Femtosecond pulses

Much of the previous section dealt with two-level systems. Real molecules, however, are not two-level systems for many purposes there are only two electronic states that participate, but each of these electronic states has many states corresponding to different quantum levels for vibration and rotation. A coherent femtosecond pulse has a bandwidth which may span many vibrational levels when the pulse impinges on the molecule it excites a coherent superposition of all tliese vibrational states—a vibrational wavepacket. In this section we deal with excitation by one or two femtosecond optical pulses, as well as continuous wave excitation in section A 1.6.4 we will use the concepts developed here to understand nonlinear molecular electronic spectroscopy. 

Yelin D, Meshulach D and Silberberg Y 1997 Adaptive femtosecond pulse compression Opt. Lett. 22 1793-5... 

Seifert F, Petrov V and Woerner M 1994 Solid-state laser system for the generation of midinfrared femtosecond pulses tunable from 3.3-Mu-M to 10-Mu-M Opt. Lett. 19 2009-11... 

Unlike the typical laser source, the zero-point blackbody field is spectrally white , providing all colours, CO2, that seek out all co - CO2 = coj resonances available in a given sample. Thus all possible Raman lines can be seen with a single incident source at tOp Such multiplex capability is now found in the Class II spectroscopies where broadband excitation is obtained either by using modeless lasers, or a femtosecond pulse, which on first principles must be spectrally broad [32]. Another distinction between a coherent laser source and the blackbody radiation is that the zero-point field is spatially isotropic. By perfonuing the simple wavevector algebra for SR, we find that the scattered radiation is isotropic as well. This concept of spatial incoherence will be used to explain a certain stimulated Raman scattering event in a subsequent section. 

With the advent of short pulsed lasers, investigators were able to perfonn time resolved coherent Raman scattering. In contrast to using femtosecond pulses whose spectral widtii provides the two colours needed to produce Raman coherences, discussed above, here we consider pulses having two distinct centre frequencies whose difference drives the coherence. Since the 1970s, picosecond lasers have been employed for this purpose [113. 114], and since the late 1980s femtosecond pulses have also been used [115]. Flere we shall briefly focus on the two-colour femtosecond pulsed experiments since they and the picosecond experiments are very similar in concept. 

These limitations have recently been eliminated using solid-state sources of femtosecond pulses. Most of the femtosecond dye laser teclmology that was in wide use in the late 1980s [11] has been rendered obsolete by tliree teclmical developments the self-mode-locked Ti-sapphire oscillator [23, 24, 25, 26 and 27], the chirped-pulse, solid-state amplifier (CPA) [28, 29, 30 and 31], and the non-collinearly pumped optical parametric amplifier (OPA) [32, 33 and 34]- Moreover, although a number of investigators still construct home-built systems with narrowly chosen capabilities, it is now possible to obtain versatile, nearly state-of-the-art apparatus of the type described below Ifom commercial sources. Just as home-built NMR spectrometers capable of multidimensional or solid-state spectroscopies were still being home built in the late 1970s and now are almost exclusively based on commercially prepared apparatus, it is reasonable to expect that ultrafast spectroscopy in the next decade will be conducted almost exclusively with apparatus ifom conmiercial sources based around entirely solid-state systems. 

The spectrum of the femtosecond pulse provides some infonnation on whether the input pulse is chirped, however, causing the temporal width of I(t) to be broader than expected from the Heisenberg indetenninancy relationship. 

So far we have exclusively discussed time-resolved absorption spectroscopy with visible femtosecond pulses. It has become recently feasible to perfomi time-resolved spectroscopy with femtosecond IR pulses. Flochstrasser and co-workers [M, 150. 151. 152. 153. 154. 155. 156 and 157] have worked out methods to employ IR pulses to monitor chemical reactions following electronic excitation by visible pump pulses these methods were applied in work on the light-initiated charge-transfer reactions that occur in the photosynthetic reaction centre [156. 157] and on the excited-state isomerization of tlie retinal pigment in bacteriorhodopsin [155]. Walker and co-workers [158] have recently used femtosecond IR spectroscopy to study vibrational dynamics associated with intramolecular charge transfer these studies are complementary to those perfomied by Barbara and co-workers [159. 160], in which ground-state RISRS wavepackets were monitored using a dynamic-absorption technique with visible pulses. 

Valdmanis J A and Fork R L 1986 Design considerations for a femtosecond pulse laser balancing self phase modulation, group velocity dispersion, saturable absorption, and saturable gain IEEE J. Quantum. Electron. 22 112-18... 

Norris T B 1992 Femtosecond pulse amplification at 250 kHz with a Ti sapphire regenerative amplifier and application to continuum generation Opt. Lett. 17 1009-11... 

Greenfield S R and Wasielewski M R 1995 Near-transform-limited visible and near-IR femtosecond pulses from optical parametric amplification using Type II p-barium borate Opt. Lett. 20 1394-6... 

Kane D J and Terbino R 1993 Characterization of arbitrary femtosecond pulses using frequency-resolved optical gating IEEE J. Quantum. Electron. 29 571-9... 

It has been possible to determine transition structures computationally for many years, although not always easy. Experimentally, it has only recently become possible to examine reaction mechanisms directly using femtosecond pulsed laser spectroscopy. It will be some time before these techniques can be applied to all the compounds that are accessible computationally. Furthermore, these experimental techniques yield vibrational information rather than an actual geometry for the transition structure. 

