Fundamental studies of chemical reactions often draw molecular dynamics along a reaction coordinate in a calculated or suggested potential energy surface (PES) 1-5 . But fully mapping such dynamics experimentally, by following all nuclear motions in a timeresolved manner, that is the motions of wavepackets, is challenging and has not even been realized for the simple stereotypical bimolecular reaction 6-8 of A-B + C → A + B-C. Here we report such tracking of vibrational wavepacket trajectories during photo-induced bond formation in the gold trimer complex [Au(CN)2 -]3 in an aqueous solution, using femtosecond x-ray solution scattering (liquidography 9-12 ) at x-ray free electron lasers 13,14 . We find that the complex forms from an assembly of three monomers A, B and C clustered together through non-covalent interactions 15,16 and with the distance between A and B shorter than between B and C. Tracking of the wavepacket in three-dimensional nuclear coordinates (RAB, RBC, and RAC) reveals that within the first 60 fs 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 fs to give a linear and covalently-bonded trimer complex A-B-C. The trimer exhibits harmonic vibrations that we are also able to map, and unambiguously assign to specific normal modes using only the experimental data. More intense x-rays can in principle visualize the motion of not only highly-scattering atoms such as gold but also of lighter atoms such as carbon and nitrogen, which will open the door for the direct tracking of the atomic motions involved in many chemical reactions.The [Au(CN)2 -]3 complex has served as a valuable model system for studying photoinitiated processes in solution. Irradiation with ultraviolet light excites it from the ground state (S0) to the singlet state (S1), which within 20 fs undergoes intersystem crossing to reach a triplet excited state (T1') 18 . A further transition from T1' to another triplet excited state (T1) then occurs with a time constant of 1~2 ps, completing formation of covalent bonds and transformation of the complex from a bent to a linear structure 9,17,18 (see the Supplementary Information (SI) for details of the notations of electronic states).Formation of the bonds could involve any of the three possible candidate trajectories sketched in Fig. 1b. The equilibrium structure in the ground state determines the position of the

Energy, structure, and charge are fundamental quantities characterizing a molecule. Whereas the energy flow and structure change in chemical reactions are experimentally characterized, determining the atomic charges of a molecule in solution has been elusive, even for a triatomic molecule such as triiodide ion, I3−. Moreover, it remains to be answered how the charge distribution is coupled to the molecular geometry; which I-I bond, if two I-I bonds are unequal, dissociates depending on the electronic state. Here, femtosecond anisotropic x-ray solution scattering allows us to provide the following answers in addition to the overall rich structural dynamics. The analysis unravels that the negative charge of I3− is highly localized on the terminal iodine atom forming the longer bond with the central iodine atom, and the shorter I-I bond dissociates in the excited state, whereas the longer one in the ground state. We anticipate that this work may open a new avenue for studying the atomic charge distribution of molecules in solution and taking advantage of orientational information in anisotropic scattering data for solution-phase structural dynamics.

In this work, we explore the nonenzymatic detection of H2O2 using anodic SnO2 nanoporous channels (NPC) decorated with CuO quantum dots (QDs). The open-top and crack-free morphology of SnO2 NPC was obtained by modified anodization. The samples were characterized using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray analysis (EDAX), high-resolution transmission electron microscopy (HRTEM), Raman and X-ray photoelectron (XPS) spectroscopy. FESEM and HRTEM results show that SnO2 has a uniform channel width and pore size with an average diameter of around 40 nm. XRD, EDAX, XPS, Raman, and HRTEM measurements confirm the high purity of anodic SnO2 NPC with successful deposition of CuO QDs. Pristine (SnO2) and hybrid (SnO2-CuO) electrodes were used directly as the nonenzymatic H2O2 biosensor. The hybrid electrode demonstrated an ultrahigh sensitivity of ∼85,250 μA mM–1 cm–2 with an extremely low limit of detection (0.001 μM), broad linear detection ranges of 5–95 and 25–450 μM, and a quick response time (less than 1.9 s) toward H2O2 detection. This can be attributed to the advanced SnO2 nanoporous structure, the reduced band gap, and the formation of additional surface sites as a result of CuO QD decoration. H2O2 measurement in human blood serum demonstrates high sensitivity, good accuracy, and excellent selectivity of the fabricated hybrid electrode compared to the commercially available biosensor. Density functional theory results indicate that the formation of SnO2-CuO is energetically favorable. H2O2 is strongly and selectively adsorbed over the SnO2-CuO nanostructure possessing a large negative adsorption energy (−1.89 eV) and evinces a significant decrease in the band gap (up to 1.59 eV) of the hybrid structure. The fabricated biosensor showed the highest sensitivity, excellent selectivity, good reproducibility, repeatability, and stability, thus confirming it as a favorable candidate for nonenzymatic H2O2 sensing and quantification.