Nanosecond simulations of the dynamics of C-60 excited by intense near-infrared laser pulses: Impulsive Raman excitation, rearrangement, and fragmentation

作者：Niitsu Naoyuki^*; Kikuchi Miyu; Ikeda Hayato; Yamazaki Kaoru; Kanno Manabu; Kono Hirohiko; Mitsuke Koichiro; Toda Mikito; Nakai Katsunori

来源：Journal of Chemical Physics, 2012, 136(16): 164304.

DOI：10.1063/1.4704896

Impulsive Raman excitation of C-60 by single or double pulses of near-infrared wavelength lambda = 1800 nm was investigated by using a time-dependent adiabatic state approach combined with the density functional theory method. We confirmed that the vibrational energy stored in a Raman active mode of C-60 is maximized when T-p similar to T-vib/2 in the case of a single pulse, where T-p is the pulse length and T-vib is the vibrational period of the mode. In the case of a double pulse, mode selective excitation can be achieved by adjusting the pulse interval tau. The energy of a Raman active mode is maximized if tau is chosen to equal an integer multiple of T-vib and it is minimized if tau is equal to a half-integer multiple of T-vib. We also investigated the subsequent picosecond or nanosecond dynamics of Stone-Wales rearrangement (SWR) and fragmentation by using the density-functional based tight-binding semiempirical method. We present how SWRs are caused by the flow of vibrational kinetic energy on the carbon bond network of C-60. In the case where the h(g)(1) prolate-oblate mode is initially excited, the number of SWRs before fragmentation is larger than in the case of a(g)(1) mode excitation for the same excess vibrational energy. Fragmentation by C-2 ejection C-60 -> C-58 + C-2 is found to occur from strained, fused pentagon/pentagon defects produced by a preceding SWR, which confirms the earliest mechanistic speculations of Smalley et al. [J. Chem. Phys. 88, 220 (1988)]. The fragmentation rate of C-2 ejection in the case of h(g)(1) mode excitation does not follow a statistical description as employed for instance in the Rice-Ramsperger-Kassel (RRK) theory, whereas the rate for a(g)(1) mode excitation does follow the prediction by RRK. We also found for the h(g)(1) mode excitation that the nonstatistical nature affects the distribution of barycentric velocities of fragments C-58 and C-2. This result suggests that it is possible to control rearrangement and subsequent bond breaking in a "nonstatistical" way by initial selective mode excitation.

• 出版日期2012-4-28