Internal conversion is an inherently quantum mechanical process. To date, “ab initio” computation of internal conversion rates was limited to harmonic based approximations. These are questionable since the typical transition to the ground electronic state occurs at energies which are far from the harmonic limit. It is thus of interest to study the applicability of the Semiclassical Initial Value Representation (SCIVR) approach which is in principle amenable to “on the fly” studies even with “many” degrees of freedom. In this work we apply the Herman-Kluk-SCIVR methodology to compute the internal conversion rates for formaldehyde for a variety of initial vibronic states. The SCIVR computation gives reasonable agreement with experiment, while the harmonic approximation typically gives rates that are too high.
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21 October 2013
Research Article|
October 18 2013
On-the-fly semiclassical study of internal conversion rates of formaldehyde
Reuven Ianconescu;
Reuven Ianconescu
1Shenkar College of Engineering and Design and Chemical Physics Department,
Weizmann Institute of Science
, 76100 Rehovoth, Israel
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Jörg Tatchen;
Jörg Tatchen
2Departamento de Química,
Universidad de los Andes
, Bogotá, Colombia
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Eli Pollak
Eli Pollak
a)
3Chemical Physics Department,
Weizmann Institute of Science
, 76100 Rehovoth, Israel
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a)
Email: eli.pollak@weizmann.ac.il
J. Chem. Phys. 139, 154311 (2013)
Article history
Received:
August 26 2013
Accepted:
September 30 2013
Citation
Reuven Ianconescu, Jörg Tatchen, Eli Pollak; On-the-fly semiclassical study of internal conversion rates of formaldehyde. J. Chem. Phys. 21 October 2013; 139 (15): 154311. https://doi.org/10.1063/1.4825040
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