Asymmetric Dissociative Tunneling Ionization of Tetrafluoromethane in ω - 2ω Intense Laser Fields

Dissociative ionization of tetrafluoromethane (CF₄) in linearly polarized ω-2ω ultrashort intense laser fields (1.4 × 10¹⁴ W/cm², 800 and 400 nm) has been investigated by three-dimensional momentum ion imaging. The spatial distribution of $$ produced by CF₄ → $$ + F + e^- exhibited a clear asymmetry with respect to the laser polarization direction. The degree of the asymmetry varies by the relative phase of the ω and 2ω laser fields, showing that 1) the breaking of the four equivalent C-F bonds can be manipulated by the laser pulse shape and 2) the C-F bond directed along the larger amplitude side of the ω-2ω electric fields tends to be broken. Weak-field asymptotic theory (WFAT) shows that the tunneling ionization from the 4t ₂ second highest-occupied molecular orbital (HOMO-1) surpasses that from the 1t ₁ HOMO. This predicts the enhancement of the tunneling ionization with electric fields pointing from F to C, in the direction opposite to that observed for the asymmetric fragment ejection. Possible mechanisms involved in the asymmetric dissociative ionization, such as post-ionization interactions, are discussed.