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Electron-Transfer Reorganization Energies of Isolated Organic Molecules

Amashukeli, Xenia and Winkler, Jay R. and Gray, Harry B. and Gruhn, Nadine E. and Lichtenberger, Dennis L. (2002) Electron-Transfer Reorganization Energies of Isolated Organic Molecules. Journal of Physical Chemistry A, 106 (33). pp. 7593-7598. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20170519-082618407

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Abstract

He I photoelectron spectra of phenanthrene (1), 1,10-phenanthroline (2), phenazine (3), dibenzo[a,c]anthracene (4), dibenzo[a,c]phenazine (5), and dipyrido[3,2-a;2‘3‘-c]phenazine (6) have been obtained. Assignment of the π ionization states was aided by electronic structure calculations:  the first ionization state of 1, ^2B_1(π_1), is observed at 7.888 ± 0.002 eV, ^2B_2(π_1) of 2 is at 8.342 ± 0.002 eV, and ^2B_(1g)(π_1) of 3 is at 8.314 ± 0.002 eV. Spectra of 4−6 are reported for the first time: ^2A_2(π_1) of 4 is at 7.376 ± 0.002 eV, and both 5 (7.983 ± 0.002 eV) and 6 (8.289 ± 0.002 eV) exhibit quasi-degenerate first and second ionization states. Quantum-mechanical reorganization energies, λ^(QM), were extracted from analyses of vibrational structure:  values are 149 ± 5 (1), 167 ± 5 (2), 68 ± 2 (3), and 92 ± 4 (4) meV. Low-frequency modes were treated semiclassically:  values of λ^(SC) are estimated to be 21 ± 1 (1), 13 ± 1 (2), 22 ± 1 (3), 66 ± 1 (4), 27 ± 9 (5), and 16 ± 1 (6) meV. Reorganization energies (λ = λ^(QM) + λ^(SC)) of isolated molecules are 170 ± 5 (1), 180 ± 5 (2), 90 ± 2 (3), and 158 ± 4 (4) meV. Density functional calculations (B3LYP/6-311G++(d,p)) give λ values that are on average 63 meV lower than experimentally derived energies.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp014148wDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp014148wPublisherArticle
ORCID:
AuthorORCID
Winkler, Jay R.0000-0002-4453-9716
Gray, Harry B.0000-0002-7937-7876
Lichtenberger, Dennis L.0000-0002-9271-0311
Additional Information:© 2002 American Chemical Society. Received 13 November 2001. Published online 10 April 2002. Published in print 1 August 2002. This work was supported by NSF (CHE-0078809:  H.B.G., J.R.W.; CHE-0078457:  D.L.L.) and DOE (DE-FG03-95ER14574:  D.L.L.).
Funders:
Funding AgencyGrant Number
NSFCHE-0078809
NSFCHE-0078457
Department of Energy (DOE)DE-FG03-95ER14574
Issue or Number:33
Record Number:CaltechAUTHORS:20170519-082618407
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170519-082618407
Official Citation:Electron-Transfer Reorganization Energies of Isolated Organic Molecules Xenia Amashukeli, Jay R. Winkler, Harry B. Gray, Nadine E. Gruhn, and Dennis L. Lichtenberger The Journal of Physical Chemistry A 2002 106 (33), 7593-7598 DOI: 10.1021/jp014148w
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:77597
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:19 May 2017 16:07
Last Modified:22 Nov 2019 09:58

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