dc.creator Perry, David S. en_US dc.creator Miller, Anthony en_US dc.creator Amyay, B. en_US dc.creator Fayt, A. en_US dc.creator Herman, M. en_US dc.date.accessioned 2010-07-12T14:07:17Z dc.date.available 2010-07-12T14:07:17Z dc.date.issued 2010 en_US dc.identifier 2010-RA-10 en_US dc.identifier.uri http://hdl.handle.net/1811/46213 dc.description Author Institution: Department of Chemistry, The University of Akron, Akron OH 44325-3601; Laboratoire de Chimie Quantique et Photophysique, Universite libre de; Bruxelles, B-1050 Brussels, Belgium en_US dc.description.abstract The link between energy-resolved spectra and time-resolved dynamics is explored quantitatively for acetylene ($^{12}C_{2}H_{2}$), $\~{X}^{1}\Sigma_{g}^{+}$ with up to 8,600 \wn of vibrational energy. This comparison is based on the extensive knowledge of the vibration-rotation energy levels and on the model Hamiltonian used to fit them to high precision.}, 114301 (2009).} Simulated intensity borrowing features in high resolution absorption spectra and predicted survival probabilities for intramolecular vibrational redistribution (IVR) are first investigated for the $\nu_{4}+\nu_{5}$ and $\nu_{3}$ 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 $\phi_{d}$, the IVR lifetime $\tau_{IVR}$, and the recurrence time $\tau_{rec}$. For the two bright states $\nu_{3}+2\nu_{4}$ and $7\nu_{4}$, the collisionless dynamics for thermally averaged rotational distributions at $T$= 27, 270 and 500 K were calculated from the available spectroscopic data. For the $7\nu_{4}$ 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. en_US dc.language.iso en en_US dc.publisher Ohio State University en_US dc.title ROTATIONAL DEPENDENCE OF INTRAMOLECULAR DYNAMICS IN ACETYLENE AT LOW VIBRATIONAL EXCITATION AS DEDUCED FROM HIGH RESOLUTION SPECTROSCOPY en_US dc.type Article en_US dc.type Image en_US dc.type Presentation en_US
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