Vibration Raman active

RRS has also introduced the concept of a Raman excitation profile (REPy for thefth mode) [46, 4lZ, 48, 49, 50 and M]. An REP. is obtained by measuring the resonance Raman scattering strength of thefth mode as a fiinction of the excitation frequency [, 53]. Flow does the scattering intensity for a given (thefth) Raman active vibration vary with excitation frequency within an electronic absorption band In turn, this has led to transfomi theories that try to predict... 

CAHRS and CSHRS) [145, 146 and 147]. These 6WM spectroscopies depend on (Im for HRS) and obey the tlnee-photon selection rules. Their signals are always to the blue of the incident beam(s), thus avoiding fluorescence problems. The selection ndes allow one to probe, with optical frequencies, the usual IR spectrum (one photon), not the conventional Raman active vibrations (two photon), but also new vibrations that are synnnetry forbidden in both IR and conventional Raman methods. 

Having assigned symmetry species to each of the six vibrations of formaldehyde shown in Worked example 4.1 in Chapter 4 (pages 90-91) use the appropriate character table to show which are allowed in (a) the infrared specttum and (b) the Raman specttum. In each case state the direction of the transition moment for the infrared-active vibrations and which component of the polarizability is involved for the Raman-active vibrations. 

In a molecule with a centre of inversion all hyper Raman active vibrations are u vibrations, antisymmetric to inversion. 

The wave mixing is much more efficient when (vj — V2) = v, where is the wavenumber of a Raman-active vibrational or rotational transition of the sample. 

The example of COj discussed previously, which has no vibrations which are active in both the Raman and infrared spectra, is an illustration of the Principle of Mutual Exclusion For a centrosymmetric molecule every Raman active vibration is inactive in the infrared and any infrared active vibration is inactive in the Raman spectrum. A centrosymmetric molecule is one which possesses a center of symmetry. A center of symmetry is a point in a molecule about which the atoms are arranged in conjugate pairs. That is, taking the center of inversion as the origin (0, 0, 0), for every atom positioned at (au, yi, z ) there will be an identical atom at (-a ,-, —y%, —z,). A square planar molecule XY4 has a center of symmetry at atom X, whereas a trigonal planar molecule XYS does not possess a center of symmetry. 

We do not, in general, have to depend on conceptual approaches or on qualitative generalizations. Symmetry and group theory have provided us with a general method, called symmetry analysis, of determining the number of Raman active vibrations, the number of infrared active vibrations, and... 

Figure 2. Selected infrared and Raman active vibrational modes of C12H14.

In our tip-enhanced near-field CARS microscopy, two mode-locked pulsed lasers (pulse duration 5ps, spectral width 4cm ) were used for excitation of CARS polarization [21]. The sample was a DNA network nanostructure of poly(dA-dT)-poly(dA-dT) [24]. The frequency difference of the two excitation lasers (cOi — CO2) was set at 1337 cm, corresponding to the ring stretching mode of diazole. After the on-resonant imaging, CO2 was changed such that the frequency difference corresponded to none of the Raman-active vibration of the sample ( off-resonant ). The CARS images at the on- and off- resonant frequencies are illustrated in Figure 2.8a and b, respectively. 

Successful applications of fourth-order coherent Raman scattering are presented. Interface-selective detection of Raman-active vibrations is now definitely possible at buried interfaces. It can be recognized as a Raman spectroscopy with interface selectivity. Vibrational sum-frequency spectroscopy provides an interface-selective IR spectroscopy in which the vibrational coherence is created in the IR resonant transition. The two interface-selective methods are complementary, as has been experienced with Raman and IR spectroscopy in the bulk. 

Another valuable advantage of Raman spectroscopy, which is unique, is its capability of being used to characterise carbon species, in particular graphitic and amorphous carbon this can be of value to many degradation and pyrolysis studies. Perfectly ordered graphite is characterised by a Raman-active vibrational mode that occurs at 1,575 cm-1 this band is usually referred to as the C7 band. With increasing disorder in the carbon, a new band, the D band, appears at... 

Raman spectroscopy is a useful probe for detecting transannular S - S interactions in bicyclic or cage S-N molecules or ions. The strongly Raman active vibrations occur at frequencies in the range 180-300 cm-1, and for S- -S distances in the range 2.4-2.7 A. On the basis of symmetry considerations, the Raman spectrum of the mixed sulfur-selenium nitride S2Se2N4 was assigned to the 1,5- rather than the 1,3- isomer.37... 

