The effect of atomic substitution on electron-phonon interactions in negatively charged B, N-substituted acenes.
The effect of atomic substitution on electron-phonon interactions in negatively charged B, N-substituted acenes.
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DOI：
10.1063/1.1755671
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发表时间：
2004-06
期刊：
影响因子：
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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
B单负离子中的电子-声子相互作用，N-取代的并苯，如B（3）N（3）F（6）（1f）和B（5）N（5）F（8）（2 f），并与一元阴离子B（3）N（3）H（6）（1h）和B（5）N（5）H（8）（2 h）进行了比较，和B（3）N（3）D（6）（1d）和B（5）N（5）D（8）（2d）。500 cm（-1）附近的低频模以及高于1000 cm（-1）的频率模强烈耦合到1f和2f中的最低未占分子轨道（LUMO）。总的电子-声子耦合常数（l（LUMO））估计为2.710和2.054 eV的1f和2f，分别为0.342和0.235 eV的1d和2d，而这些估计为0.340和0.237 eV的1h和2 h，分别为。也就是说，在B，N-取代的并苯中，通过H-F取代比通过H-D取代更显著地增加I（LUMO）值。1f和2f中B和N原子在电子振动激活模中的位移大于1d和2d中的位移，这是由于氟原子质量大于氘原子质量所致; 1f和2f中LUMO的位相图与1d和2d中不同，其中N原子与相邻F原子之间的原子轨道形成强的σ-反键相互作用，其中相邻的B和N原子之间的原子轨道形成弱的π-键和π-反键相互作用是H-F取代比H-D取代使l（LUMO）值显著增加的主要原因。中性分子和相应的一元阴离子之间的重组能估计为0.122，0.063，0.733，和0.830 eV的1小时，2小时，1 f，和2 f，分别。因此，中性分子和相应的一元阴离子之间的重组能估计为1f和2f是远远大于那些为1h和2 h。
Electron-phonon interactions in the monoanions of B, N-substituted acenes such as B(3)N(3)F(6) (1f) and B(5)N(5)F(8) (2f) are studied, and compared with those in the monoanions of B(3)N(3)H(6) (1h) and B(5)N(5)H(8) (2h), and B(3)N(3)D(6) (1d) and B(5)N(5)D(8) (2d). The low frequency modes around 500 cm(-1) as well as the frequency modes higher than 1000 cm(-1) strongly couple to the lowest unoccupied molecular orbitals (LUMO) in 1f and 2f. The total electron-phonon coupling constants (l(LUMO)) are estimated to be 2.710 and 2.054 eV for 1f and 2f, respectively, and those are estimated to be 0.342 and 0.235 eV for 1d and 2d, respectively, while those were estimated to be 0.340 and 0.237 eV for 1h and 2h, respectively. That is, the l(LUMO) value increases much more significantly by H-F substitution than by H-D substitution in B, N-substituted acenes. The larger displacements of B and N atoms in the vibronic active modes in 1f and 2f than those in 1d and 2d due to larger atomic mass of fluorine than that of deuterium, and the phase patterns difference between the LUMO in 1f and 2f, in which the atomic orbitals between N and its neighboring F atoms form strong sigma-antibonding interactions, and that in 1d and 2d, in which the atomic orbitals between two neighboring B and N atoms form weak pi-bonding and pi-antibonding interactions, are the main reason why the l(LUMO) value increases much more significantly by H-F substitution than by H-D substitution. The reorganization energies between the neutral molecules and the corresponding monoanions are estimated to be 0.122, 0.063, 0.733, and 0.830 eV for 1h, 2h, 1f, and 2f, respectively. Therefore, the estimated reorganization energies between the neutral molecules and the corresponding monoanions for 1f and 2f are much larger than those for 1h and 2h.