Accurate Tunneling Splittings for Proton Transfer in Malonaldehyde and Formic Acid Dimer Using the One-Dimensional Schrödinger Equation

12 April 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


In this manuscript we present an approach for computing tunneling splittings for large amplitude motions.
The core of the approach is a solution of an effective one-dimensional Schrödinger equation with an effective mass and an effective potential energy surface composed of electronic and harmonic zero-point vibrational energies of small amplitude motions in the molecule.
The method has been shown to work in cases of three model motions: nitrogen inversion in ammonia, single proton transfer in malonaldehyde, and double proton transfer in the formic acid dimer. In the current work we also investigate the performance of different DFT and post-Hartree-Fock methods for prediction of the proton transfer tunneling splittings, quality of the effective Schrödinger equation parameters upon the isotopic substitution, and possibility of a complete basis set (CBS) extrapolation for the resulting tunneling splittings.


tunneling splitting
effective Hamiltonian
large amplitude motions
formic acid dimer

Supplementary materials

si ma fad tunneling benchmark


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