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Identification of the Jahn-Teller active trichlorosiloxy (SiCl3O) free radical in the gas phase

机译:气相中Jahn-Teller活性三氯甲硅氧基(SiCl3O)自由基的鉴定

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摘要

The (A) over tilde (2)A(1)-(X) over tilde E-2 electronic transition of the jet-cooled trichlorosiloxy (SiCl3O) free radical has been observed for the first time in the 650-590 nm region by laser induced fluorescence (LIF) detection. The radical was produced by a pulsed electric discharge through a mixture of silicon tetrachloride and oxygen in high pressure argon at the exit of a pulsed molecular beam valve. The LIF spectrum shows low frequency intervals, which we assign as activity in the normally forbidden degenerate v5 ' and v6 ' modes, indicative of a significant Jahn-Teller effect in the ground state. Single vibronic level emission spectra show level dependent spin-orbit splittings in the ground state and Jahn-Teller predictable variations depending on which upper state level is pumped. The measured lower state energy levels have been fitted to a Jahn-Teller model that simultaneously includes spin-orbit coupling and linear and quadratic multimode coupling. In SiCl3O, the Jahn-Teller interaction predominates over spin-orbit effects.
机译:激光诱导荧光(LIF)检测首次在650-590 nm区域观察到喷射冷却三氯甲烷氧基(SiCl3O)自由基的(A)过波浪号(2)A(1)-(X)过波浪号E-2电子跃迁.自由基是通过脉冲分子束阀出口处的高压氩气中的四氯化硅和氧气的混合物进行脉冲放电产生的。LIF频谱显示低频间隔,我们将其指定为通常被禁止的简并v5'和v6'模式下的活动,表明在基态下存在显着的Jahn-Teller效应。单振动能级发射光谱显示基态中与能级相关的自旋轨道分裂,以及根据泵浦的上层能级而产生的Jahn-Teller可预测变化。测得的低态能级已拟合到Jahn-Teller模型中,该模型同时包括自旋轨道耦合以及线性和二次多模耦合。在SiCl3O中,Jahn-Teller相互作用比自旋轨道效应占主导地位。

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