Theoretical exploration of the relativistic Jahn-Teller effect
Final Report Abstract
This theoretical project aimed at the demonstration of the existence of novel Jahn-Teller forces in molecules, atomic clusters and coordination complexes which arise from the spinorbit operator and are, therefore, of relativistic origin. Relativistically generalized Jahn-Teller and pseudo-Jahn-Teller Hamiltonians were derived for trigonal, tetragonal, tetrahedral and cubic systems using group-theoretical methods. In addition to a perturbative description of spin-orbit coupling, which is appropriate for systems containing moderately heavy elements, a more general theory of the relativistic Jahn-Teller effect has been derived which is based on a variational treatment of relativistic effects in electronic-structure theory and is applicable for systems with arbitrarily heavy elements. The theory has furthermore been extended to allow the construction of relativistic Jahn-Teller Hamiltonians up to arbitrarily high orders in nuclear displacements from the reference geometry. Numerical values of spin-orbit induced Jahn-Teller coupling constants were determined with ab initio electronic-structure calculations for selected systems, including tetrahedral clusters of the fifth main group and transition-metal trifluorides. Electronic and vibrational spectra of Jahn-Teller systems were computed with diagonalization methods or with time-dependent quantum wave-packet dynamics methods. Observable spectroscopic signatures of spin-orbit induced Jahn-Teller coupling could be demonstrated for some of these systems.
Publications
- Jahn-Teller and spin-orbit coupling effects in transition-metal trifluorides. Chem. Phys. 387, 56 (2011)
P. Mondal, D. Opalka, L. V. Poluyanov and W. Domcke
(See online at https://doi.org/10.1016/j.chemphys.2011.06.034) - Relativistic Jahn-Teller effects in the photoelectron spectra of tetrahedral P4, As4, Sb4, and Bi4. J. Chem. Phys. 135, 104108 (2011)
D. Opalka, L. V. Poluyanov and W. Domcke
(See online at https://doi.org/10.1063/1.3629779) - Ab initio study of dynamical E x e Jahn-Teller and spin-orbit coupling effects in the transition-metal trifluorides TiF3, CrF3, and NiF3. J. Chem. Phys. 136, 084308 (2012)
P. Mondal, D. Opalka, L. V. Poluyanov and W. Domcke
(See online at https://doi.org/10.1063/1.3687001) - Jahn-Teller, pseudo-Jahn-Teller, and spin-orbit coupling Hamiltonian of a d-electron in an octahedral environment. J. Chem. Phys. 137, 114101 (2012)
L. V. Poluyanov and W. Domcke
(See online at https://doi.org/10.1063/1.4751439) - Relativistic Jahn-Teller and pseudo-Jahn-Teller couplings in D2d systems. Chem. Phys. 407, 1 (2012)
L. V. Poluyanov and W. Domcke
(See online at https://doi.org/10.1016/j.chemphys.2012.07.014) - Jahn-Teller theory beyond the standard model. J. Phys: Conf. Series 428, 012015 (2013)
S. Bhattacharyya, D. Opalka, L. V. Poluyanov and W. Domcke
(See online at https://doi.org/10.1088/1742-6596/428/1/012015) - Infrared absorption spectra of Jahn-Teller systems: Application to transition-metal trifluorides MnF3 and NiF3. J. Phys. Chem. A 118, 3726 (2014)
P. Mondal and W. Domcke
(See online at https://doi.org/10.1021/jp4118002) - The (E + A) × (e + a) Jahn-Teller and pseudo Jahn-Teller Hamiltonian including spin-orbit coupling for trigonal systems. J. Phys. Chem. A 118, 11962 (2014)
S. Bhattacharyya, D. Opalka, L. V. Poluyanov and W. Domcke
(See online at https://doi.org/10.1021/jp506793z) - Quantum dynamics on a three-sheeted six-dimensional ab initio potential-energy surface of the phosphine cation: simulation of the photoelectron spectrum and the ultrafast radiationless decay dynamics. J. Chem. Phys. 143, 194301 (2015)
S. Bhattacharyya, Z. Dai and W. Domcke
(See online at https://doi.org/10.1063/1.4935601) - Quasi-classical nonadiabatic transition probability for G3/2 × (t2 + e) Jahn-Teller systems. Chem. Phys. 463, 1 (2015)
L. V.Poluyanov, V. Volokhov and W. Domcke
(See online at https://doi.org/10.1016/j.chemphys.2015.09.008) - Relativistic theory of the Jahn-Teller effect: p-orbitals in tetrahedral and trigonal systems. J. Chem. Phys. 144, 124101 (2016)
W. Domcke, D. Opalka and L. V. Poluyanov
(See online at https://doi.org/10.1063/1.4943863)
