Time-resolved x-ray Raman spectroscopy of photoexcited polydiacetylene oligomer: A simulation study

Abstract

Off-resonant x-ray diffraction provides a novel real-space and real-time probe of electronic and vibrational dynamics in optically excited molecules. The entire manifold of valence electronic excitations may be monitored through the dependence of the x-ray Raman peaks on the scattering wave vector Δk and energy Δω. The electronic excitation energies and transition density matrices of a polydiacetylene oligomer, computed using the time-dependent Hartree–Fock collective electronic oscillator algorithm, are used to simulate the Raman signals and illustrate their information content.