TY - JOUR
T1 - Application of MCD spectroscopy and TD-DFT to endohedral metallofullerenes for characterization of their electronic transitions
AU - Yamada, Michio
AU - Slanina, Zdenek
AU - Mizorogi, Naomi
AU - Muranaka, Atsuya
AU - Maeda, Yutaka
AU - Nagase, Shigeru
AU - Akasaka, Takeshi
AU - Kobayashi, Nagao
PY - 2013/3/14
Y1 - 2013/3/14
N2 - We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C2v-C82, La 2@Ih-C80, and Sc3N@I h-C80 can be assigned using these techniques. Particularly, a difference in the electronic transitions between La 2@Ih-C80 and Sc3N@I h-C80, which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La2@Ih-C80 were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La2@Ih-C80, although no marked difference exists in their absorption spectra.
AB - We describe, for the first time, the application of magnetic circular dichroism (MCD) spectroscopy and time-dependent density functional theory (TD-DFT) calculations using B3LYP and M06-2X functionals to characterize the electronic transitions of endohedral metallofullerenes (EMFs). Results revealed that the electronic transitions of La@C2v-C82, La 2@Ih-C80, and Sc3N@I h-C80 can be assigned using these techniques. Particularly, a difference in the electronic transitions between La 2@Ih-C80 and Sc3N@I h-C80, which is invisible in absorption spectra, was observed clearly in MCD spectra. The observed MCD bands agree well with the oscillator strengths calculated using the B3LYP functional. In addition, the MCD bands of La2@Ih-C80 were altered upon [5,6]-addition, demonstrating that the MCD spectroscopy is sensitive to chemical functionalization of EMFs, and that it is therefore powerful to distinguish [5,6]-adducts from pristine La2@Ih-C80, although no marked difference exists in their absorption spectra.
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U2 - 10.1039/c3cp44096f
DO - 10.1039/c3cp44096f
M3 - Article
C2 - 23381223
AN - SCOPUS:84874085073
VL - 15
SP - 3593
EP - 3601
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 10
ER -