Issue 37, 2024

2500 vibronic eigenstates of the NO3 radical

Abstract

The nitrate radical NO3 plays an important role in atmospheric chemistry, yet many aspects of its coupled and anharmonic vibronic structure remain elusive. Here, using an accurate, coupled full-dimensional diabatic potential that includes five electronic states, we revisit the vibronic spectrum associated with the electronic Image ID:d4cp02653e-t1.gif state. Using recently developed tensor network state methods, we are able to compute more than 2500 vibronic states, thereby increasing the number of computed full-dimensional states by a factor of 50, compared to previous work. While we obtain good agreement with experiment for most of the assigned vibronic levels, for several others, we observe striking disagreement. Further, for the antisymmetric bending motion we find remarkably large symmetry-induced level splittings that are larger than the zero-order reference. We discuss non-negligible nonadiabatic effects and show that the Born–Oppenheimer approximation leads to significant errors in the spectrum.

Graphical abstract: 2500 vibronic eigenstates of the NO3 radical

Supplementary files

Article information

Article type
Paper
Submitted
03 7月 2024
Accepted
20 8月 2024
First published
22 8月 2024

Phys. Chem. Chem. Phys., 2024,26, 24506-24523

2500 vibronic eigenstates of the NO3 radical

H. R. Larsson and A. Viel, Phys. Chem. Chem. Phys., 2024, 26, 24506 DOI: 10.1039/D4CP02653E

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