Fast Molecular Compression by a Hyperthermal Collision Gives Bond-Selective Mechanochemistry

Abstract

Using electrospray ion beam deposition, we collide a complex molecule Reichardt's Dye (C 41 H 30 NO + ) at low, hyperthermal translational energy (2 -50 eV) with a Cu(100) surface and image the outcome at single-molecule level by Scanning Tunneling Microscopy. We observe bond-selective reaction induced by the translational kinetic energy. The collision impulse compresses the molecule and bends specific bonds, prompting them to react selectively. This dynamics drives the system to seek thermally inaccessible reactive pathways, since the compression timescale (sub-ps) is much shorter than the thermalization timescale (ns), thereby yielding reaction products that are unobtainable thermally

Low-energy electron holography imaging of conformational variability of single-antibody molecules from electrospray ion beam deposition

“…The molecules are slowed down to landing energies of less than 5 eV per charge, and hence the kinetic energy at impact is around 110 to 130 eV per molecule at charge states between +22 and +26. This translates to ∼10 meV per atom, which is less than the thermal energy at room temperature (k B T = 25 meV) and hence far from a reactive collision regime (65). However, this energy is mostly transferred into soft vibrational modes of the molecule as well as into the deformation of the surface.…”

“…The occurrence of extended antibody conformations on the surface can thus be related to the dissipation of kinetic energy during the landing process or the adsorption interaction, which can convert collapsed molecules into extended conformations. Whether the transition from a collapsed into an extended structure occurs depends on the orientation of the molecule upon impact and strongly on its kinetic energy (46,65). The molecules are slowed down to landing energies of less than 5 eV per charge, and hence the kinetic energy at impact is around 110 to 130 eV per molecule at charge states between +22 and +26.…”

Atomistic-scale investigations of hyperthermal oxygen–graphene interactions via reactive molecular dynamics simulation: The gas effect

“…Predicting these interactions with the surface is important when designing the thermal protection system (TPS) to protect vehicles from severe aerodynamic heating [8][9][10][11]. Therefore, gas-surface collision dynamics under severe conditions have been investigated for a variety of surfaces both theoretically and experimentally [12][13][14][15][16][17]. Molecular beam experiments were performed where certain gas was induced and collided with various neat metallics, nonmetallic, polymers and composites under different experimental conditions [18][19][20].…”

Navigate flying molecular elephants safely to the ground: mass-selective soft landing up to the Mega-Dalton range by Electrospray Controlled Ion-Beam Deposition

“…Complementary to these analytical applications, high flux ion beams serve preparative purposes on a deposition target. Beam-energies below 10 eV/z are employed for soft-landing, i.e., gentle coating of sample-targets thereby functionalizing these [6][7][8][9] . Above 10 eV/z reactive landing of molecules or clusters prevail, whereas energies substantially above 100 eV/z lead to implantation of atoms or are used for lithographic purposes [10][11][12] .…”