Effect of cyclic chain architecture on properties of dilute solutions of polyethylene from molecular dynamics simulations

We have used molecular dynamics methods to investigate the effects of cyclic chain architecture on the properties of dilute solutions. In order to include solvent effects in estimating these properties, we use a van der Waals scaling factor determined for each solvent by matching to the theta condition. We predict that the theta temperature (theta) of cyclic PE (c-PE) is ~10% lower than for the linear case (l-PE). This can be compared to the experimental results for polystyrene (PS), where theta for cyclic PS is 2% lower. For conditions corresponding to n-pentane solvent, we predict that g2>cyclic/g2>linear is 0.59 for all temperatures above 350 K. The deviation from the ratio of 0.50–0.53 expected from analytic theory is due to the competition between chain stiffness and excluded volume effects. To calculate the intrinsic viscosity of c-PE and l-PE we extended the Bloomfield–Zimm type theory to include chain stiffness corrections. We find that for the theta temperature, the ratio of viscosities for c-PE and l-PE is 0.71, which is 7% higher than the value of 0.66 from the freely jointed chain model. This difference is caused by the larger value of g2>cyclic/g2>linear from the simulations

Conformations and charge transport characteristics of biphenyldithiol self-assembled-monolayer molecular electronic devices: A multiscale computational study

We report a computational study of conformations and charge transport characteristics of biphenyldithiol (BPDT) monolayers in the (sqrt(3)×sqrt(3))R30° packing ratio sandwiched between Au(111) electrodes. From force-field molecular-dynamics and annealing simulations of BPDT self-assembled monolayers (SAMs) with up to 100 molecules on a Au(111) substrate, we identify an energetically favorable herringbone-type SAM packing configuration and a less-stable parallel packing configuration. Both SAMs are described by the (2sqrt(3)×sqrt(3))R30° unit cell including two molecules. With subsequent density-functional theory calculations of one unit cell of the (i) herringbone SAM with the molecular tilt angle theta[approximate]15°, (ii) herringbone SAM with theta[approximate]30°, and (iii) parallel SAM with theta[approximate]30°, we confirm that the herringbone packing configuration is more stable than the parallel one but find that the energy variation with respect to the molecule tilting within the herringbone packing is very small. Next, by capping these SAMs with the top Au(111) electrode, we prepare three molecular electronic device models and calculate their coherent charge transport properties within the matrix Green's function approach. Current–voltage (I–V) curves are then obtained via the Landauer–Büttiker formula. We find that at low-bias voltages (|V|~0.5 V), the I–V characteristics of the three models show noticeable differences due to different phenyl band structures. We thus conclude that the BPDT SAM I–V characteristics in the low-bias voltage region are mainly determined by the Si–Au interaction within the individual molecule-electrode contact, while both intramolecular conformation and intermolecular interaction can affect the BPDT SAM I–V characteristics in the high-bias voltage region

First-principles study of the switching mechanism of [2]catenane molecular electronic devices

We present a first-principles study of the coherent charge transport properties of bistable [2]catenane molecular monolayers sandwiched between Au(111) electrodes. We find that conduction channels around the Fermi level are dominated by the two highest occupied molecular orbital levels from tetrathiafulvalene (TTF) and dioxynaphthalene (DNP) and the two lowest unoccupied molecular orbital levels from tetracationic cyclophane (CBPQT(4+)), and the OFF to ON switching results from the energetic shifts of these orbitals as CBPQT(4+) moves from TTF to DNP. We show that the superposition principle can be adopted for predicting the function of the composite device

Possible performance improvement in [2]catenane molecular electronic switches

Mechanically interlocked bistable supramolecular complexes are promising candidates of molecular electronics. Applying a multiscale computational approach, here we study the coherent charge transport properties of catenane monolayers sandwiched between Cu(111) electrodes. We demonstrate the robust nature of electrical switching behavior with respect to the variations in the monolayer packing density and the type of electrodes, as well as the thermal fluctuations of the molecules. We propose that the asymmetry of molecule-electrode barriers can be utilized to improve the switching ratio

Negative Differential Resistance of Oligo(Phenylene Ethynylene) Self-Assembled Monolayer Systems: The Electric-Field-Induced Conformational Change Mechanism

We investigate here a possible mechanism for the room temperature negative differential resistance (NDR) in the Au/AN-OPE/RS/Hg self-assembled monolayer (SAM) system, where AN-OPE = 2′-amino,5′-nitro-oligo(phenylene ethynylene) and RS is a C_(14) alkyl thiolate. Kiehl and co-workers showed that this molecular system leads to NDR with hysteresis and sweep-rate-dependent position and amplitude in the NDR peak. To investigate a molecular basis for this interesting behavior, we combine first-principles quantum mechanics (QM) and mesoscale lattice Monte Carlo methods to simulate the switching as a function of voltage and voltage rate, leading to results consistent with experimental observations. This simulation shows how the structural changes at the microscopic level lead to the NDR and sweep-rate-dependent macroscopic I−V curve observed experimentally, suggesting a microscopic model that might aid in designing improved NDR systems

