Diagonal Curvature in Second Order Jahn Teller Theory Can Be Negative: An Analytic Proof with First-Principles Confirmation in NH3
Abstract
We demonstrate that the diagonal curvature in second-order Jahn-Teller theory (SOJTT) can be negative, invalidating its foundational positivity assumption. Using a frozen-phonon many-body expansion, we show no quantum-mechanical principle enforces its positivity; recasting into the Kohn-Sham framework further reveals that phonon-induced eigen-energy changes arise solely from electron-nuclear, Hartree, and exchange-correlation terms, with kinetic-energy contributions canceling identically. First principles calculations on NH3 place the D3h reference configuration at an A2" saddle point; Schwarz-inequality upper-bound analysis confines the HOMO-LUMO mixing contribution to < 0.2% of the total energy drop,while 99.8% originates from the diagonal electron-nuclear term driving N (2s-2pz) electron redistribution. These findings overturn a core SOJTT tenet and establish that spontaneous structural symmetry breaking demands prior verification of a saddle point, not assumed positivity of the diagonal curvature.
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Cite
@article{arxiv.2603.14291,
title = {Diagonal Curvature in Second Order Jahn Teller Theory Can Be Negative: An Analytic Proof with First-Principles Confirmation in NH3},
author = {Zhian Li and Hanxiang Mi and Xiyue Cheng and Jurgen Kohler and Shuiquan Deng},
journal= {arXiv preprint arXiv:2603.14291},
year = {2026}
}