Tatsuhiko Ohto

Single molecular resistive switch obtained via sliding multiple anchoring points and varying effective wire length.

A single molecular resistive (conductance) switch via control of anchoring positions was examined by using a molecule consisting of more than two same anchors. For this purpose, we adopted the covered quaterthiophene (QT)-based molecular wire junction. The QT-based wire consisted of two thiophene ring anchors on each side; thus, shift of anchors was potentially possible without a change in the binding modes and distortion of the intramolecular structure. We observed three distinct conductance states by using scanning tunneling microscope-based break junction technique. A detailed analysis of the experimental data and first-principles calculations revealed that the mechanism of the resistive switch could be explained by standard length dependence (exponential decay) of conductance. Here, the length is the distance between the anchoring points, i.e., length of the bridged π-conjugated backbone. Most importantly, this effective tunneling length was variable via only controlling the anchoring positions in the same molecule. Furthermore, we experimentally showed the possibility of a dynamic switch of anchoring positions by mechanical control. The results suggested a distinct strategy to design functional devices via contact engineering.

Toward ab initio molecular dynamics modeling for sum-frequency generation spectra; an efficient algorithm based on surface-specific velocity-velocity correlation function.

Interfacial water structures have been studied intensively by probing the O-H stretch mode of water molecules using sum-frequency generation (SFG) spectroscopy. This surface-specific technique is finding increasingly widespread use, and accordingly, computational approaches to calculate SFG spectra using molecular dynamics (MD) trajectories of interfacial water molecules have been developed and employed to correlate specific spectral signatures with distinct interfacial water structures. Such simulations typically require relatively long (several nanoseconds) MD trajectories to allow reliable calculation of the SFG response functions through the dipole moment-polarizability time correlation function. These long trajectories limit the use of computationally expensive MD techniques such as ab initio MD and centroid MD simulations. Here, we present an efficient algorithm determining the SFG response from the surface-specific velocity-velocity correlation function (ssVVCF). This ssVVCF formalism allows us to calculate SFG spectra using a MD trajectory of only ∼100 ps, resulting in the substantial reduction of the computational costs, by almost an order of magnitude. We demonstrate that the O-H stretch SFG spectra at the water-air interface calculated by using the ssVVCF formalism well reproduce those calculated by using the dipole moment-polarizability time correlation function. Furthermore, we applied this ssVVCF technique for computing the SFG spectra from the ab initio MD trajectories with various density functionals. We report that the SFG responses computed from both ab initio MD simulations and MD simulations with an ab initio based force field model do not show a positive feature in its imaginary component at 3100 cm(-1).

Thermopower of benzenedithiol and C60 molecular junctions with Ni and Au electrodes.

We have performed thermoelectric measurements of benzenedithiol (BDT) and C60 molecules with Ni and Au electrodes using a home-built scanning tunneling microscope. The thermopower of C60 was negative for both Ni and Au electrodes, indicating the transport of carriers through the lowest unoccupied molecular orbital in both cases, as was expected from the work functions. On the other hand, the Ni-BDT-Ni junctions exhibited a negative thermopower, whereas the Au-BDT-Au junctions exhibited a positive thermopower. First-principle calculations revealed that the negative thermopower of Ni-BDT-Ni junctions is due to the spin-split hybridized states generated by the highest occupied molecular orbital of BDT coupled with s- and d-states of the Ni electrode.

