Control of relative tunneling rates in single molecule bipolar electron transport

The influence of relative electron tunneling rates on electron transport in a double-barrier single-molecule junction is studied. The junction is defined by positioning a scanning tunneling microscope tip above a copper phthalocyanine molecule adsorbed on a thin oxide film grown on the NiAl(110) surface. By tuning the tip-molecule separation, the ratio of tunneling rates through the two barriers, vacuum and oxide, is controlled. This results in dramatic changes in the relative intensities of individual conduction channels, associated with different vibronic states of the molecule.     

Controlled transport through a single molecule

We demonstrate how an electrode-molecule-electrode junction can be controllably opened and closed by careful tuning of the contacts' interspace and voltage. The molecule, an octanethiol, flips to bridge a ~1 nm interspace between substrate and scanning tunnelling microscope tip when an electric field exceeds a threshold (switch 'on'). Reducing the field below this threshold value leads to the reproducible detachment of the octanethiol (switch 'off'). Once contacted, a further reduction of the contacts' interspace leads to an increase of the conductance of the molecule.     

Quantum transport of the single metallocene molecule

The Quantum transport of three single metallocene molecule is investigated by performing theoretical calculations using the non-equilibrium Green's function method combined with density functional theory. We find that the three metallocen molecules structure become stretched along the transport direction, the distance between two C_p rings longer than the other theory and experiment results. The lager conductance is found in nickelocene molecule, the main transmission channel is the electron coupling between molecule and the electrodes is through the Ni d_xz and d_yz orbitals and the s, d_xz, d_yz of gold. This is also confirmed by the highest occupied molecular orbital resonance at Fermi level. In addition, negative differential resistance effect is found in the ferrocene, cobaltocene molecules, this is also closely related with the evolution of the transmission spectrum under applied bias.     

Vibronic coupling effects in the C60 molecule

Many recent experiments have established that the Jahn-Teller (JT) effect plays a very important role in determining the properties of the C₆₀ molecule. A review of the underlying theory developed by the Nottingham group is presented for cases in which distinct minima in the potential energy surface occur. This relates directly to the C₆₀ molecule through the consideration of the T ⊗ h and H ⊗ h JT systems. When only linear coupling terms exist in the T ⊗ h system, the minima form a continuous trough of SO(3) symmetry and new methods must be used. Some details of these results are presented.     

Theoretical investigation of the O2 adsorption effect in the electron transport of single Fe-porphyrin molecule

The effect of O₂ adsorption on the electron transport behavior of Fe-porphyrin molecule is investigated by the first-principles computational approach. The current-voltage characteristics of Fe-porphyrin and O₂ adsorbed Fe-porphyrin between gold electrodes are calculated. We find that the conductance of the Fe-porphyrin decreases dramatically upon the adsorption of O₂, which suggests that this system has potential application as a molecular sensor or a switch. This switching-behavior is analyzed from the evolutions of the transmission spectra and the molecular projected self-consistent Hamiltonian states of the molecular systems.     

Vibronic interaction in the lower electronic states of benzene

Results of further calculations on the dynamic coupling between the lower B _1u and E _1u electronic states of benzene via a single e _2g mode are presented. In part I we gave the ‘pseudo-cylindrical’ solutions that result when the leading coupling term, linear in the nuclear displacements, is considered (cylindrical Born-Oppenheimer potential). Here we investigate the effect of

1. (1) the next higher terms in the expansion of the coupling hamiltonian for the free molecule (hexagonal Born-Oppenheimer potential);

2. (2) a crystal field anisotropy.

From the scanty data on the coupling constants available a priori it would follow that the refinement introduced by (1) is small for benzene. On the contrary, the effect of even a small crystal field anisotropy is predicted to be appreciable.

The results of the calculations are analysed by comparison with experimental data on the benzene crystal at low temperature. A consistent interpretation of both magnetic resonance results and the triplet ← singlet absorption spectrum is obtained.     

