Hydrogen bonding in liquid water: An ab initio QM/MM MD simulation study

Pattern and dynamics of hydrogen bonds in liquid water were investigated by a quantum mechanical/molecular mechanical molecular dynamics (QM/MM MD) simulation at Hartree–Fock (HF) level of theory. A large subregion of the whole system comprising two complete coordination shells was treated quantum mechanically in order to include all polarization and charge transfer effects and to obtain accurate data about structure and dynamics of the intermolecular bonds. The results of this investigation are in agreement with recent experimental findings and suggest that in liquid water every molecule forms in average 2.8, but almost as a rule less than four intermolecular hydrogen bonds.     

Quantum Boltzmann equation solved by Monte Carlo method for nano-scale semiconductor devices simulation

A two-dimensional (2D) full band self-consistent ensemble Monte Carlo (MC) method for solving the quantum Boltzmann equation, including collision broadening and quantum potential corrections, is developed to extend the MC method to the study of nano-scale semiconductor devices with obvious quantum mechanical (QM) effects. The quantum effects both in real space and momentum space in nano-scale semiconductor devices can be simulated. The effective mobility in the inversion layer of n and p channel MOSFET is simulated and compared with experimental data to verify this method. With this method 50nm ultra thin body silicon on insulator MOSFET are simulated. Results indicate that this method can be used to simulate the 2D QM effects in semiconductor devices including tunnelling effect.     

Quantum Stark broadening of 3s–3p spectral lines in Li-like ions; Z-scaling and comparison with semi-classical perturbation theory

Quantum mechanical results for the electron impact Stark widths of the 3s–3p transitions in ten Li-like ions from C IV to P XIII are carried out. The atomic structure is obtained through a scaled Thomas-Fermi-Dirac-Amaldi potential (SST numerical code) with relativistic corrections. The distorted wave method is used for the calculation of the S-Matrix, and Feshbach resonances are included by means of the Gailitis method. A comparison with other theoretical and available experimental results is done. Except for Ne VIII, we find that the agreement between our quantum results and the experiments gets better when Z increases, which is not the case for the available close-coupling quantum ones. The behavior of the Stark width with the charge Z and the electron temperature T_e is also studied and in contrast to previous studies, an improved agreement with experimental Z-scaling is obtained. We show that the relative difference between widths of the two fine structure lines of the same multiplet increases with Z from 0.5% for C IV to about 12% for P XIII, proving the increasing importance of fine structure effects. The importance of the Feshbach resonances is discussed and a comparison with available semi-classical perturbation results is given.     

Electronic properties of model quantum-dot structures in zero and finite magnetic fields

We have computed electronic structures and total energies of circularly confined two-dimensional quantum dots and their lateral dimers in zero and finite uniform external magnetic fields using different theoretical schemes: the spin-density-functional theory (SDFT), the current-and-spin-density-functional theory (CSDFT), and the variational quantum Monte Carlo (VMC) method. The SDFT and CSDFT calculations employ a recently-developed, symmetry-unrestricted real-space algorithm allowing solutions which break the spin symmetry. Results obtained for a six-electron dot in the weak confinement limit and in zero magnetic field as well as in a moderate confinement and in finite magnetic fields enable us to draw conclusions about the reliability of the more approximative SDFT and CSDFT schemes in comparison with the VMC method. The same is true for results obtained for the two-electron quantum dot dimer as a function of inter-dot distance. The structure and role of the symmetry-breaking solutions appearing in the SDFT and CSDFT calculations for the above systems are discussed. Received 16 October 2001 and Received in final form 17 January 2002     

Quantum mechanical effects on heat generation in nano-scale MOSFETs

The Monte Carlo simulation is performed to investigate the quantum mechanical (QM) effects on heat generation in nano-scale metal oxide semiconductor field effect transistors (MOSFETs) by solving the quantum Boltzmann equation. The influence of QM effects both in real space and $K$ space on the heat generation is investigated.     

