Fast Vibrational Spectroscopy

Ultrafast (femtosecond) pulsed two-color mid-infrared spectroscopy was used by Bakker et al. in a series of papers to study the effect of ions on the structural dynamics of their aqueous solutions as recently reviewed (Bakker 2008). The first intense pulse (pump pulse) excites the O-H (or O-D) stretch vibration to the first excited state and the second pulse (probe pulse), red-shifted with respect to the first, probes the decay of this state. This technique has been applied to aqueous (0.1-0.5 M HDO in D2O) solutions of LiX, NaX, and MgX2 (X = Cl, Br, I), KF, NaC104, and Mg(C104)2 over wide concentration ranges, 0.5-10 mol dm.  

The reorientation dynamics of water molecules in the electrolyte solutions are related to the rotational anisotropy  

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As mentioned, we also carried out IR studies (a fast vibrational spectroscopy) early in our work on carbocations. In our studies of the norbornyl cation we obtained Raman spectra as well, although at the time it was not possible to theoretically calculate the spectra. Comparison with model compounds (the 2-norbornyl system and nortri-cyclane, respectively) indicated the symmetrical, bridged nature of the ion. In recent years, Sunko and Schleyer were able, using the since-developed Fourier transform-infrared (FT-IR) method, to obtain the spectrum of the norbornyl cation and to compare it with the theoretically calculated one. Again, it was rewarding that their data were in excellent accord with our earlier work. 

For on-bead analysis vibrational spectroscopy (IR-spectroscopy) can be employed attenuated total reflection is a method allowing fast and nondestructive on-bead analysis of small samples (single bead analysis) without significant sample preparation. Solid phase NMR is the method of choice if complex structural analysis is intended on the support. Spatially resolved analysis on the resin is possible with microscopic techniques. 

The importance of the degree of esterification (%DE) to the gelation properties of pectins makes it desirable to obtain a fast and robust method to determine (predict) the %DE in pectin powders. Vibrational spectroscopy is a good candidate for the development of such fast methods as spectrometers and quantitative software algorithms (chemometric methods) becomes more reliable and sophisticated. Present poster is a preliminary report on the quantitative performance of different instrumentations, spectral regions, sampling techniques and software algorithms developed within the area of chemometrics. 

Smith GD, Palmer RA (2002) Fast time-resolved mid-infrared spectroscopy using an interferometer. In Chalmers JM, Griffiths PR (eds) Handbook of vibrational spectroscopy, vol 1. Wiley, Chichester, p 625... 

In addition to the surface/interface selectivity, IR-Visible SFG spectroscopy provides a number of attractive features since it is a coherent process (i) Detection efficiency is very high because the angle of emission of SFG light is strictly determined by the momentum conservation of the two incident beams, together with the fact that SFG can be detected by a photomultiplier (PMT) or CCD, which are the most efficient light detectors, because the SFG beam is in the visible region, (ii) The polarization feature that NLO intrinsically provides enables us to obtain information about a conformational and lateral order of adsorbed molecules on a flat surface, which cannot be obtained by traditional vibrational spectroscopy [29-32]. (iii) A pump and SFG probe measurement can be used for an ultra-fast dynamics study with a time-resolution determined by the incident laser pulses [33-37]. (iv) As a photon-in/photon-out method, SFG is applicable to essentially any system as long as one side of the interface is optically transparent. 

For comparison, the calculated linear and 2D spectra using ft = 12.3 cm-1 and 6 = 52°, which correspond to an a-helical structure (see the contour plot Fig. 19) for the isotopomer Ala -Ala-Ala are shown in Figure 21. The observed spectra for Ala -Ala-Ala are strikingly different from the calculated spectra for a molecule in an a-helical conformation. We emphasize here an important point In contrast to the NMR results on oligo(Ala), in which averaging of different backbone conformations might be present because measurements are made on a time scale that is slow compared to that of conformational motions, these vibrational spectroscopy results are detected on a very fast time scale (Hamm et al, 1999 Woutersen and Hamm, 2000, 2001). This rules out conformational averaging. 

