Quantum control of electronic fluxes during adiabatic attosecond charge migration in degenerate superposition states of benzene

•The control of adiabatic attosecond charge migration in benzene using rationally designed pulses is demonstrated.•The analysis of transient angular electronic fluxes is performed using wave function based methods.•The electronic phase aquired during the laser preparation step has a marked influence on the charge migration mechanism.

We design four linearly x- and y-polarized as well as circularly right (+) and left (−) polarized, resonant π/2-laser pulses that prepare the model benzene molecule in four different degenerate superposition states. These consist of equal (0.5) populations of the electronic ground state S0(1A1g) plus one of four degenerate excited states, all of them accessible by dipole-allowed transitions. Specifically, for the molecule aligned in the xy-plane, these excited states include different complex-valued linear combinations of the 1E1u,x and 1E1u,y degenerate states. As a consequence, the laser pulses induce four different types of periodic adiabatic attosecond (as) charge migrations (AACM) in benzene, all with the same period, 504 as, but with four different types of angular fluxes. One of the characteristic differences of these fluxes are the two angles for zero fluxes, which appear as the instantaneous angular positions of the “source” and “sink” of two equivalent, or nearly equivalent branches of the fluxes which flow in pincer-type patterns from one molecular site (the “source”) to the opposite one (the “sink”). These angles of zero fluxes are either fixed at the positions of two opposite carbon nuclei in the yz-symmetry plane, or at the centers of two opposite carbon-carbon bonds in the xz-symmetry plane, or the angles of zero fluxes rotate in angular forward (+) or backward (−) directions, respectively. As a resume, our quantum model simulations demonstrate quantum control of the electronic fluxes during AACM in degenerate superposition states, in the attosecond time domain, with the laser polarization as the key knob for control.

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