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 p ∼ 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 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.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Kroto HW, Heath JR, O’Brien SC, Curl RF, Smalley RE (1985) Nature 318:162
Dresselhaus MS, Dresselhaus G, Eklund PC (1996) Science of fullerenes and carbon nano- tubes. Academic, San Diego
Kroto HW, Walton DRM (2011) In: Langa F, Nierengarten JF (eds) Fullerenes: principles and applications, 2nd edn. Royal Society of Chemistry, Cambridge
Hertel IV, Laarmann T, Schulz CP (2005) Adv Atom Mol Opt Phys 50:219
O’Brien SC, Heath JR, Curl RF, Smalley RE (1988) J Chem Phys 88:220
Matt S, Echt O, Scheier P, Märk TD (2001) Chem Phys Lett 348:194
de Vries J, Steger H, Kamke B, Menzel C, Weisser B, Kamke W, Hertel IV (1992) Chem Phys Lett 188:159
Reinköster A, Korica S, Prümper G, Viefhaus J, Godehusen K, Schwarzkopf O, Mast M, Becker U (2004) J Phys B 37:2135
Laarmann T, Shchatsinin I, Stalmashonak A, Boyle M, Zhavoronkov N, Handt J, Schmidt R, Schulz CP, Hertel IV (2007) Phys Rev Lett 98:058302
Foltin V, Foltin M, Matt S, Scheier P, Becker K, Deutsch H, Märk TD (1998) Chem Phys Lett 289:181
Jensen J, Zettergren H, Schmidt HT, Cederquist H, Tomita S, Nielsen SB, Rangama J, Hvelplund P, Manil B, Huber BA (2004) Phys Rev A 69:053203
Campbell EEB, Raz T, Levine RD (1996) Chem Phys Lett 253:261
Hansen K, Hoffmann K, Campbell EEB (2003) J Chem Phys 119:2513
Shchatsinin I, Laarmann T, Stibenz G, Steinmeyer G, Stalmashonak A, Zhavoronkov N, Schulz CP, Hertel IV (2006) J Chem Phys 125:194320
Brabec T, Côté M, Boulanger P, Ramunno L (2005) Phys Rev Lett 95:073001
Jaroń-Becker A, Becker A, Faisal FHM (2006) Phys Rev Lett 96:143006
Hertel IV, Shchatsinin I, Zhavoronkov N, Ritze H-H, Schulz CP (2009) Phys Rev Lett 102:023003
Shchatsinin I, Ritze H-H, Schulz CP, Hertel IV (2009) Phys Rev A 79:053414
Torralva B, Niehaus TA, Elstner M, Suhai S, Frauenheim T, Allen RE (2001) Phys Rev B 64:153105
Zhang GP, Sun X, George TF (2003) Phys Rev B 68:165410
Laarmann T, Schulz CP, Hertel IV (2008) In: Yamanouchi K, Chin SL, Agostini P, Ferrante G (eds) Progress in ultrafast intense laser science III. Springer, Heidelberg, pp 129–148
Antoine R, Dugourd P, Rayane D, Benichou E, Broyer M, Chandezon F, Guet C (1999) J Chem Phys 110:9771
Bhardwaj VR, Corkum PB, Rayner DM (2003) Phys Rev Lett 91:203004
Nakai K, Kono H, Sato Y, Niitsu N, Sahnoun R, Tanaka M, Fujimura Y (2007) Chem Phys 338:127
Sato Y, Kono H, Koseki S, Fujimura Y (2003) J Am Chem Soc 125:8019
Kono H, Sato Y, Tanaka N, Kato T, Nakai K, Koseki S, Fujimura Y (2004) Chem Phys 304:203
Kono H, Sato Y, Kanno M, Nakai K, Kato T (2006) Bull Chem Soc Jpn 79:196
Jortner J, Levine RD (1991) In: Jortner J, Levine RD, Pullman A (eds) Mode selective chemistry. Kluwer, Dordrecht, p 535
Porezag D, Frauenheim T, Köhler T, Seifert G, Kaschner R (1995) Phys Rev B 51:12947
Seifert G, Porezag D, Frauenheim T (1996) Int J Quant Chem 58:185
Elstner M, Porezag D, Jungnickel G, Elsner J, Haugk M, Frauenheim T, Suhai S, Seifert G (1998) Phys Rev B 58:7260
Stone AJ, Wales DJ (1986) Chem Phys Lett 128:501
Murry RL, Strout DL, Odom GK, Scuseria GE (1993) Nature 366:665
Irle S, Zheng G, Wang Z, Morokuma K (2006) J Phys Chem B 110:14531
Fedorov AS, Fedorov DA, Kuzubov AA, Avramov PV, Nishimura Y, Irle S, Witek HA (2011) Phys Rev Lett 107:175506
Yan Y-X, Gamble EB Jr, Nelson KA (1985) J Chem Phys 83:5391
