Photoinduced reaction dynamics of nanocarbons
Nanocarbons such as fullerene, carbon nanotube, and graphene are the fundamental materials for carbon-based nanotechnologies. Their optical and electronic properties heavily depend on their size and shape. In order to realize single-molecule scale structural engineering of nanocarbons using laser irradiation, we quantum-chemically investigated the mechanism of the photoinduced reaction dynamics of nanocarbons both in energy and time domains.
We first investigated the reaction paths of Stone–Wales rearrangement (SWR), i.e., π/2 rotation of two carbon atoms with respect to the midpoint of the bond, in graphene and carbon nanotube at the MS-CASPT2//SA-CASSCF level of multi-reference molecular orbital theory . We found that the vibronic (electron-phonon) coupling play a crucial role to reduce the effective reaction barriers of the photoinduced defect formation of nanographene.
We next investigated that the fragmentation dynamics of the highly charged fullerene cation C60q+ (q = 20-60) produced by the irradiation of x-ray free electron laser pulse using on-the-fly classical trajectory calculations combined with density functional based tight-binding theory. We found that a two-step explosion mechanism governs the fragmentation dynamics : C60q+ firstly ejects singly and multiply charged fast atomic cations Cz+ (z ≥ 1) to reduce its strong intramolecular Coulomb repulsion on a timescale of 10 fs. Thermal (statistical) evaporations of slow atomic and molecular fragments from the remaining core cluster subsequently occur on a timescale of 100 fs to 1 ps.
I will also briefly discuss our recent results on the real-time imaging of the near-/mid-IR induced coherent vibration of C60, which is considered as the initial step of the photoinduced fragmentation of C60 
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 K. Yamazaki et al., J. Chem. Phys. 141, 121105 (2014).
 K. Yamazaki et al., to be submitted.