2023 journal article
Cooperative Pseudo Jahn Teller distortion derives phase transitions in bismuth oxide
MATERIALS CHEMISTRY AND PHYSICS, 299.
UN Sustainable Development Goal Categories
7. Affordable and Clean Energy
(Web of Science)
Source: Web Of Science
Added: April 4, 2023
Bismuth oxide exhibits a complex array of structures with a broad range of properties of various technological importance. We derive the phase transition pathway using the in-situ heating X-ray diffraction data, evidencing four polymorphs of α, β, δ, and γ. We prove that the observed phase transitions are due to the cooperative pseudo-Jahn-Teller distortion in the crystal originating from mixing the ground state Bi6s and excited Bi6p states. Using the electron localization function and crystal orbital theory, we explore the role of the Bi3+ lone pair in the second-order phase transition. It is found that the O2p states have a critical role in stabilizing the lone pair activity, which leads to a pseudo-Jahn Teller distortion cooperatively inducing the phase transition.