Ab Initio Liquid Water Dynamics in Aqueous TMAO Solution

Ab initio molecular dynamics (AIMD) simulations in trimethylamine N-oxide (TMAO)-D2O solution are employed to elucidate the effects of TMAO on the reorientational dynamics of D2O molecules. By decomposing the O-D groups of the D2O molecules into specific subensembles, we reveal that water reorientational dynamics are retarded considerably in the vicinity of the hydrophilic TMAO oxygen (O(TMAO)) atom, due to the O-D···O(TMAO) hydrogen-bond. We find that this reorientational motion is governed by two distinct mechanisms: The O-D group rotates (1) after breaking the O-D···O(TMAO) hydrogen-bond, or (2) together with the TMAO molecule while keeping this hydrogen-bond intact. While the orientational slow-down is prominent in the AIMD simulation, simulations based on force field models exhibit much faster dynamics. The simulated angle-resolved radial distribution functions illustrate that the O-D···O(TMAO) hydrogen-bond has a strong directionality through the sp(3) orbital configuration in the AIMD simulation, and this directionality is not properly accounted for in the force field simulation. These results imply that care must be taken when modeling negatively charged oxygen atoms as single point charges; force field models may not adequately describe the hydration configuration and dynamics.

Lipid Carbonyl Groups Terminate the Hydrogen Bond Network of Membrane-Bound Water

We present a combined experimental sum-frequency generation (SFG) spectroscopy and ab initio molecular dynamics simulations study to clarify the structure and orientation of water at zwitterionic phosphatidylcholine (PC) lipid and amine N-oxide (AO) surfactant monolayers. Simulated O-H stretch SFG spectra of water show good agreement with the experimental data. The SFG response at the PC interface exhibits positive peaks, whereas both negative and positive bands are present for the similar zwitterionic AO interface. The positive peaks at the water/PC interface are attributed to water interacting with the lipid carbonyl groups, which act as efficient hydrogen bond acceptors. This allows the water hydrogen bond network to reach, with its (up-oriented) O-H groups, into the headgroup of the lipid, a mechanism not available for water underneath the AO surfactant. This highlights the role of the lipid carbonyl group in the interfacial water structure at the membrane interface, namely, stabilizing the water hydrogen bond network.

Polarizable Site Charge Model at Liquid/Solid Interfaces for Describing Surface Polarity: Application to Structure and Molecular Dynamics of Water/Rutile TiO2(110) Interface

We present a novel scheme to construct a polarizable force field for liquid/solid interfaces, which takes into account the effect of the surface polarity induced by liquid-solid interactions explicitly. We extend the charge response kernel (CRK) method for molecules to solid surfaces by introducing the surface CRK. The CRK parameters are systematically determined by the first-principles calculations in the slab model with the dipole-correction method. Our methodology is applied to the water/clean rutile TiO2(110) interface. Structures and induced charges of a single water molecule attached to the TiO2 surface optimized by our polarizable force field show good agreement with those predicted by the first-principles calculations. Further, we carried out MD simulations for the liquid water/TiO2 interface and found three stable structures of water attached to the TiO2 surface. Two of them are predicted by both the polarizable and the nonpolarizable force fields, while the polarizable force field model predicts a structure of water with the hydrogen and oxygen atoms interacting with the oxygen atom of the surface TiO2 and the hydrogen atom of the other water molecule, respectively, which was reported by the previous first-principles MD simulation. This indicates that the dipole moments of water and TiO2 induced by the water-TiO2 interactions have significant impact on molecular conformations of the water/TiO2 interface.

Surface tension of ab initio liquid water at the water-air interface

We report calculations on the surface tension of the water-air interface using ab initio molecular dynamics (AIMD) simulations. We investigate the influence of the cell size on surface tension of water from force field molecular dynamics simulations. We find that the calculated surface tension increases with increasing simulation cell size, thereby illustrating that a correction for finite size effects is essential for small systems that are customary in AIMD simulations. Moreover, AIMD simulations reveal that the use of a double-ζ basis set overestimates the experimentally measured surface tension due to the Pulay stress while more accurate triple and quadruple-ζ basis sets give converged results. We further demonstrate that van der Waals corrections critically affect the surface tension. AIMD simulations without the van der Waals correction substantially underestimate the surface tension while the van der Waals correction with the Grimmes D2 technique results in a value for the surface tension that is too high. The Grimmes D3 van der Waals correction provides a surface tension close to the experimental value. Whereas the specific choices for the van der Waals correction and basis sets critically affect the calculated surface tension, the surface tension is remarkably insensitive to the details of the exchange and correlation functionals, which highlights the impact of long-range interactions on the surface tension. Our simulated values provide important benchmarks, both for improving van der Waals corrections and AIMD simulations of aqueous interfaces.

