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Two-electron states bound to donors in silicon are important for both twoqubit gates and spin readout. We present a full configuration interactiontechnique in the atomistic tight-binding basis to capture multi-electronexchange and correlation effects taking into account the full bandstructure ofsilicon and the atomic scale granularity of a nanoscale device. Excited$s$-like states of $A_1$-symmetry are found to strongly influence the chargingenergy of a negative donor centre. We apply the technique on sub-surfacedopants subjected to gate electric fields, and show that bound triplet statesappear in the spectrum as a result of decreased charging energy. The exchangeenergy, obtained for the two-electron states in various confinement regimes,may enable engineering electrical control of spins in donor-dot hybrid qubits.

Two-electron states of a group V donor in silicon from atomistic full configuration interaction