Multidimensional H-atom tunneling in the catecholate monoanion

Abstract

We present catecholate monoanion as a new model system for the study of multidimensional tunneling. It has a symmetrical O-H···O− double-well structure, and the H atom motion between the two...

Wavepacket dynamical study of H-atom tunneling in catecholate monoanion: the role of intermode couplings and energy flow

“…Q 29 is the third most contributing mode (after Q 1 and Q 10 ) to the H-atom transfer in CM in terms of displacement between the TS and minimum geometries. Additionally, in the eigenstate calculations in the Q 1 -Q 29 space, 84 we have seen that frequencies of Q 1 and Q 29 at the local minima of this 2D space are close to each other. These are manifested in the strongly mixed Q 1 -Q 29 eigenstate structures and the difficulty in state assignments.…”

“…A full description of all the modes of CM as well as their role in H-atom tunneling from an eigenstate perspective are given in our recent work. 84 Denoting a mode space as S, the Hamiltonian for it is given as…”

“…While we have prepared such wavepackets for selected 2D and 3D eigenstate pairs from our prior work 84 and propagated them, the evolution is limited to a two-state Hilbert space and the evolving wavepacket can be understood through the original eigenstates. Snapshots of the evolving wavepacket prepared from the ground Q 1 -Q 10 -Q 29 eigenstate pair are shown in Fig.…”

“…† We note that these very 1D Hamiltonians were also used to prepare the basis sets for our multidimensional eigenstates. 84 The 1D Hamiltonians also lead to a repartitioning of H ˆ(S) in eqn (1) as…”

“…The eigenstates |Ki are defined as solutions of eqn (1): H ˆ(S) |Ki = E (S) K |Ki. 84 Recall that we have prepared initial states as the symmetric linear combination of two direct product states which are pair to each other, e.g. |1 l +10 m 29 n i and |1 l À10 m 29 n i for the 3D case.…”