Light pulse

This section begins with a brief description of the basic light-molecule interaction. As already indicated, coherent light pulses excite coherent superpositions of molecular eigenstates, known as wavepackets , and we will give a description of their motion, their coherence properties, and their interplay with the light. Then we will turn to linear and nonlinear spectroscopy, and, finally, to a brief account of coherent control of molecular motion. 

Kosloff R, Rice S A, Gaspard P, Tersigni S and Tannor D J 1989 Wavepacket dancing achieving chemical selectivity by shaping light pulses Chem. Phys. 139 201-20... 

Laubereau A and Kaiser W 1978 Vibrational dynamics of liquids and solids investigated by picosecond light pulses Rev. Mod. Phys. 50 607-65... 

Bardeen C J, Che J, WIson K R, Yakovlev V V, Cong P, Kohler B, Krause J L and Messina M 1997 Quantum control of Nal photodissociation reaction product states by ultrafast tailored light pulses J. Phys. Chem. A 101 3815-22... 

One of the most important teclmiques for the study of gas-phase reactions is flash photolysis [8, ]. A reaction is initiated by absorption of an intense light pulse, originally generated from flash lamps (duration a=lp.s). Nowadays these have frequently been replaced by pulsed laser sources, with the shortest pulses of the order of a few femtoseconds [22, 64]. 

The absorption of a light pulse instantaneously generates reactive species in high concentrations, either tlirough the fomiation of excited species or tlirough photodissociation of suitable precursors. The reaction can... 

Problems arise if a light pulse of finite duration is used. Here, different frequencies of the wave packet are excited at different times as the laser pulse passes, and thus begin to move on the upper surface at different times, with resulting interference. In such situations, for example, simulations of femtochemistry experiments, a realistic simulation must include the light field explicitely [1]. 

The emitted P particles excite the organic molecules which, in returning to normal energy levels, emit light pulses that are detected by a photomultiplier tube, amplified, and electronically counted. Liquid scintillation counting is by far the most widely used technique in tritium tracer studies and has superseded most other analytical techniques for general use (70). 

Figure 20. Influence of light pulsing frequency on PMC peaks of n-Si, in contact with a 10 nm Au at 20 mW cm-1 light intensity, compared with influence on photocurrcnt. Pulsing frequencies were 110, 1520, and 2930 cps.

Since the magnitude and shape of this PMC peak depend on the rate constants of minority charge carriers, the PMC peak provides access to kinetic measurements. It is interest that the height as well as the shape of the PMC peak change with the frequency of light pulsing. This is shown... 

Figure 23. Influence of light pulsing frequency on peak height and peak position of n-WSe2 in contact with 50 mMFe2+/3+ (5 mM H2SO4). Pulsing frequencies between 11 and 110 cps are compared forthe PMC and photocurrent curves (hght intensity, 50 mW cm-2).

Light pulsing frequency, effect on photo currents, 474... 

We present here a summary of recent work with light-pulse interferometer based inertial sensors. We first outline the general principles of operation of light-pulse interferometers. This atomic interferometer (Borde et al., 1992 Borde et al., 1989) uses two-photon velocity selective Raman transitions (Kasevich et al., 1991), to manipulate atoms while keeping them in long-lived ground states. 

Principle of a light pulse matter-wave interferometer... 

If the three light pulses of the pulse sequence are only separated in time, and not separated in space (i.e. if the velocity of the atoms is parallel to the laser beams), the interferometer is in a gravimeter or accelerometer configuration. In a uniformly accelerating frame with the atoms, the frequency of the driving... 

In the 1960s, Oppenheim et al. [10,19,20] succeeded in obtaining photographs with better resolution by means of schlieren technique with microsecond flash and then with the very short (less than 10 s) laser light pulses. This facilitated the attainment of a stroboscopic set of essentially still photographs that revealed many details of DDT. At the same time, Soloukhin [21] published a series of streak photographs taken with schlieren system and Denisov and Troshin [22] discovered that detonation leaves a record of its passage in the form of imprint on a wall coated with the thin layer of soot. 

Laser illumination, which allows for significantly fiigher photon flux, has become widespread lately. An undesirable side effect of high intensities is heating of the solution layer next to the electrode. This effect can be reduced when intermittent (pulsed) fight is used. Light pulses offer the additional possibility to examine after effects of the illumination the relaxation processes that occur when the system returns to its original condition. 

For near-field imaging based on nonlinear or ultrafast spectroscopy, light pulses from a femtosecond Ti sapphire laser (pulse width ca. 100 fs, repetition rate ca. 

Nagahara, T., Imura, K. and Okamoto, H. (2004) Time-resolved scanning near-field optical microscopy with supercontinuum light pulses generated in microstructure fiber. Rev. Sci. Instrum., 75, 4528-4533. 

Raman excitation. and I2s are the high-frequency and low-frequency components of the pump light pulse. A probe pulse of frequency 12 interacts with the coherence to present the optical response of the fundamental frequency 12 + C0fsl2. (c) Fourth-order coherent Raman scattering, the optical response of the second harmonic frequency 212 + co 2I2 is modulated by the vibrational coherence. 

A light pulse of a center frequency Q impinges on an interface. Raman-active modes of nuclear motion are coherently excited via impulsive stimulated Raman scattering, when the time width of the pulse is shorter than the period of the vibration. The ultrashort light pulse has a finite frequency width related to the Fourier transformation of the time width, according to the energy-time uncertainty relation. 

Another light pulse of frequency comes at a time delay ta and interacts with the vibrationally excited molecules. The intensity of the probe light transmitted through the interface is modulated as a function of the delay. The modulation is Fourier-transformed to provide the frequency and phase of the vibrational coherence. 

The fourth-order coherent Raman spectrum of a liquid surface was observed by Fujiyoshi et al. [28]. The same authors later reported a spectrum with an improved signal-to-noise ratio and different angle of incidence [27]. A water solution of oxazine 170 dye was placed in air and irradiated with light pulses. The SH generation at the oxazine solution was extensively studied by Steinhurst and Owrutsky [24]. The pump and probe wavelength was tuned at 630 nm to be resonant with the one-photon electronic transition of the dye. The probability of the Raman transition to generate the vibrational coherence is enhanced by the resonance. The efficiency of SH generation is also enhanced. 

A 0.2-mm thick hexadecane layer was placed on the oxazine solution. The vibrational coherence at the hexadecane/solution interface was pump-probed in a similar manner [27]. The light pulses traveled in the hexadecane layer and experienced group velocity dispersion before arriving at the interface. This undesired dispersion... 

In the time-domain detection of the vibrational coherence, the high-wavenumber limit of the spectral range is determined by the time width of the pump and probe pulses. Actually, the highest-wavenumber band identified in the time-domain fourth-order coherent Raman spectrum is the phonon band of Ti02 at 826 cm. Direct observation of a frequency-domain spectrum is free from the high-wavenum-ber limit. On the other hand, the narrow-bandwidth, picosecond light pulse will be less intense than the femtosecond pulse that is used in the time-domain method and may cause a problem in detecting weak fourth-order responses. 

Figure 8.1 (a) Block diagram of the femtosecond near-infrared laser microscope system, (b) Spectrum ofthe light pulse from the Cr F laser, (c) Interferometric autocorrelation trace of SHG signal with envelope curve calculated assuming a chirp-free Gaussian pulse with 35 fs fwhm. 

---