We conducted experiments on the role of molecular hydrogen physisorbed between two metallic surfaces. Such hydrogen leads to strong signatures in inelastic electron tunneling spectroscopy exceeding the amplitude of typical inelastic transitions by an order of magnitude and is accompanied by a step in the tunneling current leading under certain circumstances to a huge negative differential conductance. We show that the molecular vibration opens an inelastic channel as expected but simultaneously stalls the total elastic channel due to the forces exerted by the vibrating molecule on the electrodes. The required compliance of the stylus is surprisingly large but is possible in the wide spectrum of experimental conditions. Additionally, the inelastic channel experiences a saturation from which the lifetime of the molecular vibration can be deduced to be approximately 1 ns. This experiment allows resolving the forces corresponding to specific vibrational states of a single molecule.
In this paper the interaction of hydrogen molecules with atomic-sized superconducting nanojunctions is studied. It is demonstrated by conductance histogram measurements that the superconductors niobium, tantalum and aluminum show a strong interaction with hydrogen, whereas for lead a slight interaction is observed, and for tin and indium no significant interaction is detectable. For Nb, Ta and Pb subgap method is applied to determine the transmission eigenvalues of the nanojunctions in hydrogen environment. It is shown, that in Nb and Ta the mechanical behavior of the junction is spectacularly…
The interaction between hydrogen molecules and platinum (Pt)-decorated carbon nanotubes (CNTs) with boron (B)-, nitrogen (N)-dopants or sidewall vacancies is discussed from first-principle calculations. The adsorption patterns of hydrogen molecules on four types of Pt-decorated CNTs are investigated, and the partial density of states projected on the Pt atom is computed to reveal the response to the number of hydrogen molecules, dopants or vacancies. It is found that the B-, N-dopants or sidewall vacancies can adjust the binding energy between the hydrogen molecules and the Pt atom deposited o…
We study the formation of molecular states in a two-electron quantum dot as a function of the barrier potential dividing the dot. The increasing barrier potential drives the two electron system from an artificial helium atom to an artificial hydrogen molecule. To study this strongly coupled regime, we introduce variational wavefunctions which describe accurately two electrons in a single dot, and then study their mixing induced by the barrier. The evolution of the singlet-triplet gap with the barrier potential and with an external magnetic field is analyzed.
We present a many-body calculation for the conductance of a conducting bridge of a simple hydrogen molecule between $Pt$ electrodes.The experimental results showed that the conductance $G=dI/dV$ has the maximum value near the quantum unit $G_{0}=2e^{2}/h$. The $I-V$ dependence presents peak and dip and we consider that the electron-phonon interaction is responsible for this behavior. At T=0 there is a step in this dependence for the energy of phonons $ω_{0}$ which satisfies $eV=ω_{0}$. We calculated the conductance at finite temperature and showed that $dG(T)/dV\propto 1/4T\cosh^{2}\frac{eV-ω_…
We have determined the entropy, the total energy, and the specific heat of the systems consisting of $M\geq 3$ hydrogen molecules. The calculations were conducted in the framework of the nonextensive Tsallis statistics. The relation between $M$ and the entropic index $q$ is given by $q = 1 + 1/M$, which results from the fact that the temperature of the nanosystems fluctuates around the temperature of the reservoir (Wilk and Włodarczyk, Phys. Rev. Lett. {\bf 84}, 2770 (2000)). The electron energy states of the hydrogen molecule have been determined with the help of the Hubbard Hamiltonian, whic…
We study numerically the dynamics of acetanilide (ACN) molecules placed on a flat surface of a multilayer hexagonal boron nitride structure. We demonstrate that the ACN molecules, being achiral in three dimensions, become chiral after being placed on the substrate. Homochirality of the ACN molecules leads to stable secondary structures stabilized by hydrogen bonds between peptide groups of the molecules. Numerical simulations of systems of such molecules reveal that the structure of the resulting hydrogen-bond chains depends on the isomeric composition of the molecules. If all molecules are ho…
In this paper an experimental study of the interaction of hydrogen molecules with gold nanowires is presented. Our results show, that chains of Au atoms can also be pulled in hydrogen environment, however in this case the conductance of the chain is strongly reduced compared to the perfect transmission of pure Au chains. The comparison of our experiments with recent theoretical prediction for the hydrogen welding of Au nanowires implies that a hydrogen molecule can even be incorporated in the gold nanocontact, and this hydrogen clamp is strong enough to pull a chain of gold atoms.
Recently Smit et al. [Nature 419, 906 (2002)] have reported that a single hydrogen molecule can form a bridge between Pt electrodes, which has a conductance close to one quantum unit, carried by a single channel. We present density functional calculations explaining these experimental findings. We show that the symmetry of the molecular orbitals selects a single conduction channel. The transmission of this channel is close to unity due to a combination of the charge transfer between hydrogen and the Pt contacts and the strong hybridization between the bonding state of the molecule and the d-ba…
Stable, single-molecule conducting-bridge configurations are typically identified from peak structures in a conductance histogram. In previous work on Pt with H$_2$ at cryogenic temperatures it has been shown that a peak near 1 $G{_0}$ identifies a single molecule Pt-H$_{2}$-Pt bridge. The histogram shows an additional structure with lower conductance that has not been identified. Here, we show that it is likely due to a hydrogen decorated Pt chain in contact with the H$_2$ molecular bridge.
