Chin Chih-Hao, Lin Meng-Yeh, Huang Tzu-Ping, Wu Yu-Jong
National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan.
National Synchrotron Radiation Research Center, 101 Hsin-Ann Road, Hsinchu Science Park, Hsinchu 30076, Taiwan; Department of Applied Chemistry, National Chiao Tung University, 1001, Ta-Hsueh Road, Hsinchu 30010, Taiwan.
Spectrochim Acta A Mol Biomol Spectrosc. 2018 May 5;196:233-237. doi: 10.1016/j.saa.2018.02.028. Epub 2018 Feb 8.
Electron bombardment during deposition of an Ar matrix containing a small proportion of allene generated allene cations. Further irradiation of the matrix sample at 385 nm destroyed the allene cations and formed propyne cations in solid Ar. Both cations were identified according to previously reported IR absorption bands. Using a similar technique, we recorded the ultraviolet absorption spectrum of allene cations in solid Ar. The vibrationally resolved progression recorded in the range of 266-237 nm with intervals of about 800 cm was assigned to the AE ← XE transition of allene cations, and the broad continuum absorption recorded in the region of 229-214 nm was assigned to their BA ← XE transition. These assignments were made based on the observed photolytic behavior of the progressions and the vertical excitation energies and oscillator strengths calculated using time-dependent density functional theory.
在含有少量丙二烯的氩气基质沉积过程中的电子轰击产生了丙二烯阳离子。在385纳米处对基质样品进行进一步辐照会破坏丙二烯阳离子，并在固态氩中形成丙炔阳离子。这两种阳离子均根据先前报道的红外吸收带进行了鉴定。使用类似的技术，我们记录了固态氩中丙二烯阳离子的紫外吸收光谱。在266 - 237纳米范围内以约800厘米的间隔记录的振动分辨进展被指定为丙二烯阳离子的A'E ← X'E跃迁，而在229 - 214纳米区域记录的宽连续吸收被指定为它们的B'A ← X'E跃迁。这些指定是基于所观察到的进展的光解行为以及使用含时密度泛函理论计算的垂直激发能和振子强度做出的。
