Near‐Infrared Spectrum of the First Excited State of Au 2 +
| العنوان: | Near‐Infrared Spectrum of the First Excited State of Au 2 + |
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| المؤلفون: | Otto Dopfer, Marko Förstel, Kai Pollow, Taarna Studemund |
| المصدر: | Chemistry – A European Journal. 27:15075-15080 |
| بيانات النشر: | Wiley, 2021. |
| سنة النشر: | 2021 |
| مصطلحات موضوعية: | Chemistry, Excited state, Organic Chemistry, Photodissociation, Density functional theory, General Chemistry, Electronic structure, Electron, Antibonding molecular orbital, Ground state, Molecular physics, Catalysis, Excitation |
| الوصف: | Au2+ is a simple but crucial model system for understanding the diverse catalytic activity of gold. While the Au2+ ground state (X2 Σg+ ) is understood reasonably well from mass spectrometry and computations, no spectroscopic information is available for its first excited state (A2 Σu+ ). Herein, we present the vibrationally resolved electronic spectrum of this state for cold Ar-tagged Au2+ cations. This exceptionally low-lying and well isolated A2 Σ(u)+ ←X2 Σ(g)+ transition occurs in the near-infrared range. The observed band origin (5738 cm-1 , 1742.9 nm, 0.711 eV) and harmonic Au-Au and Au-Ar stretch frequencies (201 and 133 cm-1 ) agree surprisingly well with those predicted by standard time-dependent density functional theory calculations. The linearly bonded Ar tag has little impact on either the geometric or electronic structure of Au2+ , because the Au2+ ⋅⋅⋅Ar bond (∼0.4 eV) is much weaker than the Au-Au bond (∼2 eV). As a result of 6 s←5d excitation of an electron from the antibonding σu* orbital (HOMO-1) into the bonding σg orbital (SOMO), the Au-Au bond contracts substantially (by 0.1 A). |
| تدمد: | 1521-3765 0947-6539 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_________::9543a2cbe7735264b6330795a5c50047 https://doi.org/10.1002/chem.202102542 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi...........9543a2cbe7735264b6330795a5c50047 |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15213765 09476539 |
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