Spin-orbit coupling and the intersection of potential energy surfaces in polyatomic molecules
Spin-orbit coupling and the intersection of potential energy surfaces in polyatomic molecules
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多原子分子中的自旋轨道耦合和势能面的交集
DOI：
10.1098/rspa.1976.0134
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发表时间：
1976
期刊：
影响因子：
--
通讯作者：
A. Stone
中科院分区：
文献类型：
--
作者：
A. Stone
朗格-希金斯定理表明，势能面之间存在交叉点可以从波函数在远离交叉点的行为中推断出来，该定理被推广到涵盖哈密顿量为复数的情况。结论是，由于核构型空间的一个区域中的对称性而产生的相交可能意味着相同的表面在更高维度和更低对称性的区域上相交，其中它们的波函数属于相同的对称性种类。结果表明，在存在自旋轨道耦合的情况下，这种行为会发生在 d1 八面体配合物中。
Longuet-Higgins’ theorem, which shows that the existence of intersections between potential energy surfaces may be deduced from the behaviour of the wavefunction at points remote from the intersection, is generalized to cover cases where the Hamiltonian is complex. It is concluded that an intersection due to symmetry in one region of nuclear configuration space may imply that the same surfaces intersect over a region of higher dimension and lower symmetry where their wavefunctions belong to the same symmetry species. It is shown that this behaviour occurs in d1 octahedral complexes in the presence of spin-orbit coupling.