Rotation of a single molecule within a supramolecular bearing

Experimental visualization and verification of a single-molecule rotor operating within a supramolecular bearing is reported. Using a scanning tunneling microscope, single molecules were observed to exist in one of two spatially defined states laterally separated by 0.26 nanometers. One was identified as a rotating state and the other as an immobilized state. Calculations of the energy barrier for rotation of these two states show that it is below the thermal energy at room temperature for the rotating state and above it for the immobilized state.     

Current-induced hydrogen tautomerization and conductance switching of naphthalocyanine molecules

The bistability in the position of the two hydrogen atoms in the inner cavity of single free-base naphthalocyanine molecules constitutes a two-level system that was manipulated and probed by low-temperature scanning tunneling microscopy. When adsorbed on an ultrathin insulating film, the molecules can be switched in a controlled fashion between the two states by excitation induced by the inelastic tunneling current. The tautomerization reaction can be probed by resonant tunneling through the molecule and is expressed as considerable changes in the conductivity of the molecule. We also demonstrated a coupling of the switching process so that the charge injection in one molecule induced tautomerization in an adjacent molecule.     

Vibrationally resolved fluorescence excited with submolecular precision

Tunneling electrons from a scanning tunneling microscope (STM) were used to excite photon emission from individual porphyrin molecules adsorbed on an ultrathin alumina film grown on a NiAl(110) surface. Vibrational features were observed in the light-emission spectra that depended sensitively on the different molecular conformations and corresponding electronic states obtained by scanning tunneling spectroscopy. The high spatial resolution of the STM enabled the demonstration of variations in light-emission spectra from different parts of the molecule. These experiments realize the feasibility of fluorescence spectroscopy with the STM and enable the integration of optical spectroscopy with a nanoprobe for the investigation of single molecules.     

Atomic-scale coupling of photons to single-molecule junctions

Spatial resolution at the atomic scale has been achieved in the coupling of light to single molecules adsorbed on a surface. Electron transfer to a single molecule induced by green to near-infrared light in the junction of a scanning tunneling microscope (STM) exhibited spatially varying probability that is confined within the molecule. The mechanism involves photo-induced resonant tunneling in which a photoexcited electron in the STM tip is transferred to the molecule. The coupling of photons to the tunneling process provides a pathway to explore molecular dynamics with the combined capabilities of lasers and the STM.     

Molecule cascades

Carbon monoxide molecules were arranged in atomically precise configurations, which we call "molecule cascades," where the motion of one molecule causes the subsequent motion of another, and so on in a cascade of motion similar to a row of toppling dominoes. Isotopically pure cascades were assembled on a copper (111) surface with a low-temperature scanning tunneling microscope. The hopping rate of carbon monoxide molecules in cascades was found to be independent of temperature below 6 kelvin and to exhibit a pronounced isotope effect, hallmarks of a quantum tunneling process. At higher temperatures, we observed a thermally activated hopping rate with an anomalously low Arrhenius prefactor that we interpret as tunneling from excited vibrational states. We present a cascade-based computation scheme that has all of the devices and interconnects required for the one-time computation of an arbitrary logic function. Logic gates and other devices were implemented by engineered arrangements of molecules at the intersections of cascades. We demonstrate a three-input sorter that uses several AND gates and OR gates, as well as the crossover and fan-out units needed to connect them.     

Reversible rotation of antimony dimers on the silicon (001) surface with a scanning tunneling microscope

The scanning tunneling microscope (STM) was used to control the configuration of antimony clusters on the (001) surface of silicon. In particular, the STM tip induced a reversible rotation between two orthogonal orientations of individual antimony dimers on the surface. This simple rotation can be explained by an atomic-scale torque exerted on the antimony dimers by the STM tip. The reversibility of this process could provide a basis for making atomic-scale memory cells.     

Probing high-barrier pathways of surface reactions by scanning tunneling microscopy

The ability of scanning tunneling microscopy to probe the pathways of thermally activated high-barrier surface processes is frequently limited by competing low-barrier processes that can confuse measurement of the true initial and final configuration. We introduce an approach to circumvent this difficulty by driving the surface process with nanosecond laser heating. The method is applied to determine the pathway of recombinative desorption in the H/Si(001) system. The observed configuration of dangling bonds after laser heating reveals that the desorbed hydrogen molecules are not formed on single dimers, but rather from neighboring silicon dimers via an interdimer reaction pathway.     

