Intramolecular vibrational energy redistribution and conformational isomerization in vibrationally excited 2-fluoroethanol: High-resolution, microwave-infrared double-resonance spectroscopy investigation of the asymmetric stretch near 2980 cm−1
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62.The asymmetry splitting between the and rotational levels of the ground state is 81 MHz.
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65.Our model Hamiltonian consists of one matrix for each parity component. The density of states is 50 states/cm−1, for each parity. The density of the nondegenerate Tt/delocalized states is also 50 states/cm−1 for each parity. Therefore, the total state density for the model spectrum is 200 states/cm−1. The coupling matrix element distribution between and the Tt/delocalized states is Gaussian with a mean of zero and a standard deviation of 0.01 cm−1. The cross-coupling terms are chosen from a Gaussian distribution with a mean of zero and a variable standard deviation. The infrared spectrum is calculated by selecting a single state as the bright state. A signal to noise cutoff of 200:1 is used to filter the calculated spectrum, better simulating an experimental spectrum. The normalized level spacing distribution for a set of 30 different samples of the Hamiltonian is compared to the experimental distribution.
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