Vibronic spectra of aluminium monochloride relevant to circumstellar molecule

The A^1Π→ X^1Σ^+ transition system of aluminium monochloride is determined by using ab initio quantum chemistry.Based on the multi-reference configuration interaction method in conjugate to the Davidson correction(MRCI + Q), the potential energy curves(PECs) of the three electronic states are obtained. Transition dipole moments(TDMs) and the vibrational energy levels are studied by employing the aug-cc-pwCV5Z-DK basis set with 4220-active space. The rovibrational constants are first determined from the analytic potential by solving the rovibrational Schr ¨odinger equation, and then the spectroscopic constants are determined by fitting the vibrational levels, and these values are well consistent with the experimental data. The effect of spin–orbit coupling(SOC) on the spectra and vibrational properties are evaluated.The results show that the SOC effect has almost no influence on the spectroscopic constants of AlCl molecules. For the A^1Π→ X^1Σ^+transition, the highly diagonalized Frank–Condon factor(FCF) is f(00)=0.9988. Additionally, Einstein coefficients and radiative lifetimes are studied, where the vibrational bands include ν'= 0–19→ν'=0–9. The ro-vibrational intensity is calculated at a temperature of 296 K, which can have certain astrophysical applications. At present, there is no report on the calculation of Al Cl ro-vibrational intensity, so we hope that our results will be useful in analyzing the interstellar Al Cl based on the absorption from A^1Π→ X^1Σ^+.     

Effect of surface states on electron transport in individual ZnO nanowires

The current–voltage (I–V$I\text{–}V$) characteristics of single ZnO nanowires have been studied in the humid air, dry air, vacuum, and under ultraviolet (UV) irradiation. A model of a single ZnO nanowire connected with two opposite diodes was proposed to calculate the observed I–V$I\text{–}V$ behaviors. The results show that the electrical characteristics are dominated by the reverse barrier height, and the barrier height can be adjusted by surface adsorption, which is ascribed to the effect of surface states on surface band bending and Fermi level pining. Furthermore, the nanowire exhibited an enormous increase of conductance upon UV irradiation and a considerable persistent photocurrent after withdraw of the UV excitation, which further confirms the surface states have a pronounced effect on the electronic transport in single ZnO nanowires.     

Vibronic instabilities in a system with nonrigid electron bands

The vibronic dynamical lattice destabilization of a gapped two-band system with moving upper band bottom is investigated in one, two and three dimensions. The second order electron energy renormalization leading to possible destabilization has been calculated for various characteristic physical dispositions. The position of the chemical potential in the upper band near the gap edge promotes the destabilization. The dimensionality of the system does not change the general trends in the behavior of the destabilization. However, in low dimensional cases the chemical potential entering the singularity in the density of states enhances the speed of destabilization rapidly.     

Few-electron molecular states and their transitions in a single InAs quantum dot molecule

We study electronic configurations in a single pair of vertically coupled self-assembled InAs quantum dots, holding just a few electrons. By comparing the experimental data of nonlinear single-electron transport spectra in a magnetic field with many-body calculations, we identify the spin and orbital configurations to confirm the formation of molecular states by filling both the quantum mechanically coupled symmetric and antisymmetric states. Filling of the antisymmetric states is less favored with increasing magnetic field, and this leads to various magnetic field induced transitions in the molecular states.     

Counting statistics of single electron transport in a quantum dot

We have measured the full counting statistics of current fluctuations in a semiconductor quantum dot (QD) by real-time detection of single electron tunneling with a quantum point contact. This method gives direct access to the distribution function of current fluctuations. Suppression of the second moment (related to the shot noise) and the third moment (related to the asymmetry of the distribution) in a tunable semiconductor QD is demonstrated experimentally. With this method we demonstrate the ability to measure very low current and noise levels.     

