Detection and Characterization of Anharmonic Overtone Vibrations of Single Molecules on a Metal Surface.

Inelastic electron tunneling spectroscopy (IETS) with the scanning tunneling microscope (STM) is a powerful technique used to characterize the vibration and spin states at the single-molecule level. While IETS lacks hard selection rules, historically it has been assumed that vibrational overtones are rarely seen or even absent. Here we provide definitive experimental evidence that the hindered rotation overtone excitation of carbon monoxide molecules adsorbed on Ag(110) can be detected with STM-IETS via isotope substitution.

Imaging the halogen bond in self-assembled halogenbenzenes on silver.

Halogens are among the most electronegative elements, and the variations in size and polarizability of halogens require different descriptions of the intermolecular bonds they form. Here we use the inelastic tunneling probe (itProbe) to acquire real-space imaging of intermolecular-bonding structures in the two-dimensional self-assembly of halogenbenzene molecules on a metal surface. Direct visualization is obtained for the intermolecular attraction and the "windmill" pattern of bonding among the fully halogenated molecules.

Probing Intermolecular Coupled Vibrations between Two Molecules.

Intermolecular interactions can induce energy shifts and coupling of molecular vibrations. However, the detection of intermolecular coupled vibrations has not been reported at the single molecule level. Here we detected an intermolecular coupled vibration between two CO molecules, one on the surface and another on the tip within the gap of a subkelvin scanning tunneling microscope, and analyzed the results by density functional calculations.

Imaging van der Waals Interactions.

The van der Waals interactions are responsible for a large diversity of structures and functions in chemistry, biology, and materials. Discussion of van der Waals interactions has focused on the attractive potential energy that varies as the inverse power of the distance between the two interacting partners. The origin of the attractive force is widely discussed as being due to the correlated fluctuations of electron charges that lead to instantaneous dipole-induced dipole attractions.

Quantitative Understanding of van der Waals Interactions by Analyzing the Adsorption Structure and Low-Frequency Vibrational Modes of Single Benzene Molecules on Silver.

The combination of a sub-Kelvin scanning tunneling microscope and density functional calculations incorporating van der Waals (vdW) corrections has been used successfully to probe the adsorption structure and low-frequency vibrational modes of single benzene molecules on Ag(110). The inclusion of optimized vdW functionals and improved C6-based vdW dispersion schemes in density functional theory is crucial for obtaining the correct adsorption structure and low-energy vibrational modes. These results demonstrate the emerging capability to quantitatively probe the van der Waals interactions between a physisorbed molecule and an inert substrate.

Nature of Asymmetry in the Vibrational Line Shape of Single-Molecule Inelastic Electron Tunneling Spectroscopy with the STM.

Single molecule vibrational spectroscopy and microscopy was demonstrated in 1998 by inelastic electron tunneling with the scanning tunneling microscope. To date, the discussion of its application has mainly focused on the spatial resolution and the spectral energy and intensity. Here we report on the vibrational line shape for a single carbon monoxide molecule that qualitatively exhibits inversion symmetry when it is transferred from the surface to the tip.

Trapping and Characterization of a Single Hydrogen Molecule in a Continuously Tunable Nanocavity.

Using inelastic electron tunneling spectroscopy with the scanning tunneling microscope (STM-IETS) and density functional theory calculations (DFT), we investigated properties of a single H2 molecule trapped in nanocavities with controlled shape and separation between the STM tip and the Au (110) surface. The STM tip not only serves for the purpose of characterization, but also is directly involved in modification of chemical environment of molecule. The bond length of H2 expands in the atop cavity, with a tendency of dissociation when the gap closes, whereas it remains unchanged in the trough cavity.

Real-space imaging of molecular structure and chemical bonding by single-molecule inelastic tunneling probe.

The arrangement of atoms and bonds in a molecule influences its physical and chemical properties. The scanning tunneling microscope can provide electronic and vibrational signatures of single molecules. However, these signatures do not relate simply to the molecular structure and bonding.

Rotational and vibrational excitations of a hydrogen molecule trapped within a nanocavity of tunable dimension.

The rotational and vibrational transitions of a hydrogen molecule weakly adsorbed on the Au(110) surface at 10 K were detected by inelastic electron tunneling spectroscopy with a scanning tunneling microscope. The energies of the j=0 to j=2 rotational transition for para-H(2) and HD indicate that the molecule behaves as a three-dimensional rigid rotor trapped within the tunnel junction. An increase in the bond length of H(2) was precisely measured from the downshift in the rotational energy as the tip-substrate distance decreases.