Relativistic theory of the Jahn-Teller effect: p-orbitals in tetrahedral and trigonal systems.
Relativistic theory of the Jahn-Teller effect: p-orbitals in tetrahedral and trigonal systems.
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DOI：
10.1063/1.4943863
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发表时间：
2016-03
期刊：
影响因子：
--
通讯作者：
W. Domcke;Daniel Opalka;L. V. Poluyanov
中科院分区：
文献类型：
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作者：
W. Domcke;Daniel Opalka;L. V. Poluyanov
本文提出了一种相对论性的Jahn-Teller理论的推广，它包括了振动坐标中低阶泰勒展开式以外的自旋轨道耦合效应。对于四面体和三角形环境中的p-电子的例子，Breit-Pauli自旋轨道耦合算子的矩阵元表示为静电电子势的矩阵元。利用核坐标系下的不变多项式展开式，导出了任意高阶的T2 ×（t2 + e）和（E + A）×（e + a）Jahn-Teller问题的自旋-轨道诱导Jahn-Teller耦合项.本文将Moffitt和Thorson [Phys.Rev.108，1251（1957）]的四面体系统的线性G ~（3/2）×（t_2 + e）Jahn-Teller哈密顿量推广到高阶振动位移。本文导出的Jahn-Teller哈密顿量可用于分子和重元素络合物的Jahn-Teller畸变势能面的内插和外推，也可用于计算这类体系的电子振动谱。
A relativistic generalization of Jahn-Teller theory is presented which includes spin-orbit coupling effects beyond low-order Taylor expansions in vibrational coordinates. For the example of a p-electron in tetrahedral and trigonal environments, the matrix elements of the Breit-Pauli spin-orbit-coupling operator are expressed in terms of the matrix elements of the electrostatic electronic potential. Employing expansions of the latter in invariant polynomials in symmetry-adapted nuclear coordinates, the spin-orbit induced Jahn-Teller coupling terms are derived for the T2 × (t2 + e) and (E + A) × (e + a) Jahn-Teller problems up to arbitrarily high orders. The linear G3/2 × (t2 + e) Jahn-Teller Hamiltonian of Moffitt and Thorson [Phys. Rev. 108, 1251 (1957)] for tetrahedral systems is generalized to higher orders in vibrational displacements. The Jahn-Teller Hamiltonians derived in the present work are useful for the interpolation and extrapolation of Jahn-Teller distorted potential-energy surfaces of molecules and complexes with heavy elements as well as for the calculation of vibronic spectra of such systems.