Rigid ground state structure of 1,2-dihydro-3H-benz[e]inden-3-one deformed in the lowest electronic triplet state

The X-ray diffraction of crystalline 1,2-dihydro-3H-benz[e]inden-3-one (DHBI) reveals that the molecular geometry is fully planar in the electronic ground state. Glassy solutions of naphthaldehyde, 2-acetonaphthone and methyl 2-naphthoate in the mixtures methylcyclohexane/iso-pentane (MIP) and methanol/ethanol (ME) are phosphorescent. DHBI in ME shows phosphorescence, but in MIP it is non-phosphorescent. The phosphorescence spectra of these compounds and of naphthalene have a strong resemblance. This is in accordance with a molecular distortion in the lowest triplet state, which decouples the π electron systems of the carbonyl group and the naphthyl group. The absence of phosphorescence of DHBI in MIP, indicates a geometry of the triplet state, having a non-planar naphthalene ring, when the molecule is in the non-hydrogen bonded form.     

STM studies on porphyrins

Porphyrins are promising components to be used in molecular electronics due to their rich electronic/photonic properties. Preparation of supramolecular architectures of porphyrins on solid surfaces would constitute a basis for further development toward molecular circuitry or other constructs for molecular electronics applications. Assemblies on surfaces can be probed with scanning tunneling microscopy (STM) at submolecular resolutions to reveal the arrangements and conformations of molecules on an individual molecule basis. The electronic characteristics within a single porphyrin molecule can also be probed by means of the same technique. This review summarizes the status quo of STM studies on porphyrins on surfaces with regard to their assemblies, structures, and electronic properties at the single molecule level.     

Controlling Single Molecule Conductance by a Locally Induced Chemical Reaction on Individual Thiophene Units

Among the prerequisites for the progress of single‐molecule‐based electronic devices are a better understanding of the electronic properties at the individual molecular level and the development of methods to tune the charge transport through molecular junctions. Scanning tunneling microscopy (STM) is an ideal tool not only for the characterization, but also for the manipulation of single atoms and molecules on surfaces. The conductance through a single molecule can be measured by contacting the molecule with atomic precision and forming a molecular bridge between the metallic STM tip electrode and the metallic surface electrode. The parameters affecting the conductance are mainly related to their electronic structure and to the coupling to the metallic electrodes. Here, the experimental and theoretical analyses are focused on single tetracenothiophene molecules and demonstrate that an in situ‐induced direct desulfurization reaction of the thiophene moiety strongly improves the molecular anchoring by forming covalent bonds between molecular carbon and copper surface atoms. This bond formation leads to an increase of the conductance by about 50 % compared to the initial state.     

Detecting Air Pollutant Molecules Using Tube-Shaped Single Electron Transistor

An air pollution detector is proposed based on a tube-shaped single-electron transistor (SET) sensor. By monitoring the flow control component of the detector, each air pollutant molecule can be placed at the center of a SET nanopore and is treated as an island of the SET device in the same framework. Electron transport in the SET was incoherent, and the performances of the SET were sensitive at the single molecule level. Employing first-principles calculations, electronic features of an air pollutant molecule within a tube-shaped SET environment were found to be independent of the molecule rotational orientations with respect to axis of symmetry, unlike the electronic features in a conventional SET environment. Charge stability diagrams of the island molecules were demonstrated to be distinct for each molecule, and thus they can serve as electronic fingerprints for detection. Using the same setup, quantification of the air pollutant can be realized at room temperature as well. The results presented herein may help provide guidance for the identification and quantification of various types of air pollutants at the molecular level by treating the molecule as the island of the SET component in the proposed detector.     

Optical properties of current carrying molecular wires

We consider several fundamental optical phenomena involving single molecules in biased metal-molecule-metal junctions. The molecule is represented by its highest occupied and lowest unoccupied molecular orbitals, and the analysis involves the simultaneous consideration of three coupled fluxes: the electronic current through the molecule, energy flow between the molecule and electron-hole excitations in the leads, and the incident and/or emitted photon flux. Using a unified theoretical approach based on the nonequilibrium Green's function method we derive expressions for the absorption line shape (not an observable but a useful reference for considering yields of other optical processes) and for the current induced molecular emission in such junctions. We also consider conditions under which resonance radiation can induce electronic current in an unbiased junction. We find that current driven molecular emission and resonant light induced electronic currents in single molecule junctions can be of observable magnitude under appropriate realizable conditions. In particular, light induced current should be observed in junctions involving molecular bridges that are characterized by strong charge-transfer optical transitions. For observing current induced molecular emission we find that in addition to the familiar need to control the damping of molecular excitations into the metal substrate the phenomenon is also sensitive to the way in which the potential bias is distributed on the junction.     

