Affiliation
Univ Arizona, Dept Chem & BiochemIssue Date
2017-07-07
Metadata
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AMER INST PHYSICSCitation
Electron affinity and excited states of methylglyoxal 2017, 147 (1):013934 The Journal of Chemical PhysicsJournal
The Journal of Chemical PhysicsRights
© 2017 Author(s). Published by AIP Publishing.Collection Information
This item from the UA Faculty Publications collection is made available by the University of Arizona with support from the University of Arizona Libraries. If you have questions, please contact us at repository@u.library.arizona.edu.Abstract
Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X(2)A" electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X(1)A'), the lowest triplet state (a(3)A"), and the open-shell singlet state (A(1)A"). The adiabatic electron affinity (EA) of the ground state, EA(X(1)A') = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a(3)A") = 3.27(2) eV and EA(A(1)A") = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a(3)A" <- X(2)A" and A(1)A" <- X(2)A" photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X(1)A' state, which corresponds to a 60 degrees internal rotation of the methyl group, compared to the anion structure. Accordingly, the X(1)A' <- X(2)A" transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory. Published by AIP Publishing.Note
12 month embargo; published online 11 May 2017.ISSN
0021-96061089-7690
Version
Final published versionSponsors
U.S. National Science Foundation [CHE-1266152]Additional Links
http://aip.scitation.org/doi/10.1063/1.4982948ae974a485f413a2113503eed53cd6c53
10.1063/1.4982948