Consider the wave packet populating just one vibrational level. This occurs for only a short period of time (the length of the femtosecond pulse). Then we can think of vibration occurring in a classical fashion. The wave packet travels along the vibrational level until it reaches the other extremity when it may be reflected and continue to travel backwards and forwards along the level. Because of the strongly anharmonic nature of the vibration the wave packet is broadened, as shown, as r increases. 

Nonlinear refraction phenomena, involving high iatensity femtosecond pulses of light traveling in a rod of Tfsapphire, represent one of the most important commercial exploitations of third-order optical nonlinearity. This is the realization of mode-locking ia femtosecond Tfsapphire lasers (qv). High intensity femtosecond pulses are focused on an output port by the third-order Kerr effect while the lower intensity continuous wave (CW) beam remains unfocused and thus is not effectively coupled out of the laser. 

So far powerful lasers with picosecond to nanosecond pulse duration have usually been used for the ablation of material from a solid sample. The very first results from application of the lasers with femtosecond pulse duration were published only quite recently. The ablation thresholds vary within a pretty wide interval of laser fluences of 0.1-10 J cm , depending on the type of a sample, the wavelength of the laser, and the pulse duration. Different advanced laser systems have been tested for LA ... 

Less pronounced thermal diffusion provides better lateral and depth resolution and is the basis of successful application of femtosecond pulses in material processing and microstructuring [4.231, 4.232]. All-solid-state femtosecond lasers with a pulse duration of 100-200 fs and a pulse energy of approximately 1 mj have recently become commercially available [4.233, 4.234]. 

Figure 10-2. Experimental setup for pump and probe measurements. Two femtosecond pulses are focused onto the same spot of the sample. The pump pulse-induced changes A7/T0 of the normalized transmission of the probe pulse are measured as a function of the time delay between the two pulses.

Figure 10-7. (a) Absorption spectrum of 3 LPPP. The arrow indicates the spectral po-.oj, silion of the excitation pulse in the time-re- i solved measurements, (b) PL spectrum for LPPP for low excitation pulse energies, (c) Differential transmission spectrum observed in LPPP after photoexcitation with a femtosecond pulse having a pulse energy of 80 uJ at a wavelength of 400 nm. The arrow indicates the spectral position of the probe pulses used for a more detailed investigation of the gain dynamics. 

The last problem of this series concerns femtosecond laser ablation from gold nanoparticles [87]. In this process, solid material transforms into a volatile phase initiated by rapid deposition of energy. This ablation is nonthermal in nature. Material ejection is induced by the enhancement of the electric field close to the curved nanoparticle surface. This ablation is achievable for laser excitation powers far below the onset of general catastrophic material deterioration, such as plasma formation or laser-induced explosive boiling. Anisotropy in the ablation pattern was observed. It coincides with a reduction of the surface barrier from water vaporization and particle melting. This effect limits any high-power manipulation of nanostructured surfaces such as surface-enhanced Raman measurements or plasmonics with femtosecond pulses. 

For studies in molecular physics, several characteristics of ultrafast laser pulses are of crucial importance. A fundamental consequence of the short duration of femtosecond laser pulses is that they are not truly monochromatic. This is usually considered one of the defining characteristics of laser radiation, but it is only true for laser radiation with pulse durations of a nanosecond (0.000 000 001s, or a million femtoseconds) or longer. Because the duration of a femtosecond pulse is so precisely known, the time-energy uncertainty principle of quantum mechanics imposes an inherent imprecision in its frequency, or colour. Femtosecond pulses must also be coherent, that is the peaks of the waves at different frequencies must come into periodic alignment to construct the overall pulse shape and intensity. The result is that femtosecond laser pulses are built from a range of frequencies the shorter the pulse, the greater the number of frequencies that it supports, and vice versa. 

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. 

C. P. J., Wilson, K. R., Muller, M. and Brakenhoff, G. J. (1998) Characterization of femtosecond pulses focused with high numerical aperture optics using interferometric surface-third-harmonic generation. Opt. Commun., 147, 153-156. 

Venkatakrishnan K, Tan B, Sivakumar NR. 2002. Sub-micron ablation of metallic thin film by femtosecond pulse laser. Opt Laser Tech 34 575-578. 

This technique will allow compression of a 100-femtosecond pulse down to 12 femtoseconds or even to 8 femtoseconds. (A femtosecond is a millionth of a billionth of a second or 1 x 10-15 s.) Pulse compression can be used to study chemical reactions, particularly intermediate states, at very high speeds. Alternatively, these optical pulses can be converted to electrical pulses to study electrical phenomena. This aspect, of course, is of great interest to people in the electronics industry because of their concern with the operation of high-speed electronic devices. It also is of great interest to people who are trying to understand the motion of biological objects such as bacteria. 

Figure 4.16. Experimental setting of the combined femtosecond pulsed laser and step scan IR spectrometer (left) and modifications of the infrared interferogram after the laser pulse (right) [187].

The experiment is performed with a spectrofluorometer similar to the ones used for linear fluorescence and quantum yield measurements (Sect. 2.1). The excitation, instead of a regular lamp, is done using femtosecond pulses, and the detector (usually a photomultiplier tube or an avalanche photodiode) must either have a very low dark current (usually true for UV-VIS detectors but not for the NIR), or to be gated at the laser repetition rate. Figure 11 shows a simplified schematic for the 2PF technique. 

---