title: Reaction dynamics. Vibrational relaxation and microsolvation of DF after F-atom reactions in polar solvents.
abstract: Solvent-solute interactions influence the mechanisms of chemical reactions in solution, but the response of the solvent is often slower than the reactive event. Here, we report that exothermic reactions of fluorine (F) atoms in d3-acetonitrile and d2-dichloromethane involve efficient energy flow to vibrational motion of the deuterium fluoride (DF) product that competes with dissipation of the energy to the solvent bath, despite strong solvent coupling. Transient infrared absorption spectroscopy and molecular dynamics simulations show that after DF forms its first hydrogen bond on a subpicosecond time scale, DF vibrational relaxation and further solvent restructuring occur over more than 10 picoseconds. Characteristic dynamics of gas-phase F-atom reactions with hydrogen-containing molecules persist in polar organic solvents, and the spectral evolution of the DF products serves as a probe of solvent reorganization induced by a chemical reaction.
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
authors: G T
authors: GT
authors: Dunning
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK. Department of Computer Science, Merchant Venturers Building, Woodland Road, Bristol BS8 1UB, UK. Photon Ultrafast Laser Science and Engineering (PULSE) Institute and Department of Chemistry, Stanford University, Stanford, CA 94305, USA. SLAC National Accelerator Laboratory, Menlo Park, CA 94025, USA. a.orr-ewing@bristol.ac.uk drglowacki@gmail.com.
authors: D R
authors: DR
authors: Glowacki
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
authors: T J
authors: TJ
authors: Preston
authors: School of Engineering and Physical Sciences, Heriot-Watt University, Edinburgh EH14 4AS, UK.
authors: S J
authors: SJ
authors: Greaves
authors: Central Laser Facility, Research Complex at Harwell, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, Oxfordshire OX11 0QX, UK.
authors: G M
authors: GM
authors: Greetham
authors: Central Laser Facility, Research Complex at Harwell, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, Oxfordshire OX11 0QX, UK.
authors: I P
authors: IP
authors: Clark
authors: Central Laser Facility, Research Complex at Harwell, Science and Technology Facilities Council, Rutherford Appleton Laboratory, Harwell Oxford, Didcot, Oxfordshire OX11 0QX, UK.
authors: M
authors: M
authors: Towrie
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK.
authors: J N
authors: JN
authors: Harvey
authors: School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK. a.orr-ewing@bristol.ac.uk drglowacki@gmail.com.
authors: A J
authors: AJ
authors: Orr-Ewing