Analytical study of the layered XY model with VCE method

Motivated by experiments on liquid-crystal films, we study the development of specific heat anomaly of finite layer system. With the VCE method, we introduce the strong surface interaction into the layered XY model and get the results of the forth-order analytical expansion. The results show that when the strong surface interaction becomes strong enough, the order trend defeats the quantum noise and the specific heat peak moves abnormally to the high temperature with the number of layers decreasing.

Analytical study of the antiferromagnetic Heisenberg films

With the variational cumulant expansion (VCE) method, the thermodynamic behaviors of S = 1/2 antiferromagnetic Heisenberg films in simple cubic lattices are studied analytically. From the analytic properties of the free energy, in principle we are able to calculate analytically the critical temperatures T-c(L) and the thermodynamic functions, to any order cumulant as the functions of the number of L (the hyperlayers in the hyperfilm). Explicit expressions for T-c(L) up to the fourth order are given. A comparison with the existing results for 3-dimensional system is given. The effective range of the interaction is obtained from numerical results.

Molecular Dynamics Simulations of Orientational Relaxation in Dipolar Lattice: Lack of Diffusive Decay for Second and Higher Rank Correlation Functions

Extensive molecular dynamics simulations have been carried out to calculate the orientational correlation functions Cl(t), G(t) = [4n/(21 + l)]Ci=-l (Y*lm(sZ(0)) Ylm(Q(t))) (where Y,,(Q) are the spherical harmonics) of point dipoles in a cubic lattice. The decay of Cl(t) is found to be strikingly different from higher l-correlation functions-the latter do not exhibit diffusive dynamics even in the long time. Both the cumulant expansion expression of Lynden-Bell and the conventional memory function equation provide very good description of the Cl(t) in the short time but fail to reproduce the observed slow, long time decay of c1 (t) .

Quantum master-equation approach to quantum transport through mesoscopic systems

For quantum transport through mesoscopic systems, a quantum master-equation approach is developed in terms of compact expressions for the transport current and the reduced density matrix of the system. The present work is an extension of Gurvitz's approach for quantum transport and quantum measurement, namely, to finite temperature and arbitrary bias voltage. Our derivation starts from a second-order cumulant expansion of the tunneling Hamiltonian; then follows the conditional average over the electrode reservoir states. As a consequence, in the usual weak-tunneling regime, the established formalism is applicable for a wide range of transport problems. The validity of the formalism and its convenience in application are well illustrated by a number of examples.

Determining the electronic structure and chemical potentials of molecules in solution

A simulation scheme is proposed for determining the excess chemical potential of a substance in solution. First, a Monte Carlo simulation is performed with classical models for solute and solvent molecules. A representative sample of these configurations is then used in a hybrid quantum/classical (QM/MM) calculation, where the solute is treated quantum-mechanically, and the average electronic structure is used to construct an improved classical model. This procedure is iterated to self-consistency in the classical model, which in practice is attained in one or two steps, depending on the quality of the initial guess. The excess free energy of the molecule within the QM/MM approach is determined relative to the classical model using thermodynamic perturbation theory with a cumulant expansion. The procedure provides a method of constructing classical point charge models appropriate for the solution and gives a measure of the importance of solvent fluctuations.

Quantenchemische Behandlung von elektronischem Energietransfer

Im Rahmen dieser Dissertation wurden quantenchemische Untersuchungen zum Phänomen des elektronischen Energietransfers durchgeführt. Zum einen wurden theoretische Modelle zur Berücksichtigung temperaturabhängiger Elektron-Phonon-Kopplung in vibronischen Spektren ausgearbeitet und numerischen Tests unterzogen. Zum anderen erfolgte die Bestimmung molekularer Eigenschaften bichromophorer Systeme unter Anwendung etablierter Rechenmethoden. Im Fokus stehen das Zusammenspiel elektronischer Kopplung und statischer Unordnung sowie Energietransferzeiten und der Einfluss molekularer Brücken in Dimeren auf die Kopplung. Da sich elektronischer Energietransfer spektroskopisch nachweisen lässt, wurden temperaturabhängige Simulationen der Linienform von vibronischen Übergängen, die an ein Wärmebad ankoppeln, durchgeführt. Die erforderliche Antwortfunktion zur Bestimmung der spektralen Linienform kann aus einer Kumulantenentwicklung und alternativ aus der Multi-Level Redfieldtheorie abgeleitet werden. Statt der genäherten Schwingungsstruktur des Brownschen Oszillatormodells wurde eine explizit berechnete Zustandsdichte als Ausgangspunkt verwendet. Sowohl reine Elektron-Phonon- als auch Schwingung-Phonon-Kopplung werden für verschiedene Spektraldichten der Badmoden diskutiert. Im Zuge eines Kooperationsprojekts führten wir Untersuchungen zur elektronischen Kopplung an einer homologen Reihe von Rylendimeren mit unterschiedlichen Brückenlängen durch. Zu diesem Zweck wurden Ergebnisse aus Tieftemperatureinzelmolekülmessungen und quantenchemischen Berechnungen auf Grundlage des vibronischen Kopplungsmodells herangezogen und ausgewertet. Die untersuchten Dimere zeigen einen Übergang vom Grenzfall starker Kopplung hin zu schwacher Kopplung und die mittleren Energietransferzeiten konnten in guter Übereinstimmung mit experimentellen Messwerten berechnet werden. Da eine molekulare Brücke zwischen Donor- und Akzeptoreinheit die elektronische Kopplung modifiziert, kann sie sich störend auf experimentelle Messungen auswirken. Daher wurde untersucht, ob das interchromophore Kopplungsverhalten vorwiegend durch die Polarisierbarkeit des verbrückenden Elements oder durch bindungsvermittelte Wechselwirkungen beeinflusst wird und welche Brückentypen sich folglich für experimentelle Studien eignen. Sämtliche untersuchten Brückenelemente führten zu einer Vergrößerung der elektronischen Kopplung und die Kopplungsstärke wurde maßgeblich durch brückenvermittelte Wechselwirkungen bestimmt.

