Wedler Henry B, Wendelboe Paul, Tantillo Dean J, Power Philip P
Department of Chemistry, University of California-Davis, Davis, CA, USA.
Dalton Trans. 2020 Apr 28;49(16):5175-5182. doi: 10.1039/d0dt00137f.
Second order Jahn-Teller (SOJT) effects arise from interactions between filled and empty molecular orbitals of like symmetry. These interactions often lead to structural distortions whose extent is inversely proportional to the energy difference between the interacting orbitals. The main objectives of the work described here are (1) the calculation (using density functional theory methods) of the energies of the valence molecular orbitals in the species EH3 (E = N, P, As or Sb), HEEH (E = C, Si, Ge or Sn), and H2EEH2, (E = C, Si, Ge or Sn) and (2) the correlation of these energies with barriers for planarization or linearization. The calculations suggest an upper limit of about 12 eV energy separation of the interacting levels for SOJT effects to be significant, which is considerably larger than previously thought and implies that SOJT effects may be more common than currently realized.
二阶 Jahn-Teller（SOJT）效应源于具有相同对称性的满分子轨道和空分子轨道之间的相互作用。这些相互作用常常导致结构畸变，畸变程度与相互作用轨道之间的能量差成反比。本文所述工作的主要目标是：（1）（使用密度泛函理论方法）计算物种 EH3（E = N、P、As 或 Sb）、HEEH（E = C、Si、Ge 或 Sn）以及 H2EEH2（E = C、Si、Ge 或 Sn）中价分子轨道的能量；（2）将这些能量与平面化或线性化的势垒相关联。计算结果表明，对于显著的 SOJT 效应，相互作用能级的能量间隔上限约为 12 eV，这比之前认为的要大得多，意味着 SOJT 效应可能比目前所认识到的更为普遍。