A promising recent development in the study of nitrenium ions has been the introduction of time-resolved vibrational spectroscopy for their characterization. These methods are based on pulsed laser photolysis. However, they employ either time resolved IR (TRIR) or time-resolved resonance Raman (TRRR) spectroscopy as the mode of detection. While these detection techniques are inherently less sensitive than UV-vis absorption, they provide more detailed and readily interpretable spectral information. In fact, it is possible to directly calculate these spectra using relatively fast and inexpensive DFT and MP2 methods. Thus, spectra derived from experiment can be used to validate (or falsify) various computational treatments of nitrenium ion stmctures and reactivity. In contrast, UV-vis spectra do not lend themselves to detailed structural analysis and, moreover, calculating these spectra from first principles is still expensive and highly approximate. 

We have also learned that VMP is an effective tool in molecular spectroscopy and molecular dynamics studies. It is effective, in particular, for determination of IVR lifetimes and for studying the vibrational spectroscopy of states that are difficult to study applying other methods. The above-mentioned limit of the size of the molecule is irrelevant here. For observing the mode selectivity in VMP, the vibrational excitation has to survive IVR in order to retain the selectivity since the subsequent electronic excitation has to be from the excited vibrational state. In contrast, monitoring vibrational molecular dynamics relies only on the efficacy of the excitation of the specific rovibrational state. When IVR is fast and rovibrational distribution reaches equilibrium, the subsequent electronic excitation will still reflect the efficacy of the initial rovibrational excitation. In other words, whereas fast IVR precludes mode selectivity, it facilitates the unraveling of the vibrational molecular dynamics. 

Due to the development of fast observation methods in vibrational spectroscopy, even faster reactions can now be investigated. It is possible to record an IR spectrum in a fraction of a second. For Raman spectroscopy pulsed lasers and multichannel spectrometers are used (for further information see Sec. 6.6). 

In general, stopped-flow methods provide a reasonably inexpensive means of determining a large number of fairly fast reactions. Stopped-flow mixing is usually coupled with real-time optical observation using absorbance (UV through IR see. Vibrational Spectroscopy), fluorescence emission, or circular dichroism (CD) spectroscopy. In addition, the stopped-flow technique has been implemented in conjunction with many other biophysical techniques, such as EPR, NMR (see Nuclear Magnetic Resonance (NMR) Spectroscopy... 

Separation of amino acids and their identification in different mixtures are frequent tasks encountered in biochemistry. Thin layer chromatography is a fast, simple, and inexpensive approach to attain this goal. Because some of the components are UV-inactive, other methods, such as vibrational spectroscopy, should be applied for detection and identification. Comparative study based on Raman spectroscopy of thin layer chromatography spots of some weak Raman scatterers (essential amino acids) was carried out using four different visible and near-infrared laser radiation wavelengths 532, 633,785, and 1064 nm. The best results were obtained with simple silica gel plates. 

Platinum and palladium were among the first metals that were investigated in the molecular surface chemistry approach employing free mass-selected metal clusters [159]. The clusters were generated with a laser vaporization source and reacted in a pulsed fast flow reactor [18] or were prepared by a cold cathode discharge and reacted in the flowing afterglow reactor [404] under low-pressure multicollision reaction conditions. These early measurements include the detection of reaction products and the determination of reaction rates for CO adsorption and oxidation reactions. Later, anion photoelectron spectroscopic data of cluster carbonyls became available [405, 406] and vibrational spectroscopy of metal carbonyls in matrices was extensively performed [407]. Finally, only recently, the full catalytic cycles for the CO oxidation reaction with N2O and O2 on free clusters of Pt and Pd were discovered and analyzed [7,408]. 

Fast time-resolved mid-infrared spectroscopy using an interferometer, in Handbook of Vibrational Spectroscopy, Vol. 1 (eds P.R. Griffiths and J.M. Chalmers), John Wiley Sons, Ltd, Chichester, p. 525. 

The approach is capable of achieving a resolution of about 10 ps [43]. Optical/ vibrational spectroscopies can follow events and structural changes on such fast time scales since their characteristic time scales are sub-picosecond, even femtosecond. The methodology is therefore suitable to study the dynamics of en2ymatic catalysis over multiple time scales from picoseconds to minutes [44],... 

NMR over vibrational or electronic spectroscopy is that the radiation used to probe the system is much less energetic, and therefore much less likely to alter the folding or unfolding process it is designed to investigate. The lineshape strategy cannot be used to investigate processes as fast as those accessible by electronic or vibrational spectroscopy, (cf. Example 15.2.)... 

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