Monday, December 17, 2012

My questions about condensed phase photochemistry?


For the excited state dynamics of a specific chromophore in a solvent what are the essential degrees of freedom (electronic, vibrational, and solvent) that must be included in a model Hamiltonian?

What determines if the excited state dynamics is classical, semi-classical, or fully quantum? Under what conditions does the Born-Oppenheimer approximation break down?

For a specific photochemical reaction what are the relevant vibrational degrees of freedom? What determines the relative importance of stretching, torsional, and pyramidal vibrations?

What determines the branching ratio for passage through a conical intersection? Relevant parameters may be the slope at the intersection, slanting, size of the wavepacket, and the distance of closest approach (impact parameter)

What is the interplay of the electronic, vibrational and solvent degrees of freedom in excited state dynamics?

What determines the relative importance of the viscosity and the polarity of the solvent for the dynamics? What is the role of the spatial inhomogeneity of the solvent?

In the presence of a solvent what are respective criteria for the localization/delocalization of electronic and/or vibrational excitations over different parts of the chromophore?
What are definitive experimental signatures of delocalization?

What are definitive experimental signatures of breakdown of the Born-Oppenheimer approximation?

What is the role of the solvent in non-adiabatic processes?

1 comment:

  1. I look forward to the follow up post: My answers...

    ReplyDelete