Atomic-scale intermolecular interaction of hydrogen with a single VOPc molecule on the Au(111) surface

Molecular dynamics of hydrogen molecules (H(2)) on surfaces and their interactions with other molecules have been studied with the goal of improvement of hydrogen storage devices for energy applications. Recently, the dynamic behavior of a H(2) at low temperature has been utilized in scanning tunnelling microscopy (STM) for sub-atomic resolution imaging within a single molecule. In this work, we have investigated the intermolecular interaction between H(2) and individual vanadyl phthalocyanine (VOPc) molecules on Au(111) substrates by using STM and non-contact atomic force microscopy (NC-AFM). We measured tunnelling spectra and random telegraphic noise (RTN) on VOPc molecules to reveal the origin of the dynamic behavior of the H(2). The tunnelling spectra show switching between two states with different tunnelling conductance as a function of sample bias voltage and RTN is measured near transition voltage between the two states. The spatial variation of the RTN indicates that the two-state fluctuation is dependent on the atomic-scale interaction of H(2) with the VOPc molecule. Density functional theory calculations show that a H(2) molecule can be trapped by a combination of a tip-induced electrostatic potential well and the potential formed by a VOPc underneath. We suggest the origin of the two-state noise as transition of H(2) between minima in these potentials with barrier height of 20–30 meV. In addition, the bias dependent AFM images verify that H(2) can be trapped and released at the tip–sample junction.