Recent improvements in prediction of protein structure by global optimization of a potential energy function

Recent improvements of a hierarchical ab initio or de novo approach for predicting both α and β structures of proteins are described. The united-residue energy function used in this procedure includes multibody interactions from a cumulant expansion of the free energy of polypeptide chains, with their relative weights determined by Z-score optimization. The critical initial stage of the hierarchical procedure involves a search of conformational space by the conformational space annealing (CSA) method, followed by optimization of an all-atom model. The procedure was assessed in a recent blind test of protein structure prediction (CASP4). The resulting lowest-energy structures of the target proteins (ranging in size from 70 to 244 residues) agreed with the experimental structures in many respects. The entire experimental structure of a cyclic α-helical protein of 70 residues was predicted to within 4.3 Å α-carbon (Cα) rms deviation (rmsd) whereas, for other α-helical proteins, fragments of roughly 60 residues were predicted to within 6.0 Å Cα rmsd. Whereas β structures can now be predicted with the new procedure, the success rate for α/β- and β-proteins is lower than that for α-proteins at present. For the β portions of α/β structures, the Cα rmsd's are less than 6.0 Å for contiguous fragments of 30–40 residues; for one target, three fragments (of length 10, 23, and 28 residues, respectively) formed a compact part of the tertiary structure with a Cα rmsd less than 6.0 Å. Overall, these results constitute an important step toward the ab initio prediction of protein structure solely from the amino acid sequence.

An eigenfunction expansion-variational method in prediction of the transverse thermal conductivity of fiber reinforced composites considering interfacial characteristics

An eigenfunction expansion-variational method based on a unit cell is developed to deal with the steady-state heat conduction problem of doubly-periodic fiber reinforced composites with interfacial thermal contact resistance or coating. The numerical results show a rapid convergence of the present method. The present solution provides a unified first-order approximation formula of the effective thermal conductivity for different interfacial characteristics and fiber distributions. A comparison with the present high-order results, available experimental data and micromechanical estimations demonstrates that the first-order approximation formula is a good engineering closed-form formula. An engineering equivalent parameter reflecting the overall influence of the thermal conductivities of the matrix and fibers and the interfacial characteristic on the effective thermal conductivity, is found. The equivalent parameter can greatly simplify the complicated relation of the effective thermal conductivity to the internal structure of a composite. (c) 2010 Elsevier Ltd. All rights reserved.

Risk control in transmission system expansion planning with wind generators

With the advent of large-scale wind farms and their integration into electrical grids, more uncertainties, constraints and objectives must be considered in power system development. It is therefore necessary to introduce risk-control strategies into the planning of transmission systems connected with wind power generators. This paper presents a probability-based multi-objective model equipped with three risk-control strategies. The model is developed to evaluate and enhance the ability of the transmission system to protect against overload risks when wind power is integrated into the power system. The model involves: (i) defining the uncertainties associated with wind power generators with probability measures and calculating the probabilistic power flow with the combined use of cumulants and Gram-Charlier series; (ii) developing three risk-control strategies by specifying the smallest acceptable non-overload probability for each branch and the whole system, and specifying the non-overload margin for all branches in the whole system; (iii) formulating an overload risk index based on the non-overload probability and the non-overload margin defined; and (iv) developing a multi-objective transmission system expansion planning (TSEP) model with the objective functions composed of transmission investment and the overload risk index. The presented work represents a superior risk-control model for TSEP in terms of security, reliability and economy. The transmission expansion planning model with the three risk-control strategies demonstrates its feasibility in the case study using two typical power systems

Vibration–rotation variational calculations: precise results on HCN up to 25 000 cm−1

Variation calculations of the vibration–rotation energy levels of many isotopomers of HCN are reported, for J=0, 1, and 2, extending up to approximately 8 quanta of each of the stretching vibrations and 14 quanta of the bending mode. The force field, which is represented as a polynomial expansion in Morse coordinates for the bond stretches and even powers of the angle bend, has been refined by least squares to fit simultaneously all observed data on the Σ and Π state vibrational energies, and the Σ state rotational constants, for both HCN and DCN. The observed vibrational energies are fitted to roughly ±0.5 cm−1, and the rotational constants to roughly ±0.0001 cm−1. The force field has been used to predict the vibration rotation spectra of many isotopomers of HCN up to 25 000 cm−1. The results are consistent with the axis‐switching assignments of some weak overtone bands reported recently by Jonas, Yang, and Wodtke, and they also fit and provide the assignment for recent observations by Romanini and Lehmann of very weak absorption bands above 20 000 cm−1.

