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Raman spectroscopy (; named after Sir C. V. Raman) is a spectroscopic technique used to observe vibrational, rotational, and other low-frequency modes in a system. Raman spectroscopy is commonly used in chemistry to provide a fingerprint by which molecules can be identified. It relies on inelastic scattering, or Raman scattering, of monochromatic light, usually from a laser in the visible, near infrared, or near ultraviolet range. The laser light interacts with molecular vibrations, phonons or other excitations in the system, resulting in the energy of the laser photons being shifted up or down. The shift in energy gives information about the vibrational modes in the system. Infrared spectroscopy yields similar, but complementary, information. Typically, a sample is illuminated with a laser beam. Electromagnetic radiation from the illuminated spot is collected with a lens and sent through a monochromator. Elastic scattered radiation at the wavelength corresponding to the laser line (Rayleigh scattering) is filtered out, while the rest of the collected light is dispersed onto a detector by either a notch filter or a band pass filter. Spontaneous Raman scattering is typically very weak, and as a result the main difficulty of Raman spectroscopy is separating the weak inelastically scattered light from the intense Rayleigh scattered laser light. Historically, Raman spectrometers used holographic gratings and multiple dispersion stages to achieve a high degree of laser rejection. In the past, photomultipliers were the detectors of choice for dispersive Raman setups, which resulted in long acquisition times. However, modern instrumentation almost universally employs notch or edge filters for laser rejection and spectrographs either axial transmissive (AT), Czerny–Turner (CT) monochromator, or FT (Fourier transform spectroscopy based), and CCD detectors. There are a number of advanced types of Raman spectroscopy, including surface-enhanced Raman, resonance Raman, tip-enhanced Raman, polarised Raman, stimulated Raman (analogous to stimulated emission), transmission Raman, spatially offset Raman, and hyper Raman. == Theoretical basis == The Raman effect occurs when electromagnetic radiation impinges on a molecule and interacts with the polarizable electron density and the bonds of the molecule in the phase (solid, liquid or gaseous) and environment in which the molecule finds itself. For the spontaneous Raman effect, which is a form of inelastic light scattering, a photon (electromagnetic radiation of a specific wavelength) excites (interacts with) the molecule in either the ground rovibronic state (lowest rotational and vibrational energy level of the ground electronic state) or an excited rovibronic state. This results in the molecule being in a so-called virtual energy state for a short period of time before an inelastically scattered photon results. The resulting inelastically scattered photon which is "emitted"/"scattered" can be of either lower (Stokes) or higher (anti-Stokes) energy than the incoming photon. In Raman scattering the resulting rovibronic state of the molecule is a different rotational or vibrational state than the one in which the molecule was originally, before interacting with the incoming photon (electromagnetic radiation). The difference in energy between the original rovibronic state and this resulting rovibronic state leads to a shift in the emitted photon's frequency away from the excitation wavelength, the so-called Rayleigh line. The Raman effect is due to inelastic scattering and should not be confused with emission (fluorescence or phosphorescence) where a molecule in an excited electronic state emits a photon of energy and returns to the ground electronic state, in many cases to a vibrationally excited state on the ground electronic state potential energy surface. If the final vibrational state of the molecule is more energetic than the initial state, the inelastically scattered photon will be shifted to a lower frequency for the total energy of the system to remain balanced. This shift in frequency is designated as a Stokes shift. If the final vibrational state is less energetic than the initial state, then the inelastically scattered photon will be shifted to a higher frequency, and this is designated as an anti-Stokes shift. Raman scattering is an example of inelastic scattering because of the energy and momentum transfer between the photons and the molecules during the interaction. Rayleigh scattering is an example of elastic scattering, the energy of the scattered Rayleigh scattering is of the same frequency (wavelength) as the incoming electromagnetic radiation. A change in the molecular electric dipole-electric polarizability with respect to the vibrational coordinate corresponding to the rovibronic state is required for a molecule to exhibit a Raman effect. The intensity of the Raman scattering is proportional to the electric dipole-electric dipole polarizability change. The Raman spectra (Raman scattering intensity as a function of the Stokes and anti-Stokes frequency shifts) is dependent on the rovibronic (rotational and vibrational energy levels of the ground electronic state) states of the sample. This dependence on the electric dipole-electric dipole polarizability derivative differs from infrared spectroscopy where the interaction between the molecule and light is determined by the electric dipole moment derivative, the so-called atomic polar tensor (APT); this contrasting feature allows one to analyze transitions that might not be IR active via Raman spectroscopy, as exemplified by the rule of mutual exclusion in centrosymmetric molecules. Bands which have large Raman intensities in many cases have weak infrared intensities and vice versa. For very symmetric molecules, certain vibrations may be both infrared and Raman inactive (within the harmonic approximation). In those instances, one can use a techniquie inelastic incoherent neutron scattering to determine the vibrational frequencies. The selection rules for inelastic incoherent neutron scattering (IINS) are different from those of both infrared and Raman scattering. Hence the three types of vibrational spectroscopy are complementary, all giving in theory the same frequency for a given vibrational transion, but the relative intensities giving different information due to the types of interaction between the molecule and the electromagnetic radiation for infrared and Raman spectroscopy and with the neutron beam for IINS. 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「Raman spectroscopy」の詳細全文を読む スポンサード リンク
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