Molecular electronegativity in density functional theory (VI)

Based on the density functional theory and partitioning the molecular electron density ρ (r) into atomic electronic densities and bond electronic densities, the expressions of the total molecular energy and the “effective electronegativity” of an atom or a bond in a molecule are obtained. The atom-bond electronegativity equalization model is then proposed for the direct calculation of the total molecular energy and the charge distribution of large molecules. Practical calculations show that the atom-bond electronegativity equalization model can reproduce the correspondingab initio values of the total molecular energies and charge distributions for a series of large molecules with a very satisfactory accuracy.     

Amino-carboxylic recognition on surfaces: from 2D to 2D + 1 nano-architectures

The control of the electronic properties of the interfaces between small organic molecules and the substrate is key for the development of efficient and reliable organic-based devices. A promising and widely covered route is to interpose a Self-Assembled Monolayer (SAM) to bridge the molecular film and the electrode. The morphology and the electronic level alignment of the triple substrate-SAM-organic layered system can be tuned by properly selecting the SAM composition. We have recently proposed a novel approach to the problem where, under ultra-high vacuum conditions, a molecular film is anchored to the SAM by exploiting the recognition between molecules functionalized, respectively, with -NH(2) and -COOH end-groups. Here we briefly review the role of the amino-carboxylic interaction in the formation of ordered organic 2-dimensional architectures on solid surfaces. We then describe the anchoring process of carboxylic molecules on amine based SAMs we have recently reported on. New results are presented showing how multiple anchoring sites per molecule may be exploited for tailoring the molecular orientation as well as the density of the anchored molecules.     

1,8-二巯基芘分子电学特性的理论研究

Based on the first principle,electrical properties of a molecular junction consisting of pyrene-1,8-dithiol molecule and gold surface have been investigated. The cluster of three gold atoms is used to simulate the gold surface. Density functional theory is employed to obtain the electronic structures of the molecule and the extended molecule. Then the frontier orbital theory and the perturbation theory are used to determine the interaction energy between the molecule and the gold surface quantitatively. The elastic Green function method is applied to study the current-voltage properties of the molecular junction. Numerical results show that the sulfur atoms can be chemically absorbed on the gold surface and the bonding between the molecule and gold is mainly covalent-typed. The fermienergy of the extended molecular system lies between the HOMO and the LUMO and closer to the HOMO of the system. When the external applied bias is lower than 1 V,there is a current gap for the molecular junction. With the increasing of the bias,the conductance of the junction exhibits plateaus. These electrical properties are closely related with the electronic structures of the molecular junction. The extended molecular orbits have great contribution to the charge transport. Localized molecular orbits give little contribution to the current while charge transport is taken place by tunneling.     

Tunneling currents that increase with molecular elongation

We present a model molecular system with an unintuitive transport-extension behavior in which the tunneling current increases with forced molecular elongation. The molecule consists of two complementary aromatic units (1,4-anthracenedione and 1,4-anthracenediol) hinged via two ether chains and attached to gold electrodes through thiol-terminated alkenes. The transport properties of the molecule as it is mechanically elongated in a single-molecule pulling setting are computationally investigated using a combination of equilibrium molecular dynamics simulations of the pulling with gDFTB computations of the transport properties in the Landauer limit. Contrary to the usual exponential decay of tunneling currents with increasing molecular length, the simulations indicate that upon elongation electronic transport along the molecule increases 10-fold. The structural origin of this inverted trend in the transport is elucidated via a local current analysis that reveals the dual role played by H-bonds in both stabilizing π-stacking for selected extensions and introducing additional electronic couplings between the complementary aromatic rings that also enhance tunneling currents across the molecule. The simulations illustrate an inverted electromechanical single-molecule switch that is based on a novel class of transport-extension behavior that can be achieved via mechanical manipulation and highlight the remarkable sensitivity of conductance measurements to the molecular conformation.     

Mereology and quantum chemistry: the approximation of molecular orbital

Mulliken proposed an Aufbauprinzip for the molecules on the basis of molecular spectroscopy while establishing, point by point, his concept of molecular orbit. It is the concept of electronic state which becomes the lever for his attribution of electronic configurations to a molecule. In 1932, the concept of orbit was transmuted into that of the molecular orbital to integrate the probabilistic approach of Born and to achieve quantitative accuracy. On the basis of the quantum works of Hund, Wigner, Lennard-Jones and group theory, he suggested the fragment method to establish the characteristics of molecular orbital for polyatomic molecules. These developments make it possible to bring elements of thought on the relation between a molecular “whole” and its “parts”. An operational realism combined with the second law of thermodynamics can pave the way for interesting tracks in the mereological study of chemical systems.     

