摘要
oneelectron 的几何学减少 / 氧化种类([顶]/[VOP ]+) vanadyl，卟啉(VOP ) 与 PBE1PBE 被计算了方法。结果为两个显示出那[VOP ] 并且[VOP ] 地面说的 + 是三位字节，在哪个二个奇电子占据 V 原子轨道的 d xy 当其它占据时卟啉戒指轨道。因此两[VOP ] 并且[VOP ]+ 能被看作激进分子。中立 VOP 分子的扎根的状态是有占据 V 原子轨道的 d xy 的奇电子的马甲。在到中立 VOP 分子的 C4v 对称的合同，[VOP ] 阴离子由于 JahnTeller 有矩形的弄歪的 C2v 结构效果。为 JahnTeller 活跃模式的线性电子振动的联合常数[顶] 被评估，边疆 KS orbitals 的节点模式被用来解释失真沿着特定的模式发生的原因。扎根的状态[VOP ]+ 由于 pseudoJahnTeller 效果与显著契约长度引申有一枚卟啉戒指，引起它的对称从 C4v 衰退了到 C4。契约长度引申很好与重建的边疆 KS orbitals 的节点模式被解释。
The geometries of one-electron reduced/oxidized species （[TOP]-/[VOP] ＋） of vanadyl por- phyrin （VOP） have been calculated with PBE1PBE method. The results show that for both [VOP]- and [VOP]＋ the ground states are triplet, in which one of the two unpaired electron occupies the dxy orbital of the V atom while the other occupies the n-orbital of porphyrin ring. Thus both [VOP]- and [VOP]＋ can be considered as n-radicals. The ground state of neutral VOP molecule is doublet with the unpaired electron occupying dxy orbital of V atom. In contract to the C4v symmetry of neutral VOP molecule, [VOP]- anion has a ＂rectangular＂ distorted C2v structure due to Jahn-Teller effect. The linear vibronic coupling constants for the Jahn-Teller active modes of [TOP]- were evaluated and the node patterns of frontier KS orbitals are used to explain the reason why the distortion occurs along specific modes. The ground state [VOP]＋ has a porphyrin ring with pronounced bond length alternation due to pseudo-Jahn-Teller effect, causing its symmetry declined from C4v to Ca. The bond length alternation is well explained with the node patterns of re-constructed frontier KS orbitals.
