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Fragmentation Pathways in a Series of CH3COX Molecules in the Strong Field Regime

机译:强磁场条件下一系列CH3COX分子的碎裂途径

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In intense laser fields, fragment ions can be produced from CH_3COX (X = CH_3, CF_3, and C_6H_5) either by absorption and dissociation followed by ionization (ADI) or absorption and ionization followed by dissociation (AID). Electronic structure calculations were carried out using Hartree-Fock, density functional, and correlated levels of theory to understand the possible fragmentation pathways. The calculated ionization potentials are in very good agreement with the available experimental data. For acetone, the acetyl ion is predicted to be the most preferred dissociation product and can be produced by either mechanism. The very low C-CF_3 bond energy in the parent ion of trifluoroacetone provides a clear reason for the absence of CF_3COCH_3~+ and CF_3CO~+ ion peaks from the mass spectrum of CF_3COCH_3 after intense laser excitation and indicates that fragmentation occurs by AID. For acetophenone, both CH_3CO~+ and C_6H_5CO~+ are stable fragments, with the latter being produced by an AID mechanism.
机译:在强激光场中,CH_3COX(X = CH_3,CF_3和C_6H_5)可以通过吸收和解离,然后电离(ADI)或吸收和电离,然后解离(AID)产生碎片离子。电子结构计算使用Hartree-Fock,密度泛函和相关理论水平进行,以了解可能的断裂途径。计算出的电离电势与可用的实验数据非常吻合。对于丙酮,乙酰基离子被认为是最优选的离解产物,并且可以通过任何一种机理产生。三氟丙酮的母离子中非常低的C-CF_3键能提供了明确的原因,说明在强烈激光激发后,CF_3COCH_3的质谱图中没有CF_3COCH_3〜+和CF_3CO〜+离子峰,并且表明AID发生了断裂。对于苯乙酮,CH_3CO〜+和C_6H_5CO〜+均为稳定片段,后者是通过AID机制产生的。

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