Diagonal Curvature in Second Order Jahn Teller Theory Can Be Negative: An Analytic Proof with First-Principles Confirmation in NH3

TL;DR

This paper proves that the diagonal curvature in second-order Jahn-Teller theory can be negative, challenging a fundamental assumption, with first-principles calculations on NH3 supporting this claim and emphasizing the need for careful saddle point verification.

Contribution

It provides an analytic proof and first-principles confirmation that the diagonal curvature in SOJTT can be negative, overturning a core tenet of the theory.

Findings

Diagonal curvature in SOJTT can be negative.

First-principles calculations on NH3 support the negative curvature.

Spontaneous symmetry breaking requires saddle point verification.

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.