Molecular orbital imprint in laser-driven electron recollision

Electrons released by strong-field ionization from atoms and molecules or in solids can be accelerated in the oscillating laser field and driven back to their ion core. The ensuing interaction, phase-locked to the optical cycle, initiates the central processes underlying attosecond science. A common assumption assigns a single, well-defined return direction to the recolliding electron. We study laser-induced electron rescattering associated with two different ionization continua in the same, spatially aligned, polyatomic molecule. We show by experiment and theory that the electron return probability is molecular frame-dependent and carries structural information on the ionized orbital. The returning wave packet structure has to be accounted for in analyzing strong-field spectroscopy experiments that critically depend on the interaction of the laser-driven continuum electron, such as laser-induced electron diffraction.