Using Simulations to Study Vibrational Relaxation of Molecules in Liquids
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The aim of this contribution to the summer school is to show how atomistic computer simulations can be used to study and interpret vibrational relaxation in solutions. In the first part of the article the three distinct relaxation rates (population relaxation T , decoherence rate T 2 -1 and the pure dephasing rate (T2*)-1) are introduced and theoretical expressions for the rates involving solventsolute forces and solute-solvent energy derivatives are developed from perturbation theory. In the second part the way in which relaxation rates can be determined from simulations of flexible molecules is illustrated using the example of the stretching modes of the triiodide ion. The origin and explanation of the variations in rate are then discussed combining data from simulations of rigid solute molecule and the expressions from perturbation theory.
KeywordsRelaxation Rate Instantaneous Frequency Energy Relaxation Symmetric Mode Vibrational Relaxation
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