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Simulation of Nuclear Dynamics of C60: From Vibrational Excitation by Near-IR Femtosecond Laser Pulses to Subsequent Nanosecond Rearrangement and Fragmentation

  • N. Niitsu
  • M. Kikuchi
  • H. Ikeda
  • K. Yamazaki
  • M. Kanno
  • H. Kono
  • K. Mitsuke
  • M. Toda
  • K. Nakai
  • S. Irle
Conference paper
Part of the Progress in Theoretical Chemistry and Physics book series (PTCP, volume 26)

Abstract

Impulsive Raman excitation of C60 by single or double near-IR femtosecond pulses of λ = 1,800 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 C60 is maximized when T pT 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 τ. The energy of a Raman active mode is maximized if τ is chosen to equal an integer multiple of T vib, and it is minimized if τ is equal to a half-integer multiple of T vib. The energy stored can be larger than the barrier heights for rearrangement or fragmentation processes. The picosecond or nanosecond dynamics of resulting Stone-Wales rearrangement (SWR) and fragmentation are also investigated 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 network of C60. In the case where the hg(1) prolate-oblate mode is initially excited, the number of SWRs prior to fragmentation is larger than in the case of ag(1) mode excitation for the same excess vibrational energy. Fragmentation by C2-ejection 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 C60 → C58 + C2 in the case of hg(1) prolate-oblate mode excitation does not follow a statistical description as employed for instance in the Rice-Ramsperger-Kassel (RRK) theory, whereas the rate for ag(1) mode excitation does follow predictions made by RRK. We also found for the hg(1) mode excitation that the nonstatistical nature still remains in the distribution of barycentric velocities of fragments C58 and C2. This result suggests that it is possible to control rearrangement and subsequent bond breaking in a “nonstatistical” way by initial selective mode excitation.

Keywords

Vibrational Energy Neutral Model Mode Excitation Double Pulse Raman Active Mode 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgments

This work was partly supported by the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan, for Scientific Research No. 21350005, and the Joint Studies Program (2011) of the Institute for Molecular Science. The authors are grateful to Prof. I.V. Hertel for his valuable discussion on the dynamics of C60. We thank Prof. Thomas Frauenheim for providing the DFTB + program and parameters and also Prof. Keiji Morokuma for advice on the use of the DFTB + program.

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Copyright information

© Springer Science+Business Media Dordrecht 2012

Authors and Affiliations

  • N. Niitsu
    • 1
  • M. Kikuchi
    • 1
  • H. Ikeda
    • 1
  • K. Yamazaki
    • 1
  • M. Kanno
    • 1
  • H. Kono
    • 1
  • K. Mitsuke
    • 2
  • M. Toda
    • 3
  • K. Nakai
    • 4
  • S. Irle
    • 5
  1. 1.Department of Chemistry, Graduate School of ScienceTohoku UniversitySendaiJapan
  2. 2.Institute for Molecular ScienceOkazakiJapan
  3. 3.Department of PhysicsNara Women’s UniversityNaraJapan
  4. 4.Department of Chemistry, School of ScienceThe University of TokyoTokyoJapan
  5. 5.Department of Chemistry, Graduate School of ScienceNagoya UniversityNagoyaJapan

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