The Negative Ion Photoelectron Spectrum of Cyclopropane-1,2,3-Trione Radical Anion, (CO)3鈥⑩€?/sup> 鈥?A Joint Experimental and Computational Study

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• 作者：Bo Chen ; David A. Hrovat ; Robert West ; Shihu H. M. Deng ; Xue-Bin Wang ; Weston Thatcher Borden
• 刊名：Journal of the American Chemical Society
• 出版年：2014
• 出版时间：September 3, 2014
• 年：2014
• 卷：136
• 期：35
• 页码：12345-12354
• 全文大小：438K
• ISSN：1520-5126

文摘

Negative ion photoelectron (NIPE) spectra of the radical anion of cyclopropane-1,2,3-trione, (CO)₃^{鈥⑩€?/sup>, have been obtained at 20 K, using both 355 and 266 nm lasers for electron photodetachment. The spectra show broadened bands, due to the short lifetimes of both the singlet and triplet states of neutral (CO)₃ and, to a lesser extent, to the vibrational progressions that accompany the photodetachment process. The smaller intensity of the band with the lower electron binding energy suggests that the singlet is the ground state of (CO)₃. From the NIPE spectra, the electron affinity (EA) and the singlet鈥搕riplet energy gap of (CO)₃ are estimated to be, respectively, EA = 3.1 卤 0.1 eV and 螖E_ST = 鈭?4 卤 3 kcal/mol. High-level, (U)CCSD(T)/aug-cc-pVQZ//(U)CCSD(T)/aug-cc-pVTZ, calculations give EA = 3.04 eV for the 1A₁鈥?ground state of (CO)₃ and 螖E_ST = 鈭?3.8 kcal/mol for the energy gap between the 1A₁鈥?and 3A₂ states, in excellent agreement with values from the NIPE spectra. In addition, simulations of the vibrational structures for formation of these states of (CO)₃ from the 2A₂鈥?state of (CO)₃鈥⑩€?/sup> provide a good fit to the shapes of broad bands in the 266 nm NIPE spectrum. The NIPE spectrum of (CO)₃鈥⑩€?/sup> and the analysis of the spectrum by high-quality electronic structure calculations demonstrate that NIPES can not only access and provide information about transition structures but NIPES can also access and provide information about hilltops on potential energy surfaces.}