Abstract
Dissociative ionization of tetrafluoromethane (CF(4)) in linearly polarized ω-2ω ultrashort intense laser fields (1.4 × 10(14) W/cm(2), 800 and 400 nm) has been investigated by three-dimensional momentum ion imaging. The spatial distribution of CF3+ produced by CF(4) → CF3+ + 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.