Electron-transfer reorganization energies of isolated organic molecules

Xenia Amashukeli, Jay R. Winkler, Harry B. Gray, Nadine E. Gruhn, Dennis L Lichtenberger

Research output: Contribution to journalArticle

47 Citations (Scopus)

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, 2B11), is observed at 7.888 ± 0.002 eV, 2B21) of 2 is at 8.342 ± 0.002 eV, and 2B1g1) of 3 is at 8.314 ± 0.002 eV. Spectra of 4-6 are reported for the first time: 2A21) 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, λQM, 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 λSC 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 = λQM + λSC) 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.

Original languageEnglish (US)
Pages (from-to)7593-7598
Number of pages6
JournalJournal of Physical Chemistry A
Volume106
Issue number33
DOIs
StatePublished - Aug 22 2002

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Energy transfer
Ionization
electron transfer
ionization
Molecules
Electrons
molecules
phenanthrene
anthracene
Photoelectrons
Electronic structure
Density functional theory
energy
photoelectrons
electronic structure
low frequencies
phenazine
1,10-phenanthroline
dibenzo(a,c)phenazine
benzotriphenylene

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Electron-transfer reorganization energies of isolated organic molecules. / Amashukeli, Xenia; Winkler, Jay R.; Gray, Harry B.; Gruhn, Nadine E.; Lichtenberger, Dennis L.

In: Journal of Physical Chemistry A, Vol. 106, No. 33, 22.08.2002, p. 7593-7598.

Research output: Contribution to journalArticle

Amashukeli, Xenia ; Winkler, Jay R. ; Gray, Harry B. ; Gruhn, Nadine E. ; Lichtenberger, Dennis L. / Electron-transfer reorganization energies of isolated organic molecules. In: Journal of Physical Chemistry A. 2002 ; Vol. 106, No. 33. pp. 7593-7598.
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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, 2B1(π1), is observed at 7.888 ± 0.002 eV, 2B2(π1) of 2 is at 8.342 ± 0.002 eV, and 2B1g(π1) of 3 is at 8.314 ± 0.002 eV. Spectra of 4-6 are reported for the first time: 2A2(π1) 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, λQM, 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 λSC 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 = λQM + λSC) 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.",
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AU - Amashukeli, Xenia

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AB - 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, 2B1(π1), is observed at 7.888 ± 0.002 eV, 2B2(π1) of 2 is at 8.342 ± 0.002 eV, and 2B1g(π1) of 3 is at 8.314 ± 0.002 eV. Spectra of 4-6 are reported for the first time: 2A2(π1) 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, λQM, 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 λSC 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 = λQM + λSC) 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.

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