Raman-active

This spectrum is called a Raman spectrum and corresponds to the vibrational or rotational changes in the molecule. The selection rules for Raman activity are different from those for i.r. activity and the two types of spectroscopy are complementary in the study of molecular structure. Modern Raman spectrometers use lasers for excitation. In the resonance Raman effect excitation at a frequency corresponding to electronic absorption causes great enhancement of the Raman spectrum. 

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... 

Of great interest to physical chemists and chemical physicists are the broadening mechanisms of Raman lines in the condensed phase. Characterization of tliese mechanisms provides infomiation about the microscopic dynamical behaviour of material. The line broadening is due to the interaction between the Raman active chromophore and its environment. 

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. 

Plenary 14. A K Ramdas et al, e-mail address akr phYsics.purdue.edu (RS). Electronic RS studies of doped diamond as potential semiconducting materials. A Raman active Is (p3 2) ls (Pi/2 transition of a hole... 

For a circularly polarized light experiment, one can measure the cross sections for either right (r) or left (1) polarized scattered light. Suppose that right polarized light is made incident on a Raman active sample. The general expressions for the Raman cross sections are [176]... 

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. 

An interesting variation of Raman spectroscopy is coherent anti-Stokes Raman spectroscopy (CARS) (99). If two laser beams, with angular frequencies CO and CO2 are combined in a material, and if cjj — is close to a Raman active frequency of the material, then radiation at a new frequency CJ3 = 2cJ2 — may be produced. Detection of this radiation can be used to characterize the material. Often one input frequency is fixed and the other frequency, from a tunable laser, varied until matches the Raman frequency. CARS has the capabiHty for measurements in flames, plasmas, and... 

The thiosulfate ion has tetrahedral symmetry and the six fundamental modes are both infrared and Raman active. The calculated frequencies (3) are in good agreement with experimental values (4). 

At higher frequencies (above 200 cm ) the vibrational spectra for fullerenes and their cry.stalline solids are dominated by the intramolecular modes. Because of the high symmetry of the Cgo molecule (icosahedral point group Ih), there are only 46 distinct molecular mode frequencies corresponding to the 180 6 = 174 degrees of freedom for the isolated Cgo molecule, and of these only 4 are infrared-active (all with Ti symmetry) and 10 are Raman-active (2 with Ag symmetry and 8 with Hg symmetry). The remaining 32 eigcnfrequencies correspond to silent modes, i.e., they are not optically active in first order. 

Raman and infrared spectroscopy provide sensitive methods for distinguishing Ceo from higher molecular weight fullerenes with lower symmetry (eg., C70 has >5/1 symmetry). Since most of the higher molecular weight fullerenes have lower symmetry as well as more degrees of freedom, they have many more infrared- and Raman-active modes. 

The Raman and infrared spectra for C70 are much more complicated than for Cfio because of the lower symmetry and the large number of Raman-active modes (53) and infrared active modes (31) out of a total of 122 possible vibrational mode frequencies. Nevertheless, well-resolved infrared spectra [88, 103] and Raman spectra have been observed [95, 103, 104]. Using polarization studies and a force constant model calculation [103, 105], an attempt has been made to assign mode symmetries to all the intramolecular modes. Making use of a force constant model based on Ceo and a small perturbation to account for the weakening of the force constants for the belt atoms around the equator, reasonable consistency between the model calculation and the experimentally determined lattice modes [103, 105] has been achieved. 

Fig. 24. The armchair index n vs mode frequency for the Raman-active modes of single-wall armchair (n,n) carbon nanotubes [195]. From Eq. (2), the nanotube diameter is given by d = Ttac-cnj-K.

In the low frequency region, the calculations predict nanotube-specifiic Eig and E g modes around 116 cm and 377 cm respectively, for (10,10) armchair naiiotubes, but their intensities are expected to be lower than that for the A g mode. However, these Eig and E2g modes are important, since they also show a diameter dependence of their mode frequencies. In the very low frequency region below 30 cm a strong low frequency Raman-active E2g mode is expected. However, it is difficult to observe Raman lines in the very low frequency region, where the background Rayleigh scattered is very strong. 

Of these many modes there are only 7 nonvanishing modes which are infrared-active (2A2 + 5 i ) and 15 modes that are Raman-active. Thus, by increasing the diameter of the zigzag tubules, modes with different symmetries are added, though the number and symmetry of the optically active modes remain the... 

Abstract—Experimental and theoretical studies of the vibrational modes of carbon nanotubes are reviewed. The closing of a 2D graphene sheet into a tubule is found to lead to several new infrared (IR)- and Raman-active modes. The number of these modes is found to depend on the tubule symmetry and not on the diameter. Their diameter-dependent frequencies are calculated using a zone-folding model. Results of Raman scattering studies on arc-derived carbons containing nested or single-wall nanotubes are discussed. They are compared to theory and to that observed for other sp carbons also present in the sample. 

Graphite exhibits strong second-order Raman-active features. These features are expected and observed in carbon tubules, as well. Momentum and energy conservation, and the phonon density of states determine, to a large extent, the second-order spectra. By conservation of energy hut = huty + hbi2, where bi and ill) (/ = 1,2) are, respectively, the frequencies of the incoming photon and those of the simultaneously excited normal modes. There is also a crystal momentum selection rule hV. = -I- q, where k and q/... 

Activity R = Raman-active, ir = infrared-active, S = optically silent, observed in neutron scattering. tCarbon atom displacement il or J. to C. 

Fig. 4. Diameter dependence of the first order (a) IR-active and. (b) Raman-active mode frequencies for...

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