Familiarization with Excitation and Emission Spectra, Mirror Image Relation and Stokes Shift
Pre-Assignment
- What are the spin multiplicity and the spin of triplet state?
- Why two electrons are always present in two different orbitals of the molecule in triplet state?
- Internal conversion (takes place at a time scale of 10-12 s) is faster than the fluorescence emission. Then how does radiative emission (fluorescence) compete with the non-radiative transition? (Hint: Significantly larger energy gap between S1 and S0 and longer lifetime of S1.)
- Transitions between states of different multiplicity are formally forbidden. What are the mechanisms that make the intersystem crossing probable?
- How can you justify that the relaxation to ground state occurs via "vertical" transition?
- In most of the cases, the S1 potential energy curve shifts to the right with respect to S0 potential energy curve. Justify it. (Hint: In the excited state, the electron is promoted to an anti-bonding orbital.)
Post-Assignment
- What happens in Stokes shift: The fluorescence light is red-shifted (shifts to longer wavelength than the excitation light) or blue-shifted relative to the absorbed light?
- How does the solvent effect affect the magnitude of the Stokes shift?
- Why is the same fluorescence emission wavelength observed irrespective of the excitation wavelength?
- Vibrational levels of which of the electronic states - electronic ground state or electronically excited state - are reflected by an emission spectrum?
- "The detection of a fluorescent molecule becomes easier when the Stokes shift is larger." Why?
- Do both the fluorophores obey the mirror image rule and why?
- Which of the two fluorophores has larger area of overlapping region between the absorption and emission spectra? (Note: The overlapping region relates to the auto-absorption in inner filter effects.)