Advanced Organic Chemistry. Reactions and Synthesis, 4th by Carey F., Sundberg R.

By Carey F., Sundberg R.

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Extra resources for Advanced Organic Chemistry. Reactions and Synthesis, 4th Edition

Example text

1), the interaction of electromagnetic radiation with excited molecules gives rise to stimulated emission, the microscopic counterpart of (stimulated) absorption. 1). 3), in equilibrium with an electromagnetic field of radiant energy density r emanating from a black-body light source such as the Sun. 6 Planck distribution of a black-body radiator where T is the temperature of the black body. Once the gas has reached equilibrium with the radiation field, the populations of its energy levels m and n, Nm and Nn, must be constant, dNm/dt ¼ dNn/dt ¼ 0.

1 Heisenberg uncertainty principle The ‘uncertainties’ d are defined as the standard deviations of simultaneous measurements of time and energy. During an electronic transition of a molecule in the presence of an electromagnetic field, the indeterminacy dE of the molecular energy is on the order of the photon energy, Ep ¼ hn ¼ hc/l. Hence dt ! l/(4pc) % 1 Â 10À16 s for l ¼ 300 nm. Absorption of electromagnetic radiation in the UV–VIS range always populates an electronically excited state, notwithstanding the high density of vibrationally (and rotationally) excited states in that region.

F is thus proportional to the product of two factors, the density rf of excited vibrational levels of the final state that match the energy of the initial state and the square of the vibronic coupling term between the initial and final BO state, Vif ¼ hCij^ hjCfi, where ^ h is a perturbation operator that couples nuclear with electronic motion to promote IC and couples electron spin with orbital angular momentum (spin–orbit coupling, SOC) to allow for ISC. 9). Once the radiationless transition has occurred, intramolecular vibrational redistribution (IVR) and dissipation of the excess energy to the solvent, vibrational relaxation, are very fast, so that radiationless processes IC and ISC are generally irreversible.

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