X-Ray Absorption Spectroscopy on Free Molecules

The most recent spectroscopic method that can be applied to chemical problems is X-ray absorption spectroscopy, in which the excitation of individual core electrons of an atom is studied. The analysis of the spectra with the aid of simple theoretical models yields information both about the core orbitals of the atom and about the unoccupied molecular orbitals, from which various molecular properties can be deduced. These not only include charge distribution, electronic configuration, geometry, and spatial and energy characteristics of orbitals of the molecule under investigation; one can also obtain parameters of radicals (such as stability, bond length, ionization potential, and electronic excitation energy) that differ from the molecule under investigation in that the nuclear charge of one atom is one unit higher.     

A group contribution method applied to electronic correlation energies of molecules

A scheme for assigning molecular correlation energies to bonds within the molecule is proposed and applied to a variety of molecules for which nonempirical electronic energies and heats of formation are available. The bond correlation energies are employed to predict the molecular correlation energies of some molecules and good agreement was found between the predicted and “experimental” values.     

Nonequilibrium electronic transport of 4,4'-bipyridine molecular junction

The electronic transport properties of a 4,4'-bipyridine molecule sandwiched between two Au(111) surfaces are studied with a fully self-consistent nonequilibrium Green's-function method combined with the density-functional theory. The 4,4'-bipyridine molecule prefers to adsorb near the hollow site of the Au(111) surface and distorts slightly. The modifications on the electronic structure of the molecule due to the presence of the electrodes are described by the renormalized molecular orbitals, which correspond well to the calculated transmission peaks. The average Fermi level lies close to the lowest unoccupied renormalized molecular orbital, which determines the electronic transport property of the molecular junction under a small bias voltage. The total transmission is contributed by a single channel. The transmission peaks shift with the applied bias voltage, and this behavior depends on the spatial distribution of the renormalized molecular orbitals and the voltage drop along the molecular junction. The shape of the calculated conductance curve of the equilibrium geometric configuration reproduces the main feature of the experimental results, but the value is larger than the measured data by about 6 times. Good agreement with the experimental measurements can be obtained by elongating the molecular junction. The electronic transport behaviors depend strongly on the interface configuration.     

7,7,8,8-tetracyanoquinodimethane-based molecular dopants for p-type doping of OLEDs: a theoretical investigation

The array of organic conductivity dopants used for organic light-emitting devices (OLEDs) to reduce the operating voltage and improve power efficiency is extremely limited. Here we report a comparative theoretical study between newly proposed analogues and the standard state-of-the-art conductivity dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ). We used density functional theory to determine the bond lengths, bond angles, and electronic properties, such as the energy of the highest occupied molecular orbital (E(HOMO)) and the lowest unoccupied molecular orbital (E(LUMO)) states. The ground state structures of the proposed molecules were optimized at the B3LYP/6-31G* level. The results show that substitution of one or two fluorine groups in the F4-TCNQ core with a substituted phenyl ring or other electron-withdrawing moieties, will not substantially affect the geometry of the molecule or its electronic ability to accept electrons. The most significant finding was that the phenyl substitutions onto the TCNQ core are nearly perpendicular to the TCNQ plane, and thus there is no electronic communication between the two rings. This is extremely important, as such extension of the π conjugated system would negatively affect the E(LUMO) and thus the electron affinity of the molecule.     

Dihydroxy(4-thiomorpholinomethyl)benzoic acid: from molecular asymmetry to diode characteristics

One of the challenges in molecular electronics is to design molecules which can be used as functional units in electronic devices. The subject of our investigations is an asymmetrical molecule, dihydroxy(4-thiomorpholinomethyl)benzoic acid (TMBA), whose structural and electronic properties are characterized. The self-assembly behavior of TMBA on Au(111) surfaces resulting in highly ordered monolayers is obtained using scanning tunneling microscopy (STM). Furthermore, investigations on the electronic properties of the combined metal/molecule system reveal an orbital mediated tunneling process and tunneling decay constants for the carboxylic and thiomorpholino group. Thus, a diode-like character of TMBA is shown to be caused by intrinsic electronic properties of different molecular moieties.