Photon statistics is a powerful tool for characterizing the emission dynamics of nanoscopic systems and their photophysics. Recent advances that combine correlation spectroscopy with scanning tunneling microscopy-induced luminescence (STML) have allowed measuring the emission dynamics from individual molecules and defects demonstrating their nature as single photon emitters. The application of correlation spectroscopy to the analysis of the dynamics of a well-characterized adsorbate system in ultrahigh vacuum remained to be shown. Here we combine single photon time correlations with STML to me…
Influence of a graphene substrate on the stabilization of molecular systems with hydrogen bonds
N.N. Semenov Federal Research Center for Chemical Physics of the Russian Academy of Sciences（俄罗斯科学院N.N.谢苗诺夫化学物理联邦研究中心）；Plekhanov Russian University of Economics（普列汉诺夫俄罗斯经济大学）
Water confinement inside a carbon nanotube (CNT) has been one of the most exciting subjects of both experimental and theoretical interest. Most of the previous studies, however, considered CNT structures with simple cylindrical shapes. In this paper, we report a classical molecular dynamics study of the equilibrium structural arrangement of water molecules confined in a multiply connected carbon nanotube (MCCNT) containing two Y-junctions. We investigate the structural arrangement of the water molecules in the MCCNT in terms of the density of water molecules and the average number of hydrogen …
Molecular vibrational spectroscopy with the scanning tunneling microscope is feasible but usually detects few vibrational modes. We harness sharp Yu-Shiba-Rusinov (YSR) states observed from molecules on a superconductor to significantly enhance the vibrational signal. From a lead phthalocyanin molecule 46 vibrational peaks are resolved enabling a comparison with calculated modes. The energy resolution is improved beyond the thermal broadening limit and shifts induced by neighbor molecules or the position of the microscope tip are determined. Vice versa, spectra of vibrational modes are used to…
The reversible control of a single spin of an atom or a molecule is of great interest in Kondo physics and a potential application in spin based electronics.Here we demonstrate that the Kondo resonance of manganese phthalocyanine molecules on an Au(111) substrate have been reversibly switched off and on via a robust route through attachment and detachment of single hydrogen atom to the magnetic core of the molecule. As further revealed by density functional theory calculations, even though the total number of electrons of the Mn ion remains almost the same in the process, gaining one single hy…
We report a collection of lowest-energy structures of hydrocarbon molecules C_{m}H_{n} (m=1-18; n=0-2m+2). The structures are examined within a wide hydrogen chemical potential range. The genetic algorithm combined with Brenner's empirical potential is applied for the search. The resultant low-energy structures are further studied by ab initio quantum chemical calculations. The lowest-energy structures are presented with several additional low-energy structures for comparison. The results are expected to provide useful information for some unresolved astronomical spectra and the nucleation of …
Recent years have shown steady progress in research towards molecular electronics [1,2], where molecules have been investigated as switches [3-5], diodes [6], and electronic mixers [7]. In much of the previous work a Scanning Tunnelling Microscope was employed to address an individual molecule. As this arrangement does not provide long-term stability, more recently metal-molecule-metal links have been made using break junction devices [8-10]. However, it has been difficult to establish unambiguously that a single molecule forms the contact [11]. Here, we show that a single H2 molecule can form…
Pristine graphene is not suitable for hydrogen storage at ambient conditions since it binds the hydrogen molecules only by van der Waals interactions. However, the adsorption energy of the hydrogen molecules can be improved by doping or decorating metal atoms on the graphene monolayer. The doping and decoration processes are challenging due to the oxygen interference in hydrogen adsorption and the clustering issue of metal atoms. To improve the hydrogen adsorption energy in pristine graphene, we have explored the hydrogen storage capabilities of graphene monolayer in the presence of compressiv…
It is widely believed that when a molecule with thiol (S-H) end groups bridges a pair of gold electrodes, the S atoms bond to the gold and the thiol H atoms detach from the molecule. However, little is known regarding the details of this process, its time scale, and whether molecules with and without thiol hydrogen atoms can coexist in molecular junctions. Here we explore theoretically how inelastic tunneling spectroscopy (IETS) can shed light on these issues. We present calculations of the geometries, low bias conductances and IETS of propanedithiol and propanedithiolate molecular junctions w…
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. Ground state nuclear distribution, stability, and low vibrational excitation are investigated. Ground state results predict significant deviations from the BO treatment that is based on a potential energy surface (PES) obtained with the same QMC accuracy. The quantum mechanical distribution of molecular axis direction and bond length at a sub-nanom…
The graphane with chemically bonded alkali metals (Li, Na, K) was considered as potential material for hydrogen storage. The ab initio calculations show that such material can adsorb as many as 4 hydrogen molecules per Li, Na and K metal atoms. These values correspond to 12.20 wt%, 10.33 wt% and 8.56 wt% of hydrogen, respectively and exceed the DOE requirements. The thermodynamic analysis shows that Li-graphane complex is the most promising for hydrogen storage with ability to adsorb 3 hydrogen molecules per metal atom at 300 K and pressure in the range from 5 to 250 atm.
