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Vygranenko , Dorota Gryko , Daniel T. Rhodols — synthesis, photophysical properties and applications as fluorescent probes. Chemical Society Reviews , 48 20 , Pair your accounts. Your Mendeley pairing has expired. Please reconnect. This website uses cookies to improve your user experience. By continuing to use the site, you are accepting our use of cookies. Read the ACS privacy policy. The black quadratic curves are the potential wells of the nuclear separation of the S 0 and S 1 states under the simplifying assumption that the molecule is a diatomic harmonic oscillator and the red curves are the wavefunctions of the quantised vibrational levels.
The bottom of each well is the equilibrium separation distance between the nuclei in that state, i. Figure 5 The Franck-Condon Principle in a nuclear coordinate energy diagram. The arrow is vertical since the nuclei do not move during the timescale of the absorption transition. The maximum of the fluorescence spectrum will therefore always occur at a longer wavelength than the absorption maximum and this is the origin of the Stokes shift. The term Stokes shift is also used in Raman spectroscopy where it describes whether the Raman scattered radiation is at lower energy Stokes shifted or higher energy anti-Stokes shifted than the Rayleigh scattered radiation.
Stokes himself never knew of Raman scattering which was first observed 25 years after his death by C. Raman and K. Krishnan in The origin of the Stokes and anti-Stokes scattering is shown in Figure 6.
When radiation is scattered from a molecule the majority of photons scatter elastically with no change in the vibrational energy of molecule during the scattering process Rayleigh scattering. In Stokes Raman scattering the molecule gains a quantum of vibrational energy from the photon during the scattering process and the Stokes radiation, therefore, has a longer wavelength than the incident radiation.
In anti-Stokes Raman scattering the reverse occurs, with the molecule losing a quantum of vibrational energy during the scattering process and the anti-Stokes radiation, therefore, has a shorter wavelength than the incident.
Raman peaks are characterised by their wavenumber shift away from the incident radiation, with Stokes peaks having a positive wavenumber shift and anti-Stokes shifts being negative. Figure 6 Stokes and anti-Stokes Raman scattering. Figure 7 Raman spectrum of CCl 4 excited with a nm laser.
McCartney, A. Whitaker, and A. McNaught, and A. Blackwell Scientific Publications Thus any interaction of the bath molecules with the species of interest is largely limited to the ground electronic state.
These interactions lead to the relatively small solvent dependent shifts observed in absorption spectroscopy in the UV and Vis 2 - 40 nm. Fluorescence in condensed media takes place on the nanosecond time scale, a time scale during which solvent molecules in the bath can reorientate or relax around the molecule in the excited state.
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