Dynamics of protonated oxalate from machine-learned simulations and experiment: infrared signatures, proton transfer dynamics and tunneling splittings.

Authors

Valerii Andreichev, Silvan Käser, Erica L Bocanegra, Madeeha Salik, Mark A Johnson, Markus Meuwly

Published in

Physical chemistry chemical physics : PCCP. Oct 21, 2025. Epub Oct 21, 2025.

Abstract

The infrared spectroscopy and proton transfer dynamics together with the associated tunneling splittings for H/D-transfer in oxalate are investigated using a machine learning-based potential energy surface (PES) of CCSD(T) quality, calibrated against the results of new spectroscopic measurements. Second order vibrational perturbation calculations (VPT2) very successfully describe both the framework and H-transfer modes compared with the experiments. In particular, a newly observed low-intensity signature at 1666 cm^-1 was correctly predicted from the VPT2 calculations. An unstructured band centered at 2940 cm^-1 superimposed on a broad background extending from 2600 to 3200 cm^-1 is assigned to the H-transfer motion. The broad background involves a multitude of combination bands but a major role is played by the COH-bend. For the deuterated species, VPT2 and molecular dynamics simulations provide equally convincing assignments, in particular for the framework modes. Finally, based on the new PES the tunneling splitting for H-transfer is predicted as Δ_H = 35.0 cm^-1 from ring polymer instanton calculations using higher-order corrections. This provides an experimentally accessible benchmark to validate the computations, in particular the quality of the machine-learned PES.

PMID:
41117007
Bibliographic data and abstract were imported from PubMed on 21 Oct 2025.

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