Optical Pump-Probe Spectroscopy

In the typical setup, excitation light is provided by a pulsed (e.g., nanosecond) laser (emitting in the visible range, e.g., at 532 nm, if Mb is investigated), while the probe is delivered by a continuous-wave (cw) laser. The two beams are spatially overlapped in the sample, and the temporal changes in the optical properties (such as optical absorption or frequency shift) that follow the passage of the pump pulse are registered by a detector with short response time (relative to time scale of the processes monitored), such as a fast photodiode. 

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Time-resolved resonance Raman spectroscopy of 25 in 50% aqueous CH3CN proved that the final product 26 appears with a rate constant of 2.1 x 109 s 1 following pulsed excitation of 25.207 The appearance of 26 was slightly delayed with respect to the decay of (25), A = 3.0 x 109s, that was determined independently by optical pump probe spectroscopy in the same solvent. The intermediate that is responsible for the delayed appearance of 26, t 0.5 ns, is attributed to the triplet biradical 327.462 It shows weak, but characteristic, absorption bands at 445 and 420 nm, similar to those of the phenoxy radical. ISC is presumably rate limiting for the decay of 327, which cyclizes to the spiro-dienone 28. The intermediate 28 is not detectable its decay must be faster than its rate of formation under the reaction conditions. Decarbonylation of 28 to form p-quinone methide (29) competes with hydrolysis to 26 at low water concentrations. Hydrolysis of 29 then yields p-hydroxybenzyl alcohol (30) as the final product. 

The femtosecond pump-probe absorption spectroscopy was used for the investigation of the SI-photoisomerization of cis-stilbene in compressed solvents [20]. The authors of the work [21] demonstrated a technique for femtosecond time-resolved optical pump-probe spectroscopy that allowed to scan over a nanosecond time delay at a kilohertz scan rate without mechanical delay line. Two mode-locked femtosecond lasers with 1 GHz repetition rate were linked at a fixed difference frequency of =11 kHz. One laser delivers the pump pulses, the other provides the probe pulses. The techniques enabled high-speed scanning over a 1-ns time delay with a time resolution of 230 fs. 

The diatomic yttrium halides have been the topic of both ab initio and experimental studies. Fischell et al. (1980) have studied the excitation spectra of the YCl diatomic molecule using the laser-induced fluorescence (LIF) method. More recently, Xin et al. (1991) have studied the B ri-X system of YCl in high resolution. The rotational analysis of the observed bands has yielded very accurate molecular constants for the X and B states of YCl. Shirley et al. (1990) have studied the molecular-beam optical Stark spectrum of the B n(t = 0)-X (t = 0) band system of YF. The permanent dipole moment and the magnetic hyperfine parameter a for the B n state have been determined as 2.96(4) D and 146.8(3) MHz, respectively. The dipole moment of the X S state was determined as 1.82(8)D. More recently, Shirley et al. (1991) have employed the molecular-beam millimeter-wave optical pump-probe spectroscopy to study pure rotational transitions of the YF ground state. This study has yielded improved ground-state rotational constants as B = 8683.65(1) MHz and D = 0.0079(2)-MHz, respectively. 

Figure 8-1. Layout of the experimental scl-up for field-assisted pump-probe spectroscopy. PD photodiode OMA optical multichannel analyzer.

The double proton transfer of [2,2 -Bipyridyl]-3,3 -diol is investigated by UV-visible pump-probe spectroscopy with 30 fs time resolution. We find characteristic wavepacket motions for both the concerted double proton transfer and the sequential proton transfer that occur in parallel. The coherent excitation of an optically inactive, antisymmetric bending vibration is observed demonstrating that the reactive process itself and not only the optical excitation drives the vibrational motions. We show by the absence of a deuterium isotope effect that the ESIPT dynamics is entirely determined by the skeletal modes and that it should not be described by tunneling of the proton. 

The photodynamics of electronically excited indole in water is investigated by UV-visible pump-probe spectroscopy with 80 fs time resolution and compared to the behavior in other solvents. In cyclohexane population transfer from the optically excited La to the Lb state happens within 7 ps. In ethanol ultrafast state reversal is observed, followed by population transfer from the Lb to the La state within 6 ps. In water ultrafast branching occurs between the fluorescing state and the charge-transfer-to-solvent state. Presolvated electrons, formed together with indole radicals within our time resolution, solvate on a timescale of 350 fs. 

In order to learn about the true quantum efficiency of photogeneration one therefore has to study the photoinduced charge generation mechanism at faster time scales. Pump probe spectroscopy utilising a few optical-cycle laser pulses (5-6 fs) in the visible spectral range with broadband frequency conversion techniques [89] now makes it possible to study extremely fast optically-initiated events with unprecedented time resolution. Such a setup was used to time-resolve the kinetics of the charge transfer process from a polymer chain to a fullerene moiety in thin films of poly[2-methoxy, 5-(3, 7 -dimethyl-octyloxy)]-p-phenylene vinylene (MDMO-PPV) and [6,6]-phenyl C6i butyric acid methyl ester (PCBM). Solutions prepared from 1 wt% solutions of toluene on thin quartz substrates were studied. 

In the case of non-degenerate frequencies, the nonlocal third-order effects may give rise to chiral pump-probe spectroscopies. The only observation of a coherent Raman optical activity process to date is also due to a third-order pseudoscalar. Spiegel and Schneider have observed Raman optical activity in coherent anti-Stokes Raman scattering in a liquid of (-l-)-trans-pinane and report chiral signals that are 10 of the conventional electric-dipolar CARS intensity [23],... 

