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Vibration-rotation alchemy in acetylene (12C2H2), X1Σ+ g at low vibrational excitation: From high resolution spectroscopy to fast intramolecular dynamics

par Perry, D.;Miller, Aurélie ;Amyay, Badr ;Fayt, André;Herman, Michel
Référence Molecular Physics, 108, 7-9, page (1115-1132)
Publication Publié, 2010

Article révisé par les pairs

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Résumé :

The link between energy-resolved spectra and time-resolved dynamics is explored quantitatively for acetylene (12C2H2), X̃1Σ+g with up to 8600 cm -1 of vibrational energy. This comparison is based on the extensive and reliable knowledge of the vibration-rotation energy levels and on the model Hamiltonian used to fit them to high precision [B. Amyay, S. Robert, M. Herman, A. Fayt, B. Raghavendra, A. Moudens, J. Thiévin, B. Rowe, and R. Georges, J. Chem. Phys. 131, 114301 (2009)]. Simulated intensity borrowing features in high resolution absorption spectra and predicted survival probabilities in intramolecular vibrational redistribution (IVR) are first investigated for the v4 + v5 and v3 bright states, for J = 2, 30 and 100. The dependence of the results on the rotational quantum number and on the choice of vibrational bright state reflects the interplay of three kinds of off-diagonal resonances: anharmonic, rotational l-type, and Coriolis. The dynamical quantities used to characterize the calculated time-dependent dynamics are the dilution factor φd, the IVR lifetime τIVR, and the recurrence time τrec. For the two bright states v3 + 2v4 and 7v4, the collisionless dynamics for thermally averaged rotational distributions at T = 27, 270 and 500 K were calculated from the available spectroscopic data. For the 7v4 bright state, an apparent irreversible decay of is found. In all cases, the model Hamiltonian allows a detailed calculation of the energy flow among all of the coupled zeroth-order vibration-rotation states. © 2010 Taylor & Francis.