Funding OTKA T Alexander von Humboldt Foundation References [1]: F. Borondics, E. Jakab, S. Pekker: Journal of Nanoscience and Nanotechnology 7, 1551 (2007) [2]: H. Kataura, Y. Kumazawa, Y. Maniwa, I. Umezu, S. Suzuki, Y. Ohtsuka, Y. Achiba: Synth. Metals 103, 2555 (1999) [3]: C. Fantini, M. L. Usrey, M. S. Strano: J. Phys. Chem. C 111, (2007) [4]: Á. Pekker, D. Wunderlich, K. Kamarás, A. Hirsch: Phys. Stat. Sol. B 245, 1954 (2008) [5]: K. Németh, F. Borondics, E. Jakab, Á. Pekker, K. Kamarás, S. Pekker: Poster #5 on SIWAN 2008 [6]: M. Müller, J. Maultzsch, D. Wunderlich, A. Hirsch, C. Thomsen: Phys. Stat. Sol. B 244, 4056 (2007) [7]: K. Kamarás, Á. Pekker: Handbook of Nanoscience and Technology, Editors: A. V. Narlikar, Y. Y. Fu, Oxford University Press, 2009 [8]: M. S. Strano: J. Am. Chem. Soc. 125, (2003) [9]: S. Kazaoui, N. Minami, R. Jacquemin, H. Kataura, Y. Achiba: Phys. Rev. B 69, (1999) Most of the functionalization reactions are primarily selective to metallic tubes [7], as these tubes have the nonzero DOS at the Fermi level [8]. Birch-type alkylation begins with doping by excess Li, which fills both S 11, S 22 and M 11 [9].  The selectivity for metallic tubes is masked The charged nanotubes are dispersed in the liquid NH 3 solution.  The size of the cavity in the bundle does not play a role. Carbanions having greater s-character are more stable.  Smaller diameter tubes are more reactive Selectivity on tube diameter According to the RBM spectrum the small diameter semiconducting nanotubes react more readily. This is in accordance with NIR[4, 5] and Raman[6] spectroscopic measurements on alkylated HiPCO tubes. In the case of 531 nm and 676 nm laser excitation the change was obscured by the error. Explanation of the selectivity S 33 +S 44 S33S33 M 11 The samples Pulsed laser vaporization  SWCNT + Ni/Co catalyst  Refluxing with HNO 3  SWCNT-COOH  Heating to 800 ºC  SWCNT Functionalization by modified Birch reduction [1]: Li + n NH 3  Li + + e - (NH 3 ) n e - (NH 3 ) n + C  C - + nNH 3 C - + BzBr  BzC + Br - C - + BuI  BuC + I - C - + MeI  MeC + I - C - + HX  HC + X - (HX = H 2 O, NH 3, CH 3 OH) The degree of functionalization (R+H)/100C was determined from TG-MS. The samples are inhomogeneous  average spectra selected for comparison with TG-MS Depth samplingResonant Raman scattering [2] 676 nm 531 nm 468 nm Raman spectra of functionalized carbon nanotubes G. Klupp, F. Borondics, R. Hackl*, K. Kamarás, E. Jakab**, S. Pekker Research Institute for Solid State Physics and Optics, Hungarian Academy of Sciences, Budapest, Hungary, *Walther Meissner Institute, Bavarian Academy of Sciences and Humanities, Garching, Germany **Institute of Materials and Environmental Chemistry, Budapest, Hungary A complete spectrum No functional groups are visible and nanotubes are still in resonance.  Electronic structure is not collapsed due to functionalization. The same degree of functionalization leads to smaller changes in the electronic structure in the case of apolar alkyl groups than in the case of polar substituted phenyl groups [3]. Lorentzian Gaussian Selectivity on tube type I D /I G and I D /I D* increase with the degree of functionalization, as the change of the electronic structure is only minor. The ratio depends on the wavelength of the exciting laser, as in Ref. 3. If we substract the value measured in the pristine sample (arising from the defects of the pristine nanotube) the change is similar for both metallic and semiconducting nanotubes.  The reaction is not selective for tube type BzBuMe 676 nm 531 nm 468 nm BzBuMe 676 nm 531 nm 468 nm