We report femtosecond optical pump and x-ray diffraction probe experiments on SnSe. We find that under photoexcitation, SnSe has an instability towards an orthorhombically-distorted rocksalt structure that is not present in the equilibrium phase diagram. The new lattice instability is accompanied by a drastic softening of the lowest frequency A$_g$ phonon which is usually associated with the thermodynamic Pnma-Cmcm transition. However, our reconstruction of the transient atomic displacements shows that instead of moving towards the Cmcm structure, the material moves towards a more symmetric orthorhombic distortion of the rock-salt structure belonging to the Immm space group. The experimental results combined with density functional theory (DFT) simulations show that photoexcitation can act as a state-selective perturbation of the electronic distribution, in this case by promoting electrons from Se 4$p$ Sn 5$s$ derived bands from deep below the Fermi level. The subsequent potential energy landscape modified by such electronic excitation can reveal minima with metastable phases that are distinct from those accessible in equilibrium. These results may have implications for optical control of the thermoelectric, ferroelectric and topological properties of the monochalcogenides and related materials.
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