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Journal ArticleDOI

Electronic spectra of ion radicals and their molecular orbital interpretation. III. Aromatic hydrocarbons

30 May 1973-Journal of the American Chemical Society (American Chemical Society)-Vol. 95, Iss: 11, pp 3473-3483
About: This article is published in Journal of the American Chemical Society.The article was published on 1973-05-30. It has received 298 citations till now. The article focuses on the topics: Molecular orbital & Electronic structure.
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TL;DR: The trochoidal electron spectrometer as discussed by the authors is a recently developed type of instrument, capable of measuring electron transmission spectra and also inelastic cross sections (a superposition of 0° and 180° scattering).

312 citations

Journal ArticleDOI
TL;DR: In this paper, modified perylene chromophores were adsorbed with virtually constant reaction distance on the surface of a spongelike TiO2 electrode and the dominant fast time constant was 190 fs.
Abstract: Modified perylene chromophores were adsorbed with virtually constant reaction distance on the surface of a spongelike TiO2 electrode. Interfacial electron transfer was probed with femtosecond resolution in ultrahigh vacuum via transient absorption and fluorescence up-conversion measurements. Identical time constants were measured for the decay of the reactant and rise of the product states. The dominant fast time constant was 190 fs. It remained constant between 300 and 22 K.

228 citations

Journal ArticleDOI
TL;DR: In this article, the Tamm-Dancoff approximation to TDDFT was used to calculate the electronic excitation energies and oscillator strengths for a series of polycyclic aromatic hydrocarbon radical cations.
Abstract: Time-dependent density functional theory (TDDFT) and its modification, the Tamm–Dancoff approximation to TDDFT, are employed to calculate the electronic excitation energies and oscillator strengths for a series of polycyclic aromatic hydrocarbon radical cations. For the radical cations of naphthalene and anthracene, TDDFT using the Becke–Lee–Yang–Parr functional and the 6-31G** basis set provides the excitation energies that are roughly within 0.3 eV of the experimental data. The assignments of the electron transitions proposed by TDDFT accord with the previous assignments made by accurate ab initio calculations, except that TDDFT indicates the existence of a few additional transitions of π*←σ character among the several low-lying transitions. The calculated energies for these π*←σ transitions are found to be consistent with the onset of a σ electron ionization manifold in the photoelectron spectra. For the pyrene radical cation, TDDFT supports the previous assignments made by semiempirical calculations, whereas for the perylene radical cation, TDDFT suggests the energy ordering of the three lowest-lying excited states be changed from those of the semiempirical results.

199 citations