Molecular structure of DNA by scanning tunneling microscopy

Uncoated DNA molecules marked with an activated tris(l-aziridinyl) phosphine oxide (TAPO) solution were deposited on gold substrates and imaged in air with the use of a high-resolution scanning tunneling microscope (STM). Constant-current and gap-modulated STM images show clear evidence of the helicity of the DNA structure: pitch periodicity ranges from 25 to 35 angstroms, whereas the average diameter is 20 angstroms. Molecular structure within a single helix turn was also observed.     

Atomic and molecular manipulation with the scanning tunneling microscope

The prospect of manipulating matter on the atomic scale has fascinated scientists for decades. This fascination may be motivated by scientific and technological opportunities, or from a curiosity about the consequences of being able to place atoms in a particular location. Advances in scanning tunneling microscopy have made this prospect a reality; single atoms can be placed at selected positions and structures can be built to a particular design atom-by-atom. Atoms and molecules may be manipulated in a variety of ways by using the interactions present in the tunnel junction of a scanning tunneling microscope. Some of these recent developments and some of the possible uses of atomic and molecular manipulation as a tool for science are discussed.     

Intermolecular electron transfer by quantum mechanical tunneling

The transfer of electrons from one molecule to another by quantum mechanical tunneling has recently been implicated in biological electron transport. This report describes observations of electron transfer between aromatic molecules in a rigid matrix, in which electrons apparently tunnel through tens of angstroms of inert solvent. The kinetics tend to confirm the tunneling process, which is likely to be an important means of electron transfer when diffusion is blocked by steric factors or immobilization of the reactants.     

Smectic liquid crystal monolayers on graphite observed by scanning tunneling microscopy

By means of scanning tunneling microscopy, it is observed that molecules of the form n-alkylcyanobiphenyl, where n = 8 to 12, form two-dimensional crystalline domains when adsorbed onto graphite. The layer spacings measured by tunneling microscopy are 20% larger than those measured previously on bulk material by x-ray diffraction. The structure of the adsorbed molecules is quite different from that of the bulk.     

Organic molecules acting as templates on metal surfaces

The electronic connection of single molecules to nanoelectrodes on a surface is a basic, unsolved problem in the emerging field of molecular nanoelectronics. By means of variable temperature scanning tunneling microscopy, we show that an organic molecule (C90H98), known as the Lander, can cause the rearrangement of atoms on a Cu(110) surface. These molecules act as templates accommodating metal atoms at the step edges of the copper substrate, forming metallic nanostructures (0.75 nanometers wide and 1.85 nanometers long) that are adapted to the dimensions of the molecule.     

Electronically induced atom motion in engineered CoCun nanostructures

We have measured the quantum yield for exciting the motion of a single Co atom in CoCu(n) linear molecules constructed on a Cu(111) surface. The Co atom switched between two lattice positions during electron excitation from the tip of a scanning tunneling microscope. The tip location with highest probability for inducing motion was consistent with the position of an active state identified through electronic structure calculations. Atom motion within the molecule decreased with increased molecular length and reflected the corresponding variation in electronic structure.     

Inelastic electron tunneling spectroscopy

Inelastic electron tunneling spectroscopy is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of oxide layers in a metal-insulator-metal tunnel junction. The technique involves studying the effects of adsorbed molecules on the tunneling spectrum of such junctions. The data give useful information about the structure, bonding, and orientation of adsorbed molecules. One of the major advantages of inelastic electron tunneling spectroscopy is its sensitivity. It is capable of detecting on the order of 10(10) molecules (a fraction of a monolayer) on a 1-square-millimeter junction. It has been successfully used in studies of catalysis, biology, trace impurity detection, and electronic excitations. Because of its high sensitivity, this technique shows great promise in the area of solid-state electronic chemical sensing.     

