IR spectra of photopolymerized C60 films. Experimental and density functional theory study

Stepan G. Stepanian, Victor A. Karachevtsev, Alexander M. Plokhotnichenko, Ludwik Adamowicz, Apparao M. Rao

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Abstract

IR spectra of photopolymerized fullerene films obtained by simultaneous deposition and UV irradiation were measured in the range of 1500-450 cm -1. The degree of the polymerization of the G60 films was estimated to be about 95%. To assist the assignment of the experimental IR spectra of the films, quantum chemical calculations of the equilibrium structures of the C60 dimers and trimers were performed at the DFT(B3LYP)/ 3-21G level of theory. Next, IR frequencies and intensities for those structures were calculated. For the five-trimer structures found in the calculations, the relative stabilities were determined at the B3LYP/4-31G * and B3LYP/6-31G* levels and used to select the lowest-energy trimers, which are Trimer A (angle between monomer centers is 90°) and Trimer B (angle between monomer centers is 120°). Next, the IR spectra of the polymerized fullerene films were compared with the calculated frequencies of the lowest-energy dimer and the two lowest-energy trimers. On the basis of this analysis and on the comparison of the film spectra with the IR spectra of the C60 dimer and trimer spectra obtained by other methods, it was shown that the main components of the films are C60 dimers and the orthorhombic (O) polymer phase. The tetragonal (T) and rhombohedral (R) polymers, as well as small amounts of monomers, were also found. Although vibrational frequencies of different C60 phases are similar in most cases, we found several unique spectral features of the C60 dimer and other polymers that may be used to determine the composition of the polymerized C60 film.

Original languageEnglish (US)
Pages (from-to)15769-15775
Number of pages7
JournalJournal of Physical Chemistry B
Volume110
Issue number32
DOIs
StatePublished - Aug 17 2006

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trimers
Density functional theory
density functional theory
Dimers
dimers
Fullerenes
Polymers
monomers
Monomers
fullerenes
polymers
Vibrational spectra
Discrete Fourier transforms
energy
polymerization
Polymerization
Irradiation
irradiation
Chemical analysis

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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IR spectra of photopolymerized C60 films. Experimental and density functional theory study. / Stepanian, Stepan G.; Karachevtsev, Victor A.; Plokhotnichenko, Alexander M.; Adamowicz, Ludwik; Rao, Apparao M.

In: Journal of Physical Chemistry B, Vol. 110, No. 32, 17.08.2006, p. 15769-15775.

Research output: Contribution to journalArticle

Stepanian, Stepan G. ; Karachevtsev, Victor A. ; Plokhotnichenko, Alexander M. ; Adamowicz, Ludwik ; Rao, Apparao M. / IR spectra of photopolymerized C60 films. Experimental and density functional theory study. In: Journal of Physical Chemistry B. 2006 ; Vol. 110, No. 32. pp. 15769-15775.
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abstract = "IR spectra of photopolymerized fullerene films obtained by simultaneous deposition and UV irradiation were measured in the range of 1500-450 cm -1. The degree of the polymerization of the G60 films was estimated to be about 95{\%}. To assist the assignment of the experimental IR spectra of the films, quantum chemical calculations of the equilibrium structures of the C60 dimers and trimers were performed at the DFT(B3LYP)/ 3-21G level of theory. Next, IR frequencies and intensities for those structures were calculated. For the five-trimer structures found in the calculations, the relative stabilities were determined at the B3LYP/4-31G * and B3LYP/6-31G* levels and used to select the lowest-energy trimers, which are Trimer A (angle between monomer centers is 90°) and Trimer B (angle between monomer centers is 120°). Next, the IR spectra of the polymerized fullerene films were compared with the calculated frequencies of the lowest-energy dimer and the two lowest-energy trimers. On the basis of this analysis and on the comparison of the film spectra with the IR spectra of the C60 dimer and trimer spectra obtained by other methods, it was shown that the main components of the films are C60 dimers and the orthorhombic (O) polymer phase. The tetragonal (T) and rhombohedral (R) polymers, as well as small amounts of monomers, were also found. Although vibrational frequencies of different C60 phases are similar in most cases, we found several unique spectral features of the C60 dimer and other polymers that may be used to determine the composition of the polymerized C60 film.",
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