Stimulated X‑ray Raman Imaging of Conical Intersections

The conical intersection dynamics of thiophenol is studied theoretically using the stimulated X-ray Raman imaging (SXRI) technique. SXRI employs a hard X-ray narrowband/broadband hybrid probe field and provides a real-time and real-space image of the passage through conical intersections. The signal, calculated using the minimal-coupling radiation/matter Hamiltonian, carries the phase information, and the real-space image of the transition charge density can be reconstructed by its Fourier transform. The two conical intersections (S₂/S₁ (1¹ππ*/¹πσ*) and S₁/S₀ (¹πσ*/S₀)) can be distinguished and identified by the diffraction patterns in the level crossing regimes.