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Electronic Absorption

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Modern Optical Spectroscopy

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Abstract

This chapter begins with a discussion of how the oscillating electric field of light can raise a molecule to an excited electronic state. We then explore the factors that influence the wavelength, strength, linear dichroism, and shapes of molecular absorption bands. Our approach is to treat the absorbing molecule quantum mechanically with time-dependent perturbation theory, but to consider light, the perturbation, as a purely classical oscillating electric field. Because many of the phenomena associated with absorption of light can be explained well by this semiclassical approach, we defer considering the quantum nature of light until Chap. 5. Here, we develop expressions for calculating transition dipoles and dipole strengths and the rates of absorption and stimulated emission. We consider the Born-Oppenheimer approximation, Franck-Condon factors, selection rules, and effects of molecular symmetry. We also treat effects of the surroundings on electronic absorption, spectroscopic hole-burning, electronic Stark effects, charge-transfer transitions, and entropy changes in photoexcitation. The spectroscopy of aromatic amino acid side chains, porphyrins and chlorophylls receive special attention.

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    William W. Parson

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Parson, W.W. (2015). Electronic Absorption. In: Modern Optical Spectroscopy. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-662-46777-0_4

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