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研究了复合物Mg+-NCSCH3在230～440nm波段和Ca+-NCSCH3在320～560nm波段的光解离光谱. 复合物Mg+-NCSCH3, Ca+-NCSCH3 光诱导反应的产物质谱表明有非反应猝灭产物Mg+(Ca+), C—S 键断裂产物Mg+(Ca+)NC和Mg+(Ca+)NCS 以及重排反应产物Mg+(Ca+)-CHSH 通道. 在原子跃迁谱线(32S→32P, 对于Mg+; 42S→42P, 对于Ca+)的红和蓝两边, Mg+-NCSCH3的光解离光谱由两个宽峰组成; 而对于Ca+-NCSCH3, 则是由三个谱峰构成. CIS/6-311++G**等级上, 对应于基态构型的Mg+-NCSCH3电子态跃迁能量和振子强度与实验光谱较为一致; 而Ca+-NCSCH3有较大的差别. 这是因为CIS 方法忽略电子相关效应, 而Ca+-based 的跃迁中3d 和4s 轨道间存在较强的混合所致.
The photodissociation spectra of complex Mg + -NCSCH3 in the band of 230-440 nm and Ca + -NCSCH3 in the band of 320-560 nm were studied.The mass spectra of the products induced by the photoinduced reaction of Mg + -NCSCH3 and Ca + -NCSCH3 show that there is a non-reaction quenching product of Mg + (Ca +), C + S and Mg + (Ca +) NCS and the rearrangement reaction product Mg + (Ca +) - CHSH. The atomic emission spectrum (32S → 32P, , The light dissociation spectrum of Mg + -NCSCH3 consists of two broad peaks on both the red and blue sides of Ca +, whereas the Ca + -NCSCH3 consists of three peaks: CIS / 6-311 ++ G ** On the order of magnitude, the energies and oscillator intensities of Mg + -NCSCH3 corresponding to the ground state configurations are in good agreement with the experimental spectra, while Ca + -NCSCH3 has a larger difference because the CIS method ignores the electron-dependent effect whereas Ca + -based There is a strong mixture of 3d and 4s orbits in the transition.