Pump pulses

Pump-probe absorption experiments on the femtosecond time scale generally fall into two effective types, depending on the duration and spectral width of the pump pulse. If tlie pump spectrum is significantly narrower in width than the electronic absorption line shape, transient hole-burning spectroscopy [101. 102. 103. 104. 105. 106. 107. 108. 109. 110. 111. 112 and 113] can be perfomied. The second type of experiment, dynamic absorption spectroscopy [57, 114. 115. 116. 117. 118. 119. 120. 121 and 122], can be perfomied if the pump and probe pulses are short compared to tlie period of the vibrational modes that are coupled to the electronic transition. 

The main cost of this enlianced time resolution compared to fluorescence upconversion, however, is the aforementioned problem of time ordering of the photons that arrive from the pump and probe pulses. Wlien the probe pulse either precedes or trails the arrival of the pump pulse by a time interval that is significantly longer than the pulse duration, the action of the probe and pump pulses on the populations resident in the various resonant states is nnambiguous. When the pump and probe pulses temporally overlap in tlie sample, however, all possible time orderings of field-molecule interactions contribute to the response and complicate the interpretation. Double-sided Feymuan diagrams, which provide a pictorial view of the density matrix s time evolution under the action of the laser pulses, can be used to detenuine the various contributions to the sample response [125]. 

Figure B2.1.7 Transient hole-burned speetra obtained at room temperature with a tetrapyrrole-eontaining light-harvesting protein subunit, the a subunit of C-phyeoeyanin. Top fluoreseenee and absorption speetra of the sample superimposed with die speetnuu of the 80 fs pump pulses used in the experiment, whieh were obtained from an amplified CPM dye laser operating at 620 mn. Bottom absorption-diflferenee speetra obtained at a series of probe time delays.

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. 

Figure B2.5.8. Schematic representation of laser-flash photolysis using the pump-probe technique. The beam splitter BS splits the pulse coming from the laser into a pump and a probe pulse. The pump pulse initiates a reaction in the sample, while the probe beam is diverted by several mirrors M tluough a variable delay line.

The detector D monitors the absorption of the probe beam as a function of the delay between the pulses given by xHc, where c is the speed of light and v is the difference between the optical path travelled by the probe and by the pump pulse. Adapted from [110],... 

The experiment is illustrated in figure B2.5.9. The initial pump pulse generates a localized wavepacket in the first excited state of Nal, which evolves with time. The potential well in the state is the result of an avoided crossing with the ground state. Every time the wavepacket passes this region, part of it crosses to the lower surface before the remainder is reflected at the outer wall of the potential. The crossing leads to... 

Optical detectors can routinely measure only intensities (proportional to the square of the electric field), whether of optical pulses, CW beams or quasi-CW beams the latter signifying conditions where the pulse train has an interval between pulses which is much shorter than the response time of the detector. It is clear that experiments must be designed in such a way that pump-induced changes in the sample cause changes in the intensify of the probe pulse or beam. It may happen, for example, that the absorjDtion coefficient of the sample is affected by the pump pulse. In other words, due to the pump pulse the transparency of the sample becomes larger or smaller compared with the unperturbed sample. Let us stress that even when the optical density (OD) of the sample is large, let us say OD 1, and the pump-induced change is relatively weak, say 10 , it is the latter that carries positive infonnation. 

Por IR-Raman experiments, a mid-IR pump pulse from an OPA and a visible Raman probe pulse are used. The Raman probe is generated either by frequency doubling a solid-state laser which pumps the OPA [16], or by a two-colour OPA [39]. Transient anti-Stokes emission is detected with a monocliromator and photomultiplier [39], or a spectrograph and optical multichannel analyser [40]. 

FIG. IS-S Pulsed columns a) Perforated-plate column with pump pulse generator, (h) Packed column with air pulser. 

Figure 8-13. Field-induced differential transmission (-A7ZT)a - a 1-91 (solid line) and 2.53 eV (dots) as a function of pump-probe delay. In the upper panel we also show, as a dashed line, the pump-pulse autocorrelation (from Ref. [40] with permission).