Rectification of STM Current to Graphite Covered with Phthalocyanine Molecules

The scanning tunneling microscope (STM) can be used to measure current-voltage characteristics on an atomic scale. The attachment of copper phthalocyanine molecules, in contrast to a variety of other molecules, to graphite changes the electrical characteristics of the STM from relatively symmetric to highly asymmetric or rectifying. Evidence is presented to show that the asymmetry arises because of the electronic energy levels of the copper phthalocyanine. The organic molecules were bonded to the graphite by an acid-base reaction that may have wide applicability.     

Monoclonal antibody-mediated tumor regression by induction of apoptosis

To characterize cell surface molecules involved in control of growth of malignant lymphocytes, monoclonal antibodies were raised against the human B lymphoblast cell line SKW6.4. One monoclonal antibody, anti-APO-1, reacted with a 52-kilodalton antigen (APO-1) on a set of activated human lymphocytes, on malignant human lymphocyte lines, and on some patient-derived leukemic cells. Nanogram quantities of anti-APO-1 completely blocked proliferation of cells bearing APO-1 in vitro in a manner characteristic of a process called programmed cell death or apoptosis. Cell death was preceded by changes in cell morphology and fragmentation of DNA. This process was distinct from antibody- and complement-dependent cell lysis and was mediated by the antibody alone. A single intravenous injection of anti-APO-1 into nu/nu mice carrying a xenotransplant of a human B cell tumor induced regression of this tumor within a few days. Histological thin sections of the regressing tumor showed that anti-APO-1 was able to induce apoptosis in vivo. Thus, induction of apoptosis as a consequence of a signal mediated through cell surface molecules like APO-1 may be a useful therapeutic approach in treatment of malignancy.     

Electron tunneling through organic molecules in frozen glasses

Reaction rates extracted from measurements of donor luminescence quenching by randomly dispersed electron acceptors reveal an exponential decay constant of 1.23 per angstrom for electron tunneling through a frozen toluene glass (with a barrier to tunneling of 1.4 electron volts). The decay constant is 1.62 per angstrom (the barrier, 2.6 electron volts) in a frozen 2-methyl-tetrahydrofuran glass. Comparison to decay constants for tunneling across covalently linked xylyl (0.76 per angstrom) and alkyl (1.0 per angstrom) bridges leads to the conclusion that tunneling between solvent molecules separated by approximately 2 angstroms (van der Waals contact) is 20 to 50 times slower than tunneling through a comparable length of a covalently bonded bridge. Our results provide experimental confirmation that covalently bonded pathways can facilitate electron flow through folded polypeptide structures.     

Direct visualization of the formation of single-molecule conjugated copolymers

Electrochemical polymerization of two different kinds of thiophene monomers on an iodine-covered gold surface created highly assembled conjugated copolymers with different electronic structures. A scanning tunneling microscope revealed images of several linkage types: diblock, triblock, and multiblock. The single strand of conjugated copolymers exhibited an anomalous swinging motion on the surface. This technique presents the possibility of understanding the copolymerization process from the different monomers on the single-molecular scale and of building single-molecule superlattices on a surface through controlled electropolymerization.     

Single-molecule vibrational spectroscopy and microscopy

Vibrational spectra for a single molecule adsorbed on a solid surface have been obtained with a scanning tunneling microscope (STM). Inelastic electron tunneling spectra for an isolated acetylene (C2H2) molecule adsorbed on the copper (100) surface showed an increase in the tunneling conductance at 358 millivolts, resulting from excitation of the C-H stretch mode. An isotopic shift to 266 millivolts was observed for deuterated acetylene (C2D2). Vibrational microscopy from spatial imaging of the inelastic tunneling channels yielded additional data to further distinguish and characterize the two isotopes. Single-molecule vibrational analysis should lead to better understanding and control of surface chemistry at the atomic level.     

Picometer-scale electronic control of molecular dynamics inside a single molecule

Tunneling electrons from a low-temperature (5 kelvin) scanning tunneling microscope were used to control, through resonant electronic excitation, the molecular dynamics of an individual biphenyl molecule adsorbed on a silicon(100) surface. Different reversible molecular movements were selectively activated by tuning the electron energy and by selecting precise locations for the excitation inside the molecule. Both the spatial selectivity and energy dependence of the electronic control are supported by spectroscopic measurements with the scanning tunneling microscope. These experiments demonstrate the feasibility of controlling the molecular dynamics of a single molecule through the localization of the electronic excitation inside the molecule.