CCS MSU

CCS Publication Abstract

Calculating the Equilibrium Structure of the BNB Molecule: Real Vs. Artifactual Symmetry Breaking

Gwaltney, S. R., & Head-Gordon, M. (2001). Calculating the Equilibrium Structure of the BNB Molecule: Real Vs. Artifactual Symmetry Breaking. Physical Chemistry Chemical Physics. 3, 4495-4500.

Abstract

Approximate electronic structure calculations on the ground state of the BNB molecule are subject to artifactual symmetry breaking as well as a potential second-order Jahn–Teller distortion along its antisymmetric stretch coordinate. In addition, the bending mode is very floppy and has a large anharmonic coupling with the symmetric stretch. Hence, this molecule presents a major challenge for theoretical electronic structure methods. We present a series of calculations designed to distinguish the real from the artifactual symmetry breaking. Our results give the minimum structure as C∞v, with the D∞h transition state 161 ± 20 cm−1 higher in energy, thus lying below the first vibrational level.