse in e.g., a remote sensing, and an ultraviolet upconversion of the input infrared laser pulse are presented. The quantum interference due to different excitation pathways is revealed by the temporal coherent control technique while observing interferometric signals from alkali metal vapors. \n\nOn the other hand, a new spectroscopic technique based on ultrafast coherent Raman scattering is developed. The key advantage of the presented technique is to suppress the non-resonant background noise which usually obscures possible applications of the other conventional coherent Raman techniques in practice. A reduction of the background noise is achieved by shaping and delaying the third pulse which probes the coherence of the medium (i.e., an enhancement of specific vibrations of the target molecules in unison) firstly prepared by two broadband pulses. We demonstrate a robustness and superiority of signal-to-noise ratio of the developed technique by identifying as few as 10000 bacterial spores at a single laser shot level.\n\nFinally, several comparative studies between cooperative and uncooperative processes are presented. A picosecond cooperative phenomenon in a three-photon resonant medium induced by a single as well as two-color ultrashort pulses is investigated. A time-resolved study shows that a picosecond cooperative effect is crucial in the well-established fields of resonant-enhanced multiphoton ionizations and harmonic generations. We also present a quantitative analysis for spontaneous versus broadband coherent Raman scattering on pyridine molecules. The spontaneous Raman signal is enhanced by 5 orders as a result of cooperative phenomena.