Variational calculations of rovibrational states: a precise high-energy potential surface for HCN [and discussion]

We report the results of variational calculations of the rovibrational energy levels of HCN for J = 0, 1 and 2, where we reproduce all the ca. 100 observed vibrational states for all observed isotopic species, with energies up to 18000 cm$^{-1}$, to about $\pm $1 cm$^{-1}$, and the corresponding rotational constants to about $\pm $0.001 cm$^{-1}$. We use a hamiltonian expressed in internal coordinates r$_{1}$, r$_{2}$ and $\theta $, using the exact expression for the kinetic energy operator T obtained by direct transformation from the cartesian representation. The potential energy V is expressed as a polynomial expansion in the Morse coordinates y$_{i}$ for the bond stretches and the interbond angle $\theta $. The basis functions are built as products of appropriately scaled Morse functions in the bond-stretches and Legendre or associated Legendre polynomials of cos $\theta $ in the angle bend, and we evaluate matrix elements by Gauss quadrature. The hamiltonian matripx is factorized using the full rovibrational symmetry, and the basis is contracted to an optimized form; the dimensions of the final hamiltonian matrix vary from 240 $\times $ 240 to 1000 $\times $ 1000.We believe that our calculation is converged to better than 1 cm$^{-1}$ at 18 000 cm$^{-1}$. Our potential surface is expressed in terms of 31 parameters, about half of which have been refined by least squares to optimize the fit to the experimental data. The advantages and disadvantages and the future potential of calculations of this type are discussed.

Large vibrational variational calculations using 'multimode' and an iterative diagonalization technique

We have favoured the variational (secular equation) method for the determination of the (ro-) vibrational energy levels of polyatomic molecules. We use predominantly the Watson Hamiltonian in normal coordinates and an associated given potential in the variational code 'Multimode'. The dominant cost is the construction and diagonalization of matrices of ever-increasing size. Here we address this problem, using pertubation theory to select dominant expansion terms within the Davidson-Liu iterative diagonalization method. Our chosen example is the twelve-mode molecule methanol, for which we have an ab initio representation of the potential which includes the internal rotational motion of the OH group relative to CH3. Our new algorithm allows us to obtain converged energy levels for matrices of dimensions in excess of 100 000.

COMPLEX KOHN VARIATIONAL PRINCIPLE FOR 2-NUCLEON BOUND-STATE AND SCATTERING WITH THE TENSOR POTENTIAL

Complex Kohn variational principle is applied to the numerical solution of the fully off-shell Lippmann-Schwinger equation for nucleon-nucleon scattering for various partial waves including the coupled S-3(1), D-3(1), channel. Analytic expressions are obtained for all the integrals in the method for a suitable choice of expansion functions. Calculations with the partial waves S-1(0), P-1(1), D-1(2), and S-3(1)-D-3(1) of the Reid soft core potential show that the method converges faster than other solution schemes not only for the phase shift but also for the off-shell t matrix elements. We also show that it is trivial to modify this variational principle in order to make it suitable for bound-state calculation. The bound-state approach is illustrated for the S-3(1)-D-3(1) channel of the Reid soft-core potential for calculating the deuteron binding, wave function, and the D state asymptotic parameters. (c) 1995 Academic Press, Inc.

The δ expansion and the principle of minimal sensitivity

The δ-expansion is a nonperturbative approach for field theoretic models which combines the techniques of perturbation theory and the variational principle. Different ways of implementing the principle of minimal sensitivity to the δ-expansion produce in general different results for observables. For illustration we use the Nambu-Jona-Lasinio model for chiral symmetry restoration at finite density and compare results with those obtained with the Hartree-Fock approximation.

Variational and perturbative schemes for a spiked harmonic oscillator

A variational analysis of the spiked harmonic oscillator Hamiltonian operator - d2/dx2 + x2 + l(l + 1)/x2 + λ|x| -α, where α is a real positive parameter, is reported in this work. The formalism makes use of the functional space spanned by the solutions of the Schrödinger equation for the linear harmonic oscillator Hamiltonian supplemented by a Dirichlet boundary condition, and a standard procedure for diagonalizing symmetric matrices. The eigenvalues obtained by increasing the dimension of the basis set provide accurate approximations for the ground state energy of the model system, valid for positive and relatively large values of the coupling parameter λ. Additionally, a large coupling perturbative expansion is carried out and the contributions up to fourth-order to the ground state energy are explicitly evaluated. Numerical results are compared for the special case α = 5/2. © 1989 American Institute of Physics.