Magneto-optical studies of ballistic electron transport in single barrier heterostructures

We report an investigation of ballistic electron transport in GaAs/AlGaAs p-i-n single barrier structures with magnetic fields of up to 14T applied parallel to the tunneling direction (B//z). The energy distribution and relaxation processes of the non-equilibrium electron population injected into the p-doped collector from the Landau levels of the emitter accumulation layer are studied by means of electroluminescence (EL) spectroscopy. The observation of emitter Landau level structure in the ballistic electron EL spectra shows that the 2D to 3D tunneling process is elastic. In addition to the ballistic electron EL, cross-barrier recombination between the electron and hole accumulation layers is observed. This allows a precise determination of the initial energy distribution of the injected electrons.     

Quantum superposition of high spin states in the single molecule magnet Ni4

Quantum tunneling of the magnetization in a single molecule magnet has been studied in experiments that combine microwave spectroscopy with high sensitivity magnetic measurements. By monitoring spin-state populations in the presence of microwave radiation, the energy splittings between low lying superpositions of high-spin states of single molecule magnet Ni4 (S=4) have been measured. Absorption linewidths give an upper bound on the rate of decoherence. Pulsed microwave experiments provide a measure of energy relaxation time, which is found to increase with frequency.     

Vibronic state specific predissociation rates from excited electronic states

It is shown that predissociation can be perceived as a primary process due to the continuum part of a Morse oscillator potential. In the model proposed here internal conversion to the ground state is thus not necessarily the primary process of a consecutive dissociation but may be a simultaneous decay. As a consequence, dissociation rates should show strong variations from specific (ro-) vibrational states of the first excited electronic states that are similar to those known from “pure” internal conversion rates. This behaviour is demonstrated by calculating predissociation rates for the process. Especially the out-of-plane modes seem to play an extraordinary role in the excess energy behaviour of the predissociation rate. At lower excess energies, rates from single vibronic levels with out-of-plane mode characteristics may show an increase by several orders of magnitude. Received: 13 November 1998     

电声子相互作用对量子点分子中单电子隧穿的影响

研究了双量子点系统中的电子隧穿动力学过程，在考虑电子与声子相互作用的情况下用基于 正则变换的微扰方法解析地得到了电子动态隧穿电流的表达式. 并且详细分析电子与声子耦 合引起的退相干问题，在此基础上指出了可能的退耦机理. 关键词： 电声子相互作用 双量子点 隧穿     

All electron ab initio investigations of the electronic states of the FeC molecule

The low-lying electronic states of the molecule FeC have been investigated by performing all electron ab initio multi-configuration self-consistent-field (CASSCF) and multi reference configuration interaction (MRCI) calculations. The relativistic corrections for the one-electron Darwin contact term and the relativistic mass-velocity correction have been determined in perturbation calculations. The electronic structure of the FeC molecule is interpreted as antiferromagnetic couplings of the localized angular momenta of the ions and resulting in a triple bond in the valence bond sense. The electronic ground state is confirmed as being . The spectroscopic constants for the ground state and eleven excited states have been derived from the results of the MRCI calculations. The spectroscopic constants for the ground state have been determined as and ,and for the low-lying state as and . The values for the ground state agree well with the available experimental data. The FeC molecule is polar with charge transfer from Fe to C. The dipole moment has been determined as in the ground state and as 1.51 D in the state. From the results of the MRCI calculations the dissociation energy, , is determined as 2.79 eV, and D₀ as 2.74 eV. Received: 2 October 1998 / Received in final form: 30 March 1999     

Coherent electron transport through an azobenzene molecule: a light-driven molecular switch

We apply a first-principles computational approach to study a light-sensitive molecular switch. The molecule that comprises the switch can convert between a trans and a cis configuration upon photoexcitation. We find that the conductance of the two isomers varies dramatically, which suggests that this system has potential application as a molecular device. A detailed analysis of the band structure of the metal leads and the local density of states of the system reveals the mechanism of the switch.