It is more difficult to perform ultrafast spectroscopy on neat H20 (than it is on H0D/D20 or HOD/H20) since the neat fluid is so absorptive in the OH stretch region. One innovative and very informative technique, developed by Dlott, involves IR pumping and Raman probing. This technique has a number of advantages over traditional IR pump-probe experiments The scattered light is Stokes-shifted, which is less attenuated by the sample, and one can simultaneously monitor the populations of all Raman-active vibrations of the system at the same time. These experimental have been brought to bear on the spectral diffusion problem in neat water [18, 19, 75 77],... 

After the on-resonant imaging, the frequency of t 2 was changed snch that the frequency difference corresponds to none of the Raman-active vibrations ( off-resonant ). Figure 10.11 shows a normal Raman spectrum of the DNA in a part of the fingerprint region. The solid arrows on the spectrum denote the frequencies adopted for the on-resonant and off-resonant conditions in CARS imaging. 

In a centrosymmetric molecule no Raman-active vibration is also infrared-active and no infrared-active vibration is also Raman active. 

Suppose that a compound has a Raman-active vibration at vM. If it is illuminated by a probe laser (v) simulataneously with a pump continuum covering the frequency range from v to v + 3,500 cm-1, one observes an absorption at v + vM in the continuum together with emission at v. Clearly, the absorbed energy, h(v + vM), has been used for excitation (/zvM) and emission of the extra energy (hv). This upward transition is called the inverse Raman effect since the normal anti-Stokes transition occurs downward. Because the inverse Raman spectrum can be obtained in the lifetime of the pulse, it may be used for studies of shortlived species (Section 3.5). It should be noted, however, that the continuum pulse must also have the same lifetime as the giant pulse itself. Thus far, the inverse Raman effect has been observed only in a few compounds, because it is difficult to produce a continuum pulse at the desired frequency range. 

When a molecule is relatively small and/or belongs to a point group of relatively high symmetry, it is possible to elucidate the molecular structure by using the symmetry selection rules discussed in Section 1.14. Molecules of XY2 (linear or bent C2v), XY3 (planar D3h or pyramidal C3v), XY4 (square-planar D4h or tetrahedral Td) and XY5 (trigonal-bipyramidal D3h or tetragonal-pyramidal C4v) types may take one of the structures indicated in parentheses. Since the number of IR/Raman-active vibrations is different for each structure, the most probable structure can be chosen by comparing the number of observed IR/Raman bands with that predicted for each structure by symmetry selection rules. 

Table 4-3 Number of IR/Raman-Active Vibrations of Octahedral MXnY6 Type Molecules (Ref. 4)... 

A similar idea is exploited in recent work with the infrared (IR) echo, although with IR-active rather than Raman-active vibrations (35-42). Although the basic concepts in the Raman and IR echoes are the same, they each work best on different systems. The infrared echo is best for vibrations with strong IR transitions (and therefore potential for resonant energy transfer and sensitivity to local electric fields), for dilute solutes, and for systems with slow rotation. In contrast, the Raman echo is best for vibrations with strong Raman transitions (and generally weak IR transitions),... 

In CARS two ultrashort pulses of laser light (from femtoseconds to picoseconds in duration) arrive simultaneously at the sample of interest (Mukamel, 2000 Fourkas, 2001 and references herein). The difference between the frequencies (W) - w2) matches the frequency of a Raman active vibrational mode in the sample. A probe pulse (w3) emits a signal pulse of frequency Wj - w2 + w3 in a unique special direction. By scanning the delay time between the pump and probe pulses, the delay of the vibrational coherence can be measured. The distinct advantage of CARS is that it is a background free technique, since the signal propagates in a unique direction. 

Ionic nitrate D3h has 4 vibrations (3 IR active 1 Raman active), coordinated nitrate C2V has 6 IR active, and 6 Raman active vibrations. The doubly degenerate V4 band of ionic nitrate (700 cm-1) is split into V3 and V4 upon coordination. Further Raman polarization studies can distinguish between monodentate from bidentate nitrate and bridging nitrate groups. As an example La(HMPA)3(N03)3 has both ionic and coordinated nitrate [161]. 

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