On the properties of new benzothiazole derivatives for organic light emitting diodes (OLEDs): A comprehensive theoretical study

The present investigation explored theoretically the geometry structures, the electronic and the optical properties of new benzothiazole derivatives with incorporated triphenylamine/diphenylnaphthylamine or (4-vinylphenyl)acrylonitrile as highly efficient emitting molecular materials for organic light emitting diodes (OLEDs). This study is accomplished in order to provide an in-depth understanding of the structure-properties correlation and their effects on optoelectronic devices.In this contribution, we apply quantum-chemical methods (semiempirical Austin Model 1 (AM1), ab-initio Hartree-Fock (HF) and density functional theory (DFT)) to elucidate the photophysical properties of these molecules. First of all, the geometry structures of these compounds in the ground and the excited states were fully optimized, showing a non-planar configuration structures. Whereas, the geometrical structure of benzothiazole with cyano-PV unit is more planar. Structural parameters and vibrational properties of these compounds are then derived. Moreover, absorption and luminescence properties, lying in a bluish white or red light emission, were elucidated by ZINDO/S methods. The molecular orbital (highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)), the ionization potentials (IPs) and the electron affinities (EAs) of compounds under study were also investigated. It was found that the detailed results obtained from theoretical simulations are consistent with the available experimental data. This kind of theoretical approach has been proved to be reliable for the structure and spectroscopic properties, and predicts the favorable qualities of these benzothiazole derivatives, which make them as the materials of choice for high performance applications.     

Silicon clusters of intermediate size: energetics, dynamics, and thermal effects

A combination of the best available theoretical techniques for energetics, dynamics, and thermodynamics is employed in an extensive study of Si(n) ( n = 20,25) clusters. For T = 0 we solve the electronic structure by the density functional and the highly accurate quantum Monte Carlo approaches. Finite temperature and dynamical effects are investigated by the ab initio molecular dynamics method. This combination of methods enables us to find several new low-energy isomers and to explain the differences in properties, behavior, and stability of elongated versus compact types of structures and to elucidate the origin of the existing discrepancies between theory and experiments.     

Structure and Liquid-Vapor Interface of a Simple Metal

This paper presents the results of a theoretical study of the structure of the liquidvapor interface of gallium, based on density functional pseudopotential representation of the electron-ion and the ion-ion interactions, and self-consistent quantum Monte Carlo simulation. These predictions of the bulk pair correlation function and the longitudinal density distribution are in very good agreement with the results of recent experimental studies.     

Microcanonical equilibrium properties of chiral liquid crystals—a Monte Carlo study

Chiral liquid crystals have been investigated by means of a multicanonical Monte Carlo approach in order to characterize their phase behaviour by microcanonical equilibrium properties. The liquid crystals were described by three-dimensional lattice systems with intermolecular interactions given by the chiral Lebwohl-Lasher potential. Self-determined boundary conditions have been applied in order to enable the formation of chiral phases with equilibrium pitch. Selected thermodynamic properties, e.g. microcanonical entropy, temperature, heat capacity and a set of order parameters have been determined with dependence on microcanonical total energy. A cholesteric phase with temperature-induced helix inversion could be proven where the helical superstructure of the single component system studied changed its handedness through an infinite-pitch system. The thermodynamical behaviour in the microcanonical ensemble was found to be very similar to the behaviour in the canonical ensemble. The study of microcanonical equilibrium properties by means of multicanonical Monte Carlo simulations was shown to be a powerful tool for the study of the phase behaviour of model liquid crystals.     

Adaptive clustering of a quantum solvent: the LiH+ cation in bosonic helium from stochastic calculations

Calculations of the quantum structures describing the initial solvation shells of bosonic helium atoms around a polar, ionic system like LiH⁺ are reported, together with the corresponding quantum energies. The calculations were carried out using the Diffusion Monte Carlo (DMC) approach and parametric trial functions. Its final radial and angular distributions for clusters of varying size are analysed and discussed. The solvation of this ionic dopant is shown to occur in a way which is strongly affected by the orientational induction forces between the latter molecule and the solvent atoms, indicating the onset of “snowball" structures at the location of the dopant and the clear distinction between “heliophilic" and “heliophobic" regions of microsolvation.     

Monte carlo simulations of growth modes of Pb nanoislands on Si(111) surface

The growth of Pb islands on a Si(111) surface exhibits many interesting properties. For example, the self-assembled process results in a homogeneous distribution of Pb islands with uniform height. The dependence of this height on coverage and temperature can be expressed as a phase diagram [1]. In this paper we develop a model of the growth process that reflects the main features of the experimental observations and determines the key processes of quantum dot formation in a Pb/Si(111) system. The growth of islands is simulated by the Monte Carlo method. With suitably chosen parameters the model is able to reconstruct the phase diagram, via the dependence of the dynamics of Pb atoms on area and height. These dependencies are attributed to stress energy and quantum size effects.     