The inherent resolution of collinear-beam spectroscopy is still limited by the residual Doppler broadening. In beams with a broad velocity distribution the labeling of one velocity class by optical pumping, probed in a second Doppler-tuning zone, was exploited already before narrow Doppler widths were achieved. The complete elimination of the first-order Doppler effect in resonant two-photon absorption on Ne I has been discussed in Section 3.3, in connection with a precision measurement of the relativistic Doppler effect. A similar experiment was performed on In I, where the 29p Rydberg state was excited from 5p Pi/2 via 6s Si/2 and detected by field ionization. The linewidth caused by the laser jitter can be reduced to the transit-time limit of a few hundred kilohertz. 

The high costs associated with specialist ultrafast laser techniques can make their purchase prohibitive to many university research laboratories. However, centralised national and international research infrastructures hosting a variety of large scale sophisticated laser facilities are available to researchers. In Europe access to these facilities is currently obtained either via successful application to Laser Lab Europe (a European Union Research Initiative) [35] or directly to the research facility. Calls for proposals are launched at least annually and instrument time is allocated to the research on the basis of peer-reviewed evaluation of the proposal. Each facility hosts a variety of exotic techniques, enabling photoactive systems to be probed across a variety of timescales in different dimensions. For example, the STFC Central Laser Facility at the Rutherford Appleton Laboratory (UK) is home to optical tweezers, femtosecond pump-probe spectroscopy, time-resolved stimulated and resonance Raman spectroscopy, time-resolved linear and non-linear infrared transient spectroscopy, to name just a few techniques [36]. 

Although much of the book focuses on physical theory, 1 have emphasized aspects of optical spectroscopy that are especially pertinent to molecular biophysics, and 1 have drawn most of the examples from this area. The book therefore covers topics that receive little attention in most general books on molecular spectroscopy, including exciton interactions, resonance energy transfer, single molecule spectroscopy, high-resolution fluorescence microscopy, femtosecond pump-probe spectroscopy, and photon echoes. It says less than is customary about atomic spectroscopy and about rotational and vibrational spectroscopy of... 

Figure 3 Folded BOXCARS geometry applied in several transient nonlinear optical spectroscopies. In pump-probe spectroscopy, one of the three beams is blocked and the intensity of one of the incoming beams is monitored as a function of the time delay between the remaining two beams (e.g., beam 3 is blocked and beam 2 is monitored as a function of its delay with respect to beam 1, phase-matching condition would be k2 = ki — ki -I- k2>. Beams 4 and 5 are photon echo signals generated from beams 1 and 2. Beams 6 and 7 can be stimulated photon echo or transient grating signals generated from beams 1,2, and 3. In transient grating two of the beams are time coincident. In coherent anti-Stokes Raman spectroscopy, beams 1 and 3 are time coincident and carry the same frequency the difference between this frequency and that of beam 2 (so-called Stokes beam) matches a vibrational frequency of the system and beam 6 will correspond to the anti-Stokes emission.

The conceptual framework for the - semiclassical simulation of ultrafast spectroscopic observables is provided by the Wigner representation of quantum mechanics [2, 3]. Specifically, for the ultrafast pump-probe spectroscopy using classical trajectories, methods based on the semiclassical limit of the Liouville-von Neumann equation for the time evolution of the vibronic density matrix have been developed [4-8]. Our approach [4,6-8] is related to the Liouville space theory of nonlinear spectroscopy developed by Mukamel et al. [9]. It is characterized by the ability to approximately describe quantum phenomena such as optical transitions by averaging over the ensemble of classical trajectories. Moreover, quantum corrections for the nuclear dynamics can be introduced in a systematic manner, e.g. in the framework of the entangled trajectory method [10,11]. Alternatively, these effects can be also accounted for in the framework of the multiple spawning method [12]. In general, trajectory-based methods require drastically less computational effort than full quantum mechanical calculations and provide physical insight in ultrafast processes. Additionally, they can be combined directly with quantum chemistry methods for the electronic structure calculations. 

Figure 2 illustrates the basic concept of a typical pump-probe spectroscopy used in most ultrafast spectroscopy techniques. In its simplest form the output pulse train of an ultrafast laser is divided in two by a beam splitter. One pulse in train (called pump) first excites the sample under investigation. The second pulse train (called probe) will probe the sample with a suitable time delay with respect to the pump by introducing an optical delay in its path and some optical property (e.g., reflectivity, absorption, Raman scattering, luminescence, optical nonlinear responses) of the sample is then detected to investigate the changes produced by the pump. In most of the time-resolved pump-probe experiments, the time resolution is limited only by the pulse width of the laser or the jitter between the laser systems. 

In this chapter we describe advances in the femtosecond time-resolved multiphoton photoemission spectroscopy (TR-MPP) as a method for probing electronic structure and ultrafast interfacial charge transfer dynamics of adsorbate-covered solid surfaces. The focus is on surface science-based approaches that combine ultrafast optical pump probe excitation to induce nonlinear multi-photon photoemission (MPP) from clean or adsorbate covered single crystal surfaces. The photoemitted electrons transmit spectroscopic and dynamical information, which is captured by their energy analysis in real or reciprocal space. We examine how photoelectron spectroscopy and microscopy yield information on the unoccupied molecular structure, electron transfer and relaxation processes, light induced chemical and physical transformations and the evolution of coherent single particle and collective excitations at solid surfaces. 

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