The hydrogen tunneling splitting in malonaldehyde: A full-dimensional time-independent quantum mechanical method.

Abstract

The accurate time-independent quantum dynamics calculations on the ground-state tunneling splitting of malonaldehyde in full dimensionality are reported for the first time. This is achieved with an efficient method developed by us. In our method, the basis functions are customized for the hydrogen transfer process which has the effect of greatly reducing the size of the final Hamiltonian matrix, and the Lanczos method and parallel strategy are used to further overcome the memory and central processing unit time bottlenecks. The obtained ground-state tunneling splitting of 24.5 cm(-1) is in excellent agreement with the benchmark value of 23.8 cm(-1) computed with the full-dimensional, multi-configurational time-dependent Hartree approach on the same potential energy surface, and we estimate that our reported value has an uncertainty of less than 0.5 cm(-1). Moreover, the role of various vibrational modes strongly coupled to the hydrogen transfer process is revealed.