The Optical Spectrum of Au 2 +
| العنوان: | The Optical Spectrum of Au 2 + |
|---|---|
| المؤلفون: | Roland Mitrić, Otto Dopfer, Kai Pollow, Este Ainun Najib, Marko Förstel, Karim Saroukh |
| المصدر: | Angewandte Chemie (International Ed. in English) |
| بيانات النشر: | Wiley, 2020. |
| سنة النشر: | 2020 |
| مصطلحات موضوعية: | Materials science, electronic structure calculations, Electronic structure, 010402 general chemistry, 01 natural sciences, Molecular physics, Spectral line, Catalysis, Physics::Atomic and Molecular Clusters, Physics::Chemical Physics, optical spectroscopy, Spectroscopy, Coupling, Physics, 010405 organic chemistry, Communication, Polyatomic ion, Photodissociation, photodissociation, General Medicine, General Chemistry, cations, Diatomic molecule, Communications, 0104 chemical sciences, Gold, Visible spectrum |
| الوصف: | The electronic structure of the Au2 + cation is essential for understanding its catalytic activity. We present the optical spectrum of mass‐selected Au2 + measured via photodissociation spectroscopy. Two vibrationally resolved band systems are observed in the 290–450 nm range (at ca. 440 and ca. 325 nm), which both exhibit rather irregular structure indicative of strong vibronic and spin‐orbit coupling. The experimental spectra are compared to high‐level quantum‐chemical calculations at the CASSCF‐MRCI level including spin‐orbit coupling. The results demonstrate that the understanding of the electronic structure of this simple, seemingly H2 +‐like diatomic molecular ion strictly requires multireference and relativistic treatment including spin‐orbit effects. The calculations reveal that multiple electronic states contribute to each respective band system. It is shown that popular DFT methods completely fail to describe the complex vibronic pattern of this fundamental diatomic cation. The optical spectrum of the prototypical diatomic Au2 + cation is presented in high quality. The measured spectrum of this seemingly simple H2 +‐like cation cannot be explained by standard TD‐DFT methods but requires relativistic multireference treatment with spin‐orbit coupling. |
| تدمد: | 1521-3773 1433-7851 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::6125bcbe92419523f78b96485df53af1 https://doi.org/10.1002/anie.202011337 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....6125bcbe92419523f78b96485df53af1 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15213773 14337851 |
|---|