Mapping Molecular Orbital Symmetry on High-Order Harmonic Generation Spectrum Using Two-Color Laser Fields

We have measured high-order harmonic generation spectra of D-2, N-2, and CO2 by mixing orthogonally polarized 800 and 400 nm laser fields. The intensity of the high-harmonic spectrum is modulated as we change the relative phase of the two pulses. For randomly orientated molecules, the phase of the intensity modulation depends on the symmetry of the molecular orbitals from which the high harmonics are emitted. This allows us to identify the symmetry of any orbital that contributes to high-harmonic generation, even without aligning the molecule. Our approach can be a route to imaging dynamical changes in three-dimensional molecular orbitals on a time scale as short as a few hundred attoseconds.