First-principles calculation of femtosecond symmetry-breaking atomic forces in photoexcited bismuth.

We present a first-principles method for the calculation of the polarization-dependent atomic forces resulting from optical excitation in a solid. We calculate the induced force driving the E(g) phonon mode in bismuth immediately after absorption of polarized light. When radiation with polarization perpendicular to the c axis is absorbed, the photoexcited charge density breaks the threefold rotational symmetry, leading to an atomic force component perpendicular to the axis. We calculate the initial excited electronic distribution as a function of photon energy and polarization and find the resulting atomic force components parallel and perpendicular to the axis. The magnitude of the calculated force is in excellent agreement with that derived from recent measurements of the amplitude of E(g) atomic motion and the decay time of several femtoseconds for the driving force.