Mapping the emergence of molecular vibrations mediating bond formation

Fundamental studies of chemical reactions often consider the molecular dynamics along a reaction coordinate using a calculated or suggested potential energy surface 1 – 5 . But fully mapping such dynamics experimentally, by following all nuclear motions in a time-resolved manner—that is, the motions of wavepackets—is challenging and has not yet been realized even for the simple stereotypical bimolecular reaction 6 – 8 : A–B + C → A + B–C. Here we track the trajectories of these vibrational wavepackets during photoinduced bond formation of the gold trimer complex [Au(CN) 2 − ] 3 in an aqueous monomer solution, using femtosecond X-ray liquidography 9 – 12 with X-ray free-electron lasers 13 , 14 . In the complex, which forms when three monomers A, B and C cluster together through non-covalent interactions 15 , 16 , the distance between A and B is shorter than that between B and C. Tracking the wavepacket in three-dimensional nuclear coordinates reveals that within the first 60 femtoseconds after photoexcitation, a covalent bond forms between A and B to give A–B + C. The second covalent bond, between B and C, subsequently forms within 360 femtoseconds to give a linear and covalently bonded trimer complex A–B–C. The trimer exhibits harmonic vibrations that we map and unambiguously assign to specific normal modes using only the experimental data. In principle, more intense X-rays could visualize the motion not only of highly scattering atoms such as gold but also of lighter atoms such as carbon and nitrogen, which will open the door to the direct tracking of the atomic motions involved in many chemical reactions. Femtosecond X-ray liquidography is used to track the vibrational wavepacket trajectories of gold atoms in solution, enabling time-resolved observations of the emergence of vibrations and the evolution of the formation of covalent bonds.