Study of range distribution parameters for bismuth-ion implantation in silver gallium diselenide

Range distributions for bismuth ions implanted in AgGaSe₂ in the energy range 80–300 keV were investigated by using 2.1-MeV He²⁺ Rutherford backscattering spectrometry (RBS). A convolution calculation method was used to extract the true distributions of bismuth from the measured RBS spectra. The range distribution parameters, R_p and ΔR_p, were obtained and compared with those obtained from Monte Carlo simulation. The experimental R_p values agree with the Monte Carlo simulation values very well, but the experimental ΔR_p values are systematically larger than those from the theoretical simulation. Received: 28 January 2002 / Accepted: 11 April 2002 / Published online: 10 September 2002 RID="*" ID="*"Corresponding author. Fax: +86-531/856-5167, E-mail: xdliu@sdu.edu.cn     

Multireference quantum Monte Carlo study of the O4 molecule

Fixed-node diffusion quantum Monte Carlo (FN-DMC) calculations are performed to obtain the most accurate dissociation barrier and heat of formation with respect to dissociation into molecular oxygen for the chemically bound tetraoxygen molecule. Multireference trial wave functions were used and built from truncated CASSCF(16,12) through a weight-consistent scheme allowing to control the fixed-node error. Results are compared with the previous ab initio benchmark Complete Active Space SCF Averaged Coupled Pair Functional/aug-cc-pVQZ (CASSCF-ACPF/AVQZ) results. The FN-DMC barriers to dissociation and heat of formation obtained are 11.6+/-1.6 kcal/mol and 98.5+/-1.9 kcal/mol, respectively. These thermochemical energies should be taken as the theoretical references when discussing the relevance of tetraoxygen in a variety of experiments and atmospheric chemical processes.     

One-dimensional phase transitions in a two-dimensional optical lattice

A phase transition for bosonic atoms in a two-dimensional anisotropic optical lattice is considered. If the tunnelling rates in two directions are different, the system can undergo a transition between a two-dimensional superfluid and a one-dimensional Mott insulating array of strongly coupled tubes. The connection to other lattice models is exploited in order to better understand the phase transition. Critical properties are obtained using quantum Monte Carlo calculations. These critical properties are related to correlation properties of the bosons and a criterion for commensurate filling is established.     

Thermodynamic and transport properties of nitrogen and butane mixtures

A force field has been developed to describe the phase behaviour, interfacial, and transport properties of nitrogen and hydrocarbon mixtures under conditions relevant to those found in the high pressure extraction of oil from underground reservoirs. A Gibbs ensemble Monte Carlo method is used to parametrize intermolecular potentials for the pure components by matching experimental and simulated liquid and vapour coexisting densities. Also the surface tension, diffusion coefficient and shear viscosity of nitrogen and its mixtures with butane have been determined. The latter properties were obtained by canonical molecular dynamics simulations. The diffusion coefficient and shear viscosity were calculated by a Green-Kubo method. Results for pure nitrogen are given for temperatures ranging from 70 K to 110K. For mixtures of nitrogen with butane, results are presented at 339.4 K and 380.2 K. Good agreement is found between the results of simulations and available experimental data.     

Study of intrinsic anchoring in nematic liquid crystals based on modified Gruhn-Hess pair potential

A nematic liquid crystal slab composed of N molecular layers is investigated using a simple cubic lattice model, based upon the molecular pair potential which is spatially anisotropic and dependent on elastic constants of liquid crystals. A perfect nematic order is assumed in the theoretical treatment, which means the orientation of the molecular long axis coincides with the director of liquid crystal and the total free energy equals to the total interaction energy. We present a modified Gruhn-Hess model, which is relative to the splay-bend elastic constant K₁₃. Furthermore, we have studied the free nematic interfacial behavior (intrinsic anchoring) by this model in the assumption of the perfect nematic order. We find that the preferred orientation at the free interface and the intrinsic anchoring strength change with the value of modification, and that the director profile can be determined by the competition of the intrinsic anchoring with external forces present in the system. Also we simulate the intrinsic anchoring at different temperatures using Monte Carlo method and the simulation results show that the intrinsic anchoring favors planar alignment and the free interface is more disordered than the bulk.     

Modeling of MOS scaling with emphasis on gate tunneling and source/drain resistance

Two critical aspects of the MOS scaling towards sub-100 nm gate length are addressed: the gate tunneling and capacitance modeling, and optimization of shallow source/drain (S/D) extension junction to minimize the series resistance. Both advanced physics (quantum mechanics or QM) and practical solution (circuit simulation) are used to tackle the modeling approach. Good results have been obtained compared to available experimental data, validating the hierarchical methodology used in this paper. A hybrid, semi-analytical QM model for channel carrier profile and an accurate direct tunneling model have been developed. An nMOS transistor with effective channel length of 0.08 micron has been analyzed to demonstrate the methodology proposed.