The Jahn-Teller effect and its observation in titanium alum

Full text: A fundamental assumption, often employed to problems in solid state physics, is that a system may be well described within the confines of the Born-Oppenheimer approximation. As a consequence of the substantial difference of masses, the electrons are assumed to follow the motion of the nuclei adiabatically; hence, the motion of the electrons and nuclei are solved separately. As Jahn and Teller showed in 1936, any non-linear molecule having orbital degeneracy will be unstable to at least one asymmetric displacement which lifts the degeneracy. The wave equation must then be solved taking into account coupling between the electronic and nuclear motion. The E x β system, an electronic doublet coupled to a single mode of vibration, is introduced as an elementary example and is used to illustrate features characteristic of Jahn-Teller systems. The E x ε system is discussed in conjunction with work currently being undertaken on CsTi(SO4)2.12H2O. In this alum, the [Ti(OH2)6]3 + cation (3d1) is subject to an axial field which acts to leave a doubly degenerate electronic ground term. Spectroscopic and crystallographic data show the salt to undergo a phase transition at 12 K which we associate with a Co-operative Jahn-Teller Effect manifested by the interaction of the Jahn-Teller electrons with the crystal lattice. Also presented are EPR and SQUID data which illustrate how the Jahn-Teller effect leads to quenching of orbital angular momentum and spin-orbit coupling