The relationships between the electronic structures and the normal and inverse isotope effects in the electron–phonon interactions in charged cubane
The relationships between the electronic structures and the normal and inverse isotope effects in the electron–phonon interactions in charged cubane
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DOI：
10.1063/1.1599340
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发表时间：
2003-08
影响因子：
4.4
通讯作者：
Takashi Kato;T. Yamabe
中科院分区：
文献类型：
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作者：
Takashi Kato;T. Yamabe
研究了全氘立方团簇（如氘立方烷（CD）8）中电子-声子耦合和可能的正、逆同位素单阴离子效应。对带电荷的氘立方烷与带电荷的立方烷的计算结果进行了比较。计算出氘立方烷的单阴离子（lLUMO）和阳离子（lHOMO）的总电子-声子耦合常数分别为0.631和0.777 eV。由于铀的氘化作用，lLUMO值比lHOMO值的增加要显著得多。我们的计算结果表明，在立方烷的单阴离子（单离子）中，由于完全氘化，可以预期逆（正常）同位素效应。在碳原子上定位的t1g最低未占据分子轨道（LUMO）和非定域的t2g最高已占据分子轨道（HOMO）之间存在显著的相模式差异，并且由于氘化作用，碳原子在Eg模式下的位移较大，为1072 cm−1 （ωD6）。
Electron–phonon coupling and possible normal and inverse isotope effects in the monoanion and cation of fully deuterated cubic cluster such as deutero-cubane (CD)8 are studied. The calculational results for charged deutero-cubane are compared with those for charged cubane. The calculated total electron–phonon coupling constants for the monoanion (lLUMO) and cation (lHOMO) of deutero-cubane are 0.631 and 0.777 eV, respectively. The lLUMO value increases much more significantly than the lHOMO value as a consequence of deuteration in cubane. Our calculational results show that inverse (normal) isotope effects as a consequence of full deuteration can be expected in the monoanion (monocation) of cubane. Significant phase patterns difference between the t1u lowest unoccupied molecular orbitals (LUMO) rather localized on carbon atoms and delocalized t2g highest occupied molecular orbitals (HOMO), and the larger displacements of carbon atoms in the Eg mode of 1072 cm−1 (ωD6) as a consequence of deuteration are th...