Femtosecond laser pulse spectroscopy

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... 

Lozovoy, V. V., Shane, J. C., Xu, B. W., and Dantus, M. 2005. Spectral phase optimization of femtosecond laser pulses for narrow-band, low-background nonlinear spectroscopy. Opt. Exp. 13(26) 10882-87. 

Different schemes and recent results for high-resolution rotational coherence spectroscopy with picosecond and femtosecond laser pulses... 

DilTcrcm schemes and recent results for high-resolution rotational coherence spectroscopy with picosecond and femtosecond laser pulses C. Kiehn, V.-V Matylitsky. A. Weiehert, M.-F. Gclin. W. Jar/eba and B Brutschy 73... 

G. Gerber By applying two-photon ionization spectroscopy with tunable femtosecond laser pulses we recorded the absorption through intermediate resonances in cluster sizes Na with n = 3,. 21. The fragmentation channels and decay pattern vary not only for different cluster sizes but also for different resonances corresponding to a particular size n. This variation of r and the fragmentation channels cannot be explained by collective type processes (jellium model with surface plasmon excitation) but rather require molecular structure type calculations and considerations. 

D. M. Neumark We are currently carrying out somewhat different femtosecond experiments in which time-resolved photoelectron spectroscopy is used to probe the photodissociation dynamics of negative ions. In these experiments, an anion is photodissociated with a femtosecond laser pulse. After a time delay, the dissociating anion is pho-todetached with a second femtosecond pulse and the resulting photoelectron spectrum is measured. The photoelectron spectrum as a function of delay time provides a detailed probe of the anion photodissociation dynamics. First results have recently been obtained for the photodissociation of I2. 

Bandrauk s long-term research interests include the dressed-state representation of molecular spectroscopy. His contributions to the nonperturba-tive treatment of molecular spectroscopy from the weak field to strong field limits have been summarized in two chapters in a book he edited in 1993.286 Bandrauk and his coworkers published the first theoretical demonstration of the use of chirped pulses to effect laser bond breaking in less than a picosecond.287 His other firsts include the first prediction of molecular stabilization in intense laser fields288 and the first complete non-Born-Oppenheimer calculation of dissociative ionization of molecules in intense femtosecond laser pulses.289... 

This approach has the potential to resolve the time evolution of reactions at the surface and to capture short-lived reaction intermediates. As illustrated in Figure 3.23, a typical pump-probe approach uses surface- and molecule-specific spectroscopies. An intense femtosecond laser pulse, the pump pulse, starts a reaction of adsorbed molecules at a surface. The resulting changes in the electronic or vibrational properties of the adsorbate-substrate complex are monitored at later times by a second ultrashort probe pulse. This probe beam can exploit a wide range of spectroscopic techniques, including IR spectroscopy, SHG and infrared reflection-adsorption spectroscopy (IRAS). 

Blasco F, Stenz C, Salin F, Faenov AYa, Magunov AI, Pikutz TA, Skobelev IYu (2001) Portable, tunable, high-luminosity spherical crystal spectrometer with an X-ray charge coupled device, for high-resolution X-ray spectroscopy of clusters heated by femtosecond laser pulses. Rev. Sci. Instrum. 72 1956-1962... 

Following the above-mentioned spectroscopic study by Johnson and co-workers [55], Neumark and co-workers [56] explored the ultrafast real-time dynamics that occur after excitation into the CTTS precursor states of I (water) [n — 4-6) by applying a recently developed novel method with ultimate time resolution, i.e., femtosecond photoelectron spectroscopy (FPES). In anion FPES, a size-selected anion is electronically excited with a femtosecond laser pulse (the pump), and a second femtosecond laser pulse (the probe) induces photodetachment of the excess electron, the kinetic energy of which is determined. The time-ordered series of the resultant PE spectra represents the time evolution of the anion excited state projected on to the neutral ground state. In the study of 1 -(water), 263 nm (4.71 eV) and 790 nm (1.57 eV) pulses of 100 fs duration were used as pump and probe pulses, respectively. The pump pulse is resonant with the CTTS bands for all the clusters examined. 

In the last few years Nelson and co-workers [63-65] have presented a new approach to light scattering spectroscopy, named impulsive stimulated light scattering (ISS), which seems to be able to detect one particle rotational correlation functions. In ISS, one induces coherent vibrational motion by irradiating the sample with two femtosecond laser pulses, and... 

Transient grating spectroscopy is relatively easily handled compared with the transient absorption spectroscopy, and is often used to study carrier dynamics at semiconductor electrodes [32]. Figure 14 schematically shows the principle of transient grating spectroscopy. A femtosecond laser pulse for sample excitation is split into two beams, which are crossed again at the semiconductor surface to produce an optical striped interference pattern. The interference pattern produces a striped pattern of the densities of photo-generated electrons and holes near the semiconductor surface. The latter striped pattern gives rise to a striped pattern of optical refractive index near the semiconductor surface, which is monitored by measuring a diffraction pattern of a second probe laser... 

Recent developments in ultrafast laser technology have enabled the efficient generation of tunable femtosecond laser pulses from the UV to the far-infrared regions of the electromagnetic spectrum making femtosecond vibrational spectroscopy a versatile tool [8-10]. 

In principle, the theory of nonlinear spectroscopy with femtosecond laser pulses is well developed. A comprehensive and up-to-date exposition of nonlinear optical spectroscopy in the femtosecond time domain is provided by the monograph of Mukamel. ° For additional reviews, see Refs. 7 and 11-14. While many theoretical papers have dealt with the analysis or prediction of femtosecond time-resolved spectra, very few of these studies have explicitly addressed the dynamics associated with conical intersections. In the majority of theoretical studies, the description of the chemical dynamics is based on rather simple models of the system that couples to the laser fields, usually a few-level system or a set of harmonic oscillators. In the case of condensed-phase spectroscopy, dissipation is additionally introduced by coupling the system to a thermal bath, either at a phenomenological level or in a more microscopic maimer via reduced density-matrix theory. 

In this section, we discuss a manifestation of electrOTiic coherence in fluorescence spectroscopy fluorescence anisotropy exceeding the classical maximum of 0.4. Such anisotropy has been seen at short times after excitation with femtosecond laser pulses that cover a sufficiently broad band of wavelengths to excite multiple optical transitions coherently. 

A new technique to measure low-frequency spectra is optical-heterodyne-detected Raman-induced Kerr-effect spectroscopy (OHD-RIKES). A recent publication by Chang and Cast-ner contains references to previous work within this field [18]. OHD-RIKES is based on a four-wave mixing of femtosecond laser pulses. Spectra obtained by OHD-RIKES reflect the anisotropic part of the Raman polarizability. Thus, the information obtained by OHD-RIKES is very similar to that obtained by low-frequency Raman scattering in an scattering configuration. From a theoretical point of view, the spectral representation obtained from OHD-RIKES measurements corresponds to the I v) representation given in Eq. (3). In Fig. 4 is shown an OHD-RIKES spectrum of liquid A-methylformamide (NMF). In Fig. 5 are shown low-frequency Raman spectra of liquid NMF together with the R(i>),... 

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