Time-dependent extension of Koopmans' picture for ionization by a laser pulse: Application to H₂(B¹Σ_u⁺)

Ingo Barth (1) , Jörn Manz (1) , Guennaddi Paramonov (1, 2)

1 Institut für Chemie und Biochemie [Berlin]
2 Institute of Physics [Minsk]

Koopmans' picture predicts that the i-th ionization potential IP_i is approximately equal to the negative orbital energy -ε_i of the molecular orbital φ_i occupied by the single active electron (SAE), which is ionized, IP_i=-ε_i. The corresponding time-dependent extension describes ionization in terms of the time-dependent orbital φ_i(t) which is occupied by the SAE starting from the Extended Hartree-Fock (EHF) wavefunction. The Time-Dependent EHF-SAE theory for singlet states is developed, beyond previous TDHF-SAE approaches. Applications are demonstrated for ionization of (z-)aligned H₂(B¹Σ_u⁺), by means of linearly (z-)polarized laser pulses in the domain of dominant single photon ionization.

Mots clés: Physical Sciences

Ingo Barth, Jörn Manz, Guennaddi Paramonov. Time-dependent extension of Koopmans' picture for ionization by a laser pulse: Application to H₂(B¹Σ_u⁺). Molecular Physics, 2008, 106 (02-04), pp.467-483. ⟨10.1080/00268970701871007⟩. ⟨hal-00513173⟩