Anderson, N. Nanoscale vibrational analysis of single-walled carbon nanotubes. Domke, K. Toward Raman fingerprints of single dye molecules at atomically smooth Au Neacsu, C.
[Peter Larkin] Infrared and Raman Spectroscopy
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Tip-enhanced Raman spectroscopy: principles and applications
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What is Raman Spectroscopy?
Download references. The density functional theory simulations were performed in the Supercomputing Center of the University of Science and Technology of China. All authors discussed the results and commented on the manuscript. Correspondence to Zhenchao Dong or J. To obtain permission to re-use content from this article visit RightsLink.
Angewandte Chemie International Edition Carbon Analytical Chemistry Journal of the American Chemical Society Article metrics. Advanced search. Skip to main content. Subjects Nanophotonics and plasmonics Raman spectroscopy. Abstract Unambiguous chemical identification of individual molecules closely packed on a surface can offer the possibility to address single chemical species and monitor their behaviour at the individual level 1 , 2 , 3.
Rent or Buy article Get time limited or full article access on ReadCube. References 1. CAS Google Scholar 7. Article Google Scholar Google Scholar Raman who, with K. Krishnan, first observed this phenomenon in liquids in The effect had been predicted on theoretical grounds in by A. Due to its very low scattering efficiency, Raman spectroscopy did not become popular until powerful laser systems were available after the s.
Now, Raman spectroscopy has become one of the most popular approaches to study the vibrational structures of molecules together with infrared spectrum. The origin of the modified frequencies found in Raman scattering is explained in terms of energy transfer between the scattering system and the incident radiation. Alternatively, the interaction of the radiation with the system may cause a downward transition from a higher energy level E 2 to a lower energy level E 1 , in which case it makes available energy.
Such wavenumber shifts are often referred to as Raman wavenumbers.
Figure 1. Diagrammatic representation of an energy transfer model of Rayleigh scattering, Stokes Raman and anti-Stokes Raman scattering. The intensity of anti-Stokes relative to Stokes Raman scattering decreases rapidly with increase in the wavenumber shift.
This is because anti-Stokes Raman scattering involves transitions to a lower energy state from a populated higher energy states. According to the classical theory of electromagnetic radiation, electric and magnetic fields oscillating at a given frequency are able to give out electromagnetic radiation of the same frequency. One could use electromagnetic radiation theory to explain light scattering phenomena.
This dipole moment which is induced by the electric field E could be expressed by the power series.
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It is a second-rank tensor with all the components in the unit of CV -1 m 2. To make the explanation easily, we shall ignore the rotation but just consider the vibration part. It is to be expected that the polarizability will be a function of the nuclear coordinates. The variation of components in polarizability tensor with vibrational coordinates is expressed in a Taylor series.
We shall make a harmonic approximation to neglect the terms which involve powers of Q higher than first. After initially fixing our attention on one normal mode, Q k , we could get. From these mathematical manipulations, there emerges a useful qualitative picture of the mechanisms of Rayleigh and Raman scattering in terms of classical radiation theory. According to the quantum theory, radiation is emitted or absorbed as a result of a system making a downward or upward transition between two discrete energy levels.
A quantum theory of spectroscopic processes should, therefore, treat the radiation and molecule together as a complete system, and explore how energy is transferred between the radiation and the molecule as a result of their interaction. A transition between energy levels of the molecular systems takes place with the emission or absorption of radiation, provided a transition moment associated with the initial and final molecular states is non-zero.
The transition moment could be defined as. As we have discussed in the classical part, the linear induced dipole moment could be expressed by.