Understanding the evolution of molecular electronic structures is the key to explore and control photochemical reactions and photobiological processes. Subjected to strong laser fields, electronic holes are formed upon ionization and evolve in the attosecond timescale. It is crucial to probe the electronic dynamics in real time with attosecond-temporal and atomic-spatial precision. Here, we present molecular attosecond interferometry that enables the in situ manipulation of holes in carbon dioxide molecules via the interferometry of the phase-locked electrons (propagating in opposite directions) of a laser-triggered rotational wave packet. The joint measurement on high-harmonic and terahertz spectroscopy (HATS) provides a unique tool for understanding electron dynamics from picoseconds to attoseconds. The optimum phases of two-color pulses for controlling the electron wave packet are precisely determined owing to the robust reference provided with the terahertz pulse generation. It is noteworthy that the contribution of HOMO-1 and HOMO-2 increases reflecting the deformation of the hole as the harmonic order increases. Our method can be applied to study hole dynamics of complex molecules and electron correlations during the strong-field process. The threefold control through molecular alignment, laser polarization, and the two-color pulse phase delay allows the precise manipulation of the transient hole paving the way for new advances in attochemistry.

We theoretically investigate terahertz emission from solid materials pumped by intense two-color femtosecond laser field in the presence of decoherence effects. Quantum-mechanical simulations are based on the length gauge semiconductor Bloch equations describing the optical excitation and decoherence with phenomenological dephasing and depopulation times. Contributions of interband and intraband mechanisms are identified in time domain, and the latter has dominated THz generation in solid-state systems. It is found that dephasing is crucial for enhancing asymmetric intraband current and deduced that solid-state materials with short dephasing time and long depopulation time would be optimal selection for strong-field terahertz generation experiments.

We investigate the crystal-momentum-resolved contributions to high-order harmonic generation in laser-driven graphene by semi-conductor Bloch equations in the velocity gauge. It is shown that each harmonic is generated by electrons with the specific initial crystal momentum. The higher harmonics are primarily contributed by the electrons of larger initial crystal momentum because they possess larger instantaneous energies during the intra-band motion. Particularly, we observed circular interference fringes in the crystal-momentum-resolved harmonics spectrum, which result from the inter-cycle interference of harmonic generation. These circular fringes will disappear if the inter-cycle interference is disrupted by the strong dephasing effect. Our findings can help better analyze the mechanism of high harmonics in graphene.

According to the asymmetric molecular orbital reconstruction algorithm, which divides orbital into gerade and ungerade components and which does not depend on the unidirectional recollisional condition, we obtain the two-dimensional highest occupied molecular orbital (HOMO) of CO based on the directly calculated transition dipole moment and the harmonic spectra calculated by the Lewenstein model, respectively, which is the three-dimensional (3D) HOMO projected onto the plane perpendicular to the laser propagation direction. In order to retrieve the full orbital function, a 3D molecular orbital tomography (MOT) method is developed and is successfully applied to the reconstructions of the HOMO of CO, which simplifies the 3D imaging process of orbitals of linear molecules, and is expected to be extended to reconstruct the 3D orbitals of nonlinear molecules. In addition, the time-dependent density functional theory is employed to acquire the harmonic spectra of CO in a 800 nm and 1500 nm wavelength laser, respectively. The comparison of these two reconstruction results helps identify the multi-electron effects for asymmetric MOT, which requires further study. This work advances the development of MOT and is expected to reveal multi-electron effects in orbital imaging of complex polyatomic molecules.

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