A suitable method for a detailed investigation of stimulated emission and competing excited state absorption processes is the technique of transient absorption spectroscopy. Figure 10-2 shows a scheme of this technique. A strong femtosecond laser pulse (pump) is focused onto the sample. A second ultrashort laser pulse (probe) then interrogates the transmission changes due to the photoexcita-lions created by the pump pulse. The signal is recorded as a function of time delay between the two pulses. Therefore the dynamics of excited state absorption as... 

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 10-14. Inset Phololumincsccncc spectrum for low excitation pulse energy EP Main part (a) displays the spectrum for pump pulse energies well below the lasing threshold while (b) shows the spectrum obtained lor excitation with a pump energy close to the lasing threshold (c) presents the single mode-lasing spectrum emitted when the device is pumped well above threshold. The dashed lines indicate the zero line which is arbitrarily shifted in case of (b) and (c).

Sub-picosecond photoinduced absorption studies were employed to demonstrate the speed of the photoinduced electron transfer. Upon addition of C(M to P30T, the P1A spectrum, decay kinetics, and intensity dependence all change dramatically 36J. Already at 1 ps after photoexcitation by a 100 fs pump pulse at... 

Figure 10-4. Temporal behavior of the pholoinduccd transmission changes in LPPP alter excitation with a femtosecond pump pulse at 400 nnt. The two curves correspond to probe photon eneigies of 2.48 eV (dotted line) and 1.91 eV (solid line). At 2.48 eV the transmission change is positive due to stimulated emission (SE) while a photoin-dueed absorption (PIA) is observed at 1.91 eV (according to Ref.(24J).

Figure 10-5. Transient transmission changes AV/Po in PPV for different lime delays between the pump and probe pulse. The pump pulse is a 100 fs laser pulse at 325 nm obtained by frequency doubling ol amplified dye laser pulses, (a) and (b) correspond to different sides of a PPV-film. The spectra in (a) were obtained lor the unoxidized side of the sample while the set of spectra in (b) was measured for the oxidized side of the same sample. The main differences observed are a much lower stimulated emission effect for the oxidized side. The two bottom spectra depict the PL-spectra for comparison. The dashed line indicates the optical absorption (according to Kef. (281).

Figure 10-15 shows the output vs. input energy relation with a clear threshold at a pump pulse energy of approximately 1.5 nJ. This value is an order of magnitude lower than the threshold for the observation of ASE in simple planar waveguides, i.e. without distributed feedback but prepared with the same conjugated polymer. 

Figure 15.7 (b) Comparison of the photoinduced absorption spectra for near steady stale (millisecond) and ultrafast (picosecond) lime domains for P30T/C composite films. The picosecond photoinduced spectra arc taken at 300 K at various delay limes after a 2.01 eV 100 Is pump pulse for P3OT and P30T/C,., (reproduced by permission of World Scientific from Ref. I7 ). 

An alternative approach to the removal of pump pulses, which is probably the more successful but, as one might expect, the more expensive, is the use of twin pump heads. In a two-headed pump, one... 

Alster TS,McMeekin TO (1996) Improvement of facial acne scars by the 585 nm flashlamp-pumped pulsed dye laser. J Am Acad Dermatol 35 79-81... 

Manusciatti W, Fitzpatrick RE, Goldman MP (2000) Treatment of facial skin using combinations of CO Q-switched alexandrite, flashlamp-pumped pulsed dye, and Er YAG lasers in the same treatment session. Dermatol Surg 26 114-120 Jordan R, Cummins C, Burls A (2000) Laser resurfacing of the skin for the improvement of facial acne scarring a systematic review of the evidence. Br J Dermatol 142 413-423... 

An initial, ultrafast pump pulse promotes IBr to the potential energy curve Vj, where the electrostatic nuclear and electronic forces within the incipient excited IBr molecule act to force the I and Br atoms apart. contains a minimum, however, so as the atoms begin to separate the molecule remains trapped in the excited state unless it can cross over onto the repulsive potential VJ, which intersects the bound curve at an extended... 

---