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  Quantum-state resolved lifetime of triplet ((a)over-tilde(3)A(2)) formaldehyde.

Krüger, B. C., Schäfer, T., Wodtke, A. M., & Park, G. B. (2019). Quantum-state resolved lifetime of triplet ((a)over-tilde(3)A(2)) formaldehyde. Journal of Molecular Spectroscopy, 362, 61-68. doi:10.1016/j.jms.2019.06.001.

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Item Permalink: http://hdl.handle.net/21.11116/0000-0004-66D5-9 Version Permalink: http://hdl.handle.net/21.11116/0000-0004-66D7-7
Genre: Journal Article

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 Creators:
Krüger, B. C.1, Author              
Schäfer, T.1, Author              
Wodtke, A. M.1, Author              
Park, G. B.1, Author              
Affiliations:
1Department of Dynamics at Surfaces, MPI for Biophysical Chemistry, Max Planck Society, ou_578600              

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Free keywords: Formaldehyde; Intersystem crossing; Tunneling rates
 Abstract: We report state-resolved lifetimes of formaldehyde in the first excited triplet (a) over tilde (3)A(2) electronic state. Pumplaser excitation within 2800 cm(-1) of the triplet origin is followed by variably delayed F-2-laser ionization. Lifetimes fluctuate from > 100 mu s to similar to 100 ns and a large isotope effect is observed. The average decay rate increases exponentially with increasing vibrational energy above the electronic origin, consistent with a mechanism involving tunneling through the barrier on the electronic ground state to the CO + H-2/D-2 continuum. By accessing the triplet state we are able to investigate the molecular elimination reaction down to similar to 25 kJ/mol below the zero-point-energy corrected activation barrier. A model based on empirical RRKM rates allows the intersystem crossing matrix elements to be estimated. The T-1-S-0 intersystem crossing matrix elements are comparable to the S-1-S-0 internal conversion matrix elements observed at similar vibrational excitation.

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Language(s): eng - English
 Dates: 2019-08
 Publication Status: Published in print
 Pages: -
 Publishing info: -
 Table of Contents: -
 Rev. Method: Peer
 Identifiers: DOI: 10.1016/j.jms.2019.06.001
 Degree: -

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Title: Journal of Molecular Spectroscopy
Source Genre: Journal
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Publ. Info: -
Pages: - Volume / Issue: 362 Sequence Number: - Start / End Page: 61 - 68 Identifier: -