Attosecond Coherent Control of Symmetry Breaking and Restoration in Atoms and Molecules

Abstract

Symmetry is a fundamental phenomenon in science, and symmetry breaking is often the origin of subsequent processes which are important in chemistry, physics and biology. As is well-known, a laser pulse can break the electronic symmetry in atoms and molecules by creating a superposition of electronic eigenstates with different irreducible representations, which typically initiates attosecond ultrafast charge migration. In the first part of this dissertation, an original theory of coherent laser control is proposed to induce the symmetry restoration of the electronic structure in atoms and molecules after symmetry breaking, with application to the oriented benzene molecule and to the 87Rb atom. Four different strategies are proposed and corresponding sufficient conditions for symmetry restoration are derived analytically. The numerical and analytical results agree perfectly with each other. Meanwhile, the theoretical predictions for the 87Rb atom have been confirmed by experimental partners in Japan, by means of high contrast Ramsey interferometry with a precision of about three attoseconds. The second part is devoted to the electronic flux during charge migration in oriented benzene molecule. Two different patterns of adiabatic attosecond charge migration are investigated by laser induced preparation of two different non-aromatic superposition states. From the knowledge of the time-dependent many-body wave functions as a linear combination of many-electron wave functions obtained from conventional quantum chemistry calculations, we derive expressions for the timeevolution of the one-electron density and the electronic flux. This allows to specify the number of electrons flowing during a given charge migration process, together with the mechanism of charge migration. In conclusion, this dissertation shows, for the first time, that the symmetry of electronic structure in atoms and molecules can not only be broken but also be restored by means of simple laser pulses. The coherent control strategies require strict control over the time-dependent phases of electronic wave functions. In practice, the precision required is few attoseconds much shorter than the timescale of charge migration in such systems. The analysis of charge migration indicates that similar superposition states may lead to quantitative differences in the number of electrons flowing.