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Montgomery JA, Jr., Vreven T, Kudin KN, Burant JC, Millam JM, Iyengar SS, Tomasi J, Barone V, Mennucci B, Cossi M, Scalmani G, Rega N, Petersson GA, Nakatsuji H, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Klene M, Li X, Knox JE, Hratchian HP, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Ayala PY, Morokuma K, Voth GA, Salvador P, Dannenberg JJ, Zakrzewski VG, Dapprich S, Daniels AD, Strain MC, Farkas O, Malick DK, Rabuck AD, Raghavachari K, Foresman JB, Ortiz JV, Cui Q, Baboul AG, Clifford S, Cioslowski S, Stefanov BB, Liu G, Liashenko A, Piskorz P, Komaromi I, Martin RL, Fox DJ, Keith T, Al-Laham MA, Peng CY, Nanayakkara A, Challacombe M, Gill PMW, Johnson B, Chen W, Wong MW, Gonzalez C, Pople JA (2004) Gaussian, Inc., Wallingford. GAUSSIAN 03, Revision E.01
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA, Jr.,Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian, Inc., Wallingford. GAUSSIAN 09, Revision A.02
Choi CH, Kertesz M, Mihaly L (2000) J Phys Chem 104:102
Elstner M (1998) Dissertation at the University Paderborn
Zheng G, Irle S, Morokuma K (2005) Chem Phys Lett 412:210
Zheng G, Wang Z, Irle S, Morokuma K (2007) J Nanosci Nanotechnol 7:1662
Saha B, Shindo S, Irle S, Morokuma K (2009) ACS Nano 3:2241
Jakowsi J, Irle S, Morokuma K (2010) Phys Rev B 82:125443
Sahnoun R, Nakai K, Sato Y, Kono H, Fujimura Y, Tanaka M (2006) Chem Phys Lett 430:167
Sahnoun R, Nakai K, Sato Y, Kono H, Fujimura Y, Tanaka M (2006) J Chem Phys 125:184306
Kono H, Koseki S (2002) In: Bandrauk AD, Fujimura Y, Gordon RJ (eds) Laser control and manipulation of molecules. American Chemical Society, Washington, DC, pp 267–284
Zhou X, Lin Z, Jiang C, Gao M, Allen RE (2010) Phys Rev B 82:075433
Boyle M, Laarmann T, Shchatsinin I, Schulz CP, Hertel IV (2005) J Chem Phys 122:181103
Shchatsinin I, Laarmann T, Zhavoronkov N, Schulz CP, Hertel IV (2008) J Chem Phys 129:204308
Kroto HW (1987) Nature 329:529
Bettinger HF, Yakobson BI, Scuseria GE (2003) J Am Chem Soc 125:5572
Podlivaev AI, Openov LA (2005) JETP Lett 81:533
Lifshitz C (2002) Eur J Mass Spectrom 8:85
Forst W (2003) Unimolecular reactions. Cambridge, Cambridge
Baer T, Hase WL (1996) Unimolecular reaction dynamics. Oxford University Press, New York
Katayanagi H, Mitsuke K (2010) J Chem Phys 133:081101
Katayanagi H, Mitsuke K (2011) J Chem Phys 135:144307
Zettergren H, Alcami M, Martin F (2008) Chem Phys Chem 9:861
Beu TA, Horváth L, Ghişoiu I (2009) Phys Rev B 79:054112
Beu TA, Jurjiu A (2011) Phys Rev B 83:024103
Churilov GN, Fedorov AS, Novikov PV (2003) Carbon 41:173
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.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2012 Springer Science+Business Media Dordrecht
About this paper
Cite this paper
Niitsu, N. et al. (2012). Simulation of Nuclear Dynamics of C60: From Vibrational Excitation by Near-IR Femtosecond Laser Pulses to Subsequent Nanosecond Rearrangement and Fragmentation. In: Nishikawa, K., Maruani, J., Brändas, E., Delgado-Barrio, G., Piecuch, P. (eds) Quantum Systems in Chemistry and Physics. Progress in Theoretical Chemistry and Physics, vol 26. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-5297-9_7
Download citation
DOI: https://doi.org/10.1007/978-94-007-5297-9_7
Published:
Publisher Name: Springer, Dordrecht
Print ISBN: 978-94-007-5296-2
Online ISBN: 978-94-007-5297-9
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)