Influence of surface polarity on water dynamics at the water/rutile TiO2(110) interface

We report molecular dynamics (MD) simulations of the water/clean rutile TiO2 (110) interface using polarizable and non-surface polarity force field models. The effect of surface polarity on the water dynamics near the TiO2(110) surface is addressed, specifically by calculating the water hydrogen bond and reorientational dynamics. The hydrogen bond lifetime of interfacial water molecules is several times longer than that of bulk water due to the strong water-TiO2 interactions. A comparison of the dynamics simulated with the polarizable and non-surface polarity models shows that, while the hydrogen bond lifetime between the interfacial water and TiO2 surface is insensitive to the surface polarity, the reorientational dynamics around this hydrogen bond axis is significantly influenced by the surface polarity; the surface polarity of the TiO2 increases the water-TiO2 interactions, stabilizing the local structure of the interfacial water molecules and restricting their rotational motion. This reorientation occurs predominantly by rotation around the O-H group hydrogen bonded to the TiO2 surface. Furthermore, we correlate the dynamics of the induced charge on the TiO2 surface with the interfacial water dynamics. Our results show that the timescale of correlations of the atom charges induced by the local electric field in bulk water is influenced by the rotational motion, hydrogen bond rearrangement and translational motion, while the induced charge dynamics of the TiO2 surface is governed primarily by the rotational dynamics of the interfacial water molecules. This study demonstrates that the solid surface polarity has a significant impact on the dynamics of water molecules near TiO2 surfaces.

Thermoelectric Efficiency of Organometallic Complex Wires via Quantum Resonance Effect and Long-Range Electric Transport Property

Superior long-range electric transport has been observed in several organometallic wires. Here, we discuss the role of the metal center in the electric transport and examine the possibility of high thermoelectric figure of merit (ZT) by controlling the quantum resonance effects. We examined a few metal center (and metal-free) terpyridine-based complexes by first-principles calculations and clarified the role of the metals in determining the transport properties. Quasi-resonant tunneling is mediated by organic compounds, and narrow overlapping resonance states are formed when d-electron metal centers are incorporated. Distinct length (L) and temperature (T) dependencies of thermopower from semiconductor materials or organic molecular junctions are presented in terms of atomistic calculations of ZT with and without considering the phonon thermal conductance. We present an alternative approach to obtain high ZT for molecular junctions by quantum effect.

Molecular Modeling of Water Interfaces: From Molecular Spectroscopy to Thermodynamics

Understanding aqueous interfaces at the molecular level is not only fundamentally important, but also highly relevant for a variety of disciplines. For instance, electrode-water interfaces are relevant for electrochemistry, as are mineral-water interfaces for geochemistry and air-water interfaces for environmental chemistry; water-lipid interfaces constitute the boundaries of the cell membrane, and are thus relevant for biochemistry. One of the major challenges in these fields is to link macroscopic properties such as interfacial reactivity, solubility, and permeability as well as macroscopic thermodynamic and spectroscopic observables to the structure, structural changes, and dynamics of molecules at these interfaces. Simulations, by themselves, or in conjunction with appropriate experiments, can provide such molecular-level insights into aqueous interfaces. In this contribution, we review the current state-of-the-art of three levels of molecular dynamics (MD) simulation: ab initio, force field, and coarse-grained. We discuss the advantages, the potential, and the limitations of each approach for studying aqueous interfaces, by assessing computations of the sum-frequency generation spectra and surface tension. The comparison of experimental and simulation data provides information on the challenges of future MD simulations, such as improving the force field models and the van der Waals corrections in ab initio MD simulations. Once good agreement between experimental observables and simulation can be established, the simulation can be used to provide insights into the processes at a level of detail that is generally inaccessible to experiments. As an example we discuss the mechanism of the evaporation of water. We finish by presenting an outlook outlining four future challenges for molecular dynamics simulations of aqueous interfacial systems.