The geometric configuration and energy of a hydrogen molecule centered between two point-shaped tips of equal charge are calculated with the variational quantum Monte Carlo (QMC) method without the restriction of the Born-Oppenheimer (BO) approximation. The ground-state nuclear distribution, stability, and low-vibrational excitations are found to deviate significantly from the BO treatment based on a potential energy surface obtained with the same QMC accuracy. The quantum-mechanical distribution of the molecular axis direction and the bond length at a subnanometer level is fundamental for understanding nanomechanical dynamics with embedded hydrogen. The cylindrical symmetry of the tip arrangement yields a uniform azimuthal distribution of the molecular axis vector relative to the tip-tip axis. For fixed tip separation, the QMC sampling shows that the polar angle distribution of the molecular axis is centered around the equatorial plane for positive tip charge (transverse alignment) and around the tip-tip direction for negative tip charge (bridge alignment). These deviations from spherical symmetry are magnified as the tip-tip distance decreases. Our results thus show that the molecular orientation in the junction can be controlled by the tip charge and separation, suggesting an application in the field of molecular machines.

• Received 24 December 2019
• Revised 4 March 2020
• Accepted 21 April 2020

DOI:https://doi.org/10.1103/PhysRevB.101.195436