Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants, and they are also ubiquitous in the interstellar medium. Here, we report the study of a complex O-containing PAH anion, the deprotonated 2-hydroxytriphenylene (2-OtPh-), using high-resolution photoelectron imaging and photodetachment spectroscopy of cryogenically cooled anions. Vibrationally resolved photoelectron spectra yield the electron affinity of the 2-OtPh radical as 2.629(1) eV and several vibrational frequencies for its ground electronic state. Photodetachment spectroscopy reveals bound valence excited electronic states for the 2-OtPh- anion, with unprecedentedly rich vibronic features. Evidence is presented for a low-lying triplet state (T1) and two singlet states (S1 and S2) below the detachment threshold. Single-color resonant two-photon photoelectron spectroscopy uncovers rich photophysics for the 2-OtPh- anion, including vibrational relaxation in S1, internal conversion to the ground state of 2-OtPh-, intersystem crossing from S2 to T1, and a long-lived autodetaching shape resonance about 1.3 eV above the detachment threshold. The rich electronic structure and photophysics afforded by the current study suggest that 2-OtPh- would be an interesting system for pump-probe experiments to unravel the dynamics of the excited states of this complex PAH anion.
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http://dx.doi.org/10.1063/5.0209948 | DOI Listing |
J Am Chem Soc
December 2024
Department of Chemical Engineering, University of Michigan, Ann Arbor, Michigan 48109, United States.
Designing catalysts with well-defined active sites with chemical functionality responsive to visible light has significant potential for overcoming scaling relations limiting chemical reactions over heterogeneous catalyst surfaces. Visible light can be leveraged to facilitate the removal of strongly bound species from well-defined single cationic sites (Rh) under mild conditions (323 K) when they are incorporated within a photoactive perovskite oxide (Rh-doped SrTiO). CO, a key intermediate in many chemistries, forms stable geminal dicarbonyl Rh complexes (Rh(CO)), that could act as site blockers or poisons during a catalytic cycle.
View Article and Find Full Text PDFInorg Chem
December 2024
Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstr. 9-13 (D), 81377 München, Germany.
[Na(HO)][FeSe] was synthesized using hydrothermal methods and characterized by single-crystal X-ray diffraction, Fe Mössbauer spectroscopy, magnetization, and muon spin resonance (μSR) measurements. The cubic crystal structure (space group 23, = 11.785 Å, = 2) contains heterocubane-type clusters with symmetry.
View Article and Find Full Text PDFJ Phys Chem Lett
November 2024
Department of Physics and Astronomy, Uppsala University, Box 516, SE-751 20 Uppsala, Sweden.
Chemistry
November 2024
School of Natural Science, Technical University of Munich, Chair of Inorganic Chemistry with Focus on Novel Materials, Lichtenbergstraße 4, D-85747, Garching, Germany.
The large variety of structures of Zintl phases are generally well understood since their anionic substructures follow bonding rules according to the valence concept. But there are also exceptions, which make the semiconductors especially interesting in terms of structure-property relationships. Although several Na-Sn-Pnictides with a variety of structural motives are known, up to this point no ternary compound in the Na-Sn-Bi system has been described.
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October 2024
Department of Psychology, University of Warsaw, Warsaw, Poland.
This exploratory study examined the potential of word embeddings, an automated numerical representation of written text, as a novel method for emotion decomposition analysis. Drawing from a substantial dataset scraped from a Social Media site, we constructed emotion vectors to extract the dimensions of emotions, as annotated by the readers of the texts, directly from human language. Our findings demonstrated that word embeddings yield emotional components akin to those found in previous literature, offering an alternative perspective not bounded by theoretical presuppositions, as well as showing that the dimensional structure of emotions is reflected in the semantic structure of their text-based expressions.
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