Theoretical and Experimental Study of Fullerenol Molecules
and Ions C₆₀(OH)_{24 n}(OL)_n and C₆₀(OH)_{24 n}(OL)_nL⁺ Successively
Substituted by Alkali Metal Atoms L (n = 124)

O. P. Charkin^{a, 1}, N. M. Klimenko^b, Y.-S. Wang^c, C.-C Wang^c, C.-H. Chen^c, and S. H. Lin^d

^a Institute of Problems of Chemical Physics, Russian Academy of Sciences,
Institutskii pr. 18, Chernogolovka, Moscow oblast, 142432 Russia

e-mail: charkin@icp.ac.ru

^b Lomonosov State Academy of Fine Chemical Technology, pr. Vernadskogo 86, Moscow, 117571 Russia

e-mail: nmklimenko@mitht.ru

^c Genomics Research Center, Academia Sinica, 128 Academia Road, Section 2, Nankang, Taipei, 115, Taiwan

e-mail: wer@gate.sinica.edu.tw

^d Institute of Atomic and Molecular Sciences, Academia Sinica, P. O. Box 23-166 Taipei, Taiwan 106, R.O.C.

e-mail: hcschaw@po.iams.sinica.edu.tw

Received April 8, 2010

Abstract—The equilibrium geometric parameters and the energetic characteristics of fullerenol molecules and
ions C₆₀(OH)_{24 – n}(OL)_n and C₆₀(OH)_{24 – n}(OL)_nL⁺ successively substituted by alkali metal atoms L with the num-
ber of substitutions n = 1–24 have been calculated by the density functional theory B3LYP/6-31G* method. For
all compounds, the structure of the covalent [C₆₀O₂₄] cage in which the oxygen atoms are bound to the C atoms
of the six-membered [C₆] rings of the fullerene cage, six O atoms per [C₆] ring. The lithium derivatives have
been considered in most detail. Computations have shown that the first four single substitutions of Li for H in
the OH groups attached to the same C₆ ring require very low energy inputs, no more than 1 kcal/mol, and can
spontaneously occur under common conditions. The further fifth and sixth single substitutions in the same C₆ ring
are endothermic, but the required energy inputs are also modest (on the order of few kcal/mol). The first and second
cooperative substitutions of Li for H simultaneously in all four hydroxylated C₆ rings require energy inputs of
~3 and 11.6 kcal/mol, respectively; in the third and fourth fourfold substitutions, the energies increase by ~15–
16 kcal/mol. The mean partial energy per single substitution of Li for H in this series (n = 1–6) is ~2 kcal/mol.
Calculations have predicted that all C₆₀(OH)_{24 – n}(OLi)_n molecules with intermediated degrees of substitution (n
= 1–16) can be obtained under the conditions of relatively low energy inputs (for example, under the conditions
of the MALDI experiment) and can exist in the isolated state. For the sodium- and potassium-substituted ana-
logues, the qualitative pattern persists, but the H/Na and H/K substitutions are somewhat more endothermic.
The computational results are compared with the MALDI mass spectrum of the [C₆₀(OH)_x(ONa)_y–CH₃COONa)
system.

DOI: 10.1134/S0036023611040073

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