Molecular Dynamics Simulation Study on a Monolayer of Half [2]Rotaxane Self-Assembled on Au(111)

The self-assembled monolayer (SAM) structure of the tetrathiafulvalene-side half of the Stoddart−Heath type [2]rotaxane on Au(111) surface was investigated using molecular dynamics (MD) simulations. We find that the orientation of the cyclobis(paraquat-p-phenylene) (CBPQT) ring depends dramatically on the coverage, changing in order to obtain highly packed SAMs. The ring lies with its large hollow parallel to the surface at lower coverage (up to one CBPQT per 27 surface Au atoms with a footprint of 1.9 nm^2; 1/27) when free space is available around it, but as the coverage increases (up to one CBPQT per 12 surface Au atoms with a footprint of 0.9 nm^2; 1/12), it tilts completely around its axis and lies with its smaller side (paraquat or phenyl ring) parallel to the surface to accommodate the reduced area available. We find that the best packing densities correspond to one CBPQT per 12−18 surface Au atoms (1/18−1/12) with footprints in the range between 0.9 nm^2 and 1.3 nm^2

Charge Transport through Polyene Self-Assembled Monolayers from Multiscale Computer Simulations

We combine first-principles density-functional theory with matrix Green’s function calculations to predict the structures and charge transport characteristics of self-assembled monolayers (SAMs) of four classes of systems in contact with Au(111) electrodes: conjugated polyene chains (n = 4, 8, 12, 16, and 30) thiolated at one or both ends and saturated alkane chains (n = 4, 8, 12, and 16) thiolated at one or both ends. For the polyene SAMs, we find no decay in the current as a function of chain length and conclude that these 1−3 nm long polyene SAMs act as metallic wires. We also find that the polyene-monothiolate leads to a contact resistance only 2.8 times higher than that for the polyene-dithiolate chains, indicating that the device conductance is dominated by the properties of the molecular connector with less importance in having a second molecule−electrode contact. For the alkane SAMs, we observe the normal exponential decay in the current as a function of the chain length with a decay constant of βn = 0.82 for the alkane-monothiolate and 0.88 for the alkane-dithiolate. We find that the contact resistance for the alkane-monothiolate is 12.5 times higher than that for the alkane-dithiolate chains, reflecting the extra resistance due to the weak contact on the nonthiolated end. These contrasting charge transport characteristics of alkane and polyene SAMs and their contact dependence are explained in terms of the atomic projected density of states

Sodium Diffusion through Aluminum-Doped Zeolite BEA System: Effect of Water Solvation

To investigate the effect of hydration on the diffusion of sodium ions through the aluminum-doped zeolite BEA system (Si/Al = 30), we used the grand canonical Monte Carlo (GCMC) method to predict the water absorption into aluminosilicate zeolite structure under various conditions of vapor pressure and temperature, followed by molecular dynamics (MD) simulations to investigate how the sodium diffusion depends on the concentration of water molecules. The predicted absorption isotherm shows first-order-like transition, which is commonly observed in hydrophobic porous systems. The MD trajectories indicate that the sodium ions diffuse through zeolite porous structures via hopping mechanism, as previously discussed for similar solid electrolyte systems. These results show that above 15 wt % hydration (good solvation regime) the formation of the solvation cage dramatically increases sodium diffusion by reducing the hopping energy barrier by 25% from the value of 3.8 kcal/mol observed in the poor solvation regime

Free energy barrier for molecular motions in bistable [2]rotaxane molecular electronic devices

Donor−acceptor binding of the π-electron-poor cyclophane cyclobis(paraquat-p-phenylene) (CBPQT^(4+)) with the π-electron-rich tetrathiafulvalene (TTF) and 1,5-dioxynaphthalene (DNP) stations provides the basis for electrochemically switchable, bistable [2]rotaxanes, which have been incorporated and operated within solid-state devices to form ultradense memory circuits (ChemPhysChem 2002, 3, 519−525; Nature 2007, 445, 414−417) and nanoelectromechanical systems. The rate of CBPQT^(4+) shuttling at each oxidation state of the [2]rotaxane dictates critical write-and-retention time parameters within the devices, which can be tuned through chemical synthesis. To validate how well computational chemistry methods can estimate these rates for use in designing new devices, we used molecular dynamics simulations to calculate the free energy barrier for the shuttling of the CBPQT^4+ ring between the TTF and the DNP. The approach used here was to calculate the potential of mean force along the switching pathway, from which we calculated free energy barriers. These calculations find a turn-on time after the rotaxane is doubly oxidized of ~10^9−7) s (suggesting that the much longer experimental turn-on time is determined by the time scale of oxidization). The return barrier from the DNP to the TTF leads to a predicted lifetime of 2.1 s, which is compatible with experiments