Mozhayskiy Vadim A, Babikov Dmitri, Krylov Anna I
Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.
J Chem Phys. 2006 Jun 14;124(22):224309. doi: 10.1063/1.2204602.
The ground and electronically excited states of cyclic N(3) (+) are characterized at the equilibrium D(3h) geometry and along the Jahn-Teller distortions. Lowest excited states are derived from single excitations from the doubly degenerate highest occupied molecular orbitals (HOMOs) to the doubly degenerate lowest unoccupied molecular orbitals (LUMOs), which give rise to two exactly and two nearly degenerate states. The interaction of two degenerate states with two other states eliminates linear terms and results in a glancing rather than conical Jahn-Teller intersection. HOMO-2-->LUMOs excitations give rise to two regular Jahn-Teller states. Optimized structures, vertical and adiabatic excitation energies, frequencies, and ionization potential (IP) are presented. IP is estimated to be 10.595 eV, in agreement with recent experiments.
环状N(3)+的基态和电子激发态在平衡D(3h)几何结构以及沿 Jahn-Teller 畸变的情况下进行了表征。最低激发态源自从双重简并的最高占据分子轨道（HOMO）到双重简并的最低未占据分子轨道（LUMO）的单激发，这产生了两个完全简并和两个近简并态。两个简并态与另外两个态的相互作用消除了线性项，并导致了一个掠射而非锥形的 Jahn-Teller 交叉点。HOMO-2→LUMO 激发产生了两个规则的 Jahn-Teller 态。给出了优化结构、垂直和绝热激发能、频率以及电离势（IP）。IP估计为10.595 eV，与最近的实验结果一致。
