Photoelectron kinetic energy spectrum of an unaligned CO<sub>2</sub> molecule after photoionization with 90.6 eV photon energy at FLASH (black line) and fit (red line) of the photoelectron spectrum using four Gaussians with 0.5 eV FWHM centred at E<sub><em>K</em></sub> = 76.8 (<em>X</em><sup>2</sup>Π<sub><em>g</em></sub>, IP = 13.8 eV), 73 (<em>A</em><sup>2</sup>Π<sub><em>u</em></sub>, 17.6 eV), 72.5 (B^2Sigma _u^+, 18.1 eV) and 71.2 eV (C^2Sigma _g^+, 19.4 eV)

<p><strong>Figure 7.</strong> Photoelectron kinetic energy spectrum of an unaligned CO<sub>2</sub> molecule after photoionization with 90.6 eV photon energy at FLASH (black line) and fit (red line) of the photoelectron spectrum using four Gaussians with 0.5 eV FWHM centred at E<sub><em>K</em></sub> = 76.8 (<em>X</em><sup>2</sup>Π<sub><em>g</em></sub>, IP = 13.8 eV), 73 (<em>A</em><sup>2</sup>Π<sub><em>u</em></sub>, 17.6 eV), 72.5 (B^2\Sigma _u^+, 18.1 eV) and 71.2 eV (C^2\Sigma _g^+, 19.4 eV). The blue lines are the individual peaks representing the contribution of the four aforementioned states retrieved from the fitting of the spectrum. Inset: experimental 2D projection of the electron momentum distribution recorded at FLASH.</p> <p><strong>Abstract</strong></p> <p>The dissociation dynamics induced by a 100 fs, 400 nm laser pulse in a rotationally cold Br<sub>2</sub> sample was characterized by Coulomb explosion imaging (CEI) using a time-delayed extreme ultra-violet (XUV) FEL pulse, obtained from the Free electron LASer in Hamburg (FLASH). The momentum distribution of atomic fragments resulting from the 400 nm-induced dissociation was measured with a velocity map imaging spectrometer and used to monitor the internuclear distance as the molecule dissociated. By employing the simultaneously recorded in-house timing electro-optical sampling data, the time resolution of the final results could be improved to 300 fs, compared to the inherent 500 fs time-jitter of the FEL pulse. Before dissociation, the Br<sub>2</sub> molecules were transiently 'fixed in space' using laser-induced alignment. In addition, similar alignment techniques were used on CO<sub>2</sub> molecules to allow the measurement of the photoelectron angular distribution (PAD) directly in the molecular frame (MF). Our results on MFPADs in aligned CO<sub>2</sub> molecules, together with our investigation of the dissociation dynamics of the Br<sub>2</sub> molecules with CEI, show that information about the evolving molecular structure and electronic geometry can be retrieved from such experiments, therefore paving the way towards the study of complex non-adiabatic dynamics in molecules through XUV time-resolved photoion and photoelectron spectroscopy.</p>