Theoretical exploration of the relativistic Jahn-Teller effect

• Applicant: Professor Dr. Wolfgang Domcke
• Subject Area: Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2010 to 2018
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 192356176

• Final Report Year: 2018

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
  
• 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
  
• 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
  
• 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
  
• Relativistic Jahn-Teller and pseudo-Jahn-Teller couplings in D2d systems. Chem. Phys. 407, 1 (2012)
  L. V. Poluyanov and W. Domcke
  
• Jahn-Teller theory beyond the standard model. J. Phys: Conf. Series 428, 012015 (2013)
  S. Bhattacharyya, D. Opalka, L. V. Poluyanov and W. Domcke
  
• 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
  
• 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
  
• 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
  
• 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
  
• 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