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Equations of motion for natural orbitals of strongly driven two-electron systems

Natural orbital theory is a computationally useful approach to the few and many-body quantum problem. While natural orbitals are known and applied since many years in electronic structure applications, their potential for time-dependent problems is being investigated only since recently. Correlated two-particle systems are of particular importance because the structure of the two-body reduced density matrix expanded in natural orbitals is known exactly in this case. However, in the time-dependent case the natural orbitals carry time-dependent phases that allow for certain time-dependent gauge transformations of the first kind. Different phase conventions will, in general, lead to different equations of motion for the natural orbitals. A particular phase choice allows us to derive the exact equations of motion for the natural orbitals of any (laser-) driven two-electron system explicitly, i.e., without any dependence on quantities that, in practice, require further approximations. For illustration, we solve the equations of motion for a model helium system. Besides calculating the spin-singlet and spin-triplet ground states, we show that the linear response spectra and the results for resonant Rabi flopping are in excellent agreement with the benchmark results obtained from the exact solution of the time-dependent Schrödinger equation.