Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userThe Correlative Method of Unsymmetrized Self-Consistent Field (CUSF)
109
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
In this work we describe the Correlative Method of Unsymmetrized Self-Consistent Field (CUSF). This method is based on a set of nonlinear integrodifferential equations for the one-particle configurational distribution functions and for the self-consistent potentials of the atoms. Here we present the fundamental concepts of the CUSF, the hypotheses of the method, the basic equations, the self-consistent potential, the thermodynamics of the anharmonic crystalline solids, and the quantum corrections in the quasi-classical approximation. Keywords: lattice theory and statistics; anharmonic crystals; thermodynamics.
rate research
Read More
Fragmentation methods applied to multireference wave functions constitute a road towards the application of highly accurate ab initio wave function calculations to large molecules and solids. However, it is important for reproducibility and transferability that a fragmentation scheme be well-defined with minimal dependence on initial orbital guesses or user-designed ad hoc fragmentation schemes. One way to improve this sort of robustness is to ensure the energy obeys a variational principle; i.e., that the active orbitals and active space wave functions minimize the electronic energy in a certain ansatz for the molecular wave function. We extended the theory of the localized active space self-consistent field, LASSCF, method (JCTC 2019, 15, 972) to fully minimize the energy with respect to all orbital rotations, rendering it truly variational. The new method, called vLASSCF, substantially improves the robustness and reproducibility of the LAS wave function compared to LASSCF. We analyze the storage and operation cost scaling of vLASSCF compared to orbital optimization using a standard CASSCF approach and we show results of vLASSCF calculations on some simple test systems. We show that vLASSCF is energetically equivalent to CASSCF in the limit of one active subspace, and that vLASSCF significantly improves upon the reliability of LASSCF energy differences, allowing for more meaningful and subtle analysis of potential energy curves of dissociating molecules. We also show that all forms of LASSCF have a lower operation cost scaling than the orbital-optimization part of CASSCF.
We use a new configuration-based version of linear response theory to efficiently solve self-consistent mean field equations relating an effective single particle potential to the induced density. The versatility and accuracy of the method is illustrated by applications to dewetting of a hard sphere solute in a Lennard-Jones fluid, the interplay between local hydrogen bond structure and electrostatics for water confined between two hydrophobic walls, and to ion pairing in ionic solutions. Simulation time has been reduced by more than an order of magnitude over previous methods.
Phonon lifetime calculations from first principles usually rely on time consuming molecular dynamics calculations, or density functional perturbation theory (DFPT) where the zero temperature crystal structure is assumed to be dynamically stable. Here a new and effective method for calculating phonon lifetimes from first principles is presented, not limited to crystal structures stable at 0 K, and potentially much more effective than most corresponding molecular dynamics calculations. The method is based on the recently developed self consistent lattice dynamical method and is here tested by calculating the bcc phase phonon lifetimes of Li, Na, Ti and Zr, as representative examples.
We describe a hierarchy of stochastic boundary conditions (SBCs) that can be used to systematically eliminate finite size effects in Monte Carlo simulations of Ising lattices. For an Ising model on a $100 times 100$ square lattice, we measured the specific heat, the magnetic susceptibility, and the spin-spin correlation using SBCs of the two lowest orders, to show that they compare favourably against periodic boundary conditions (PBC) simulations and analytical results. To demonstrate how versatile the SBCs are, we then simulated an Ising lattice with a magnetized boundary, and another with an open boundary, measuring the magnetization, magnetic susceptibility, and longitudinal and transverse spin-spin correlations as a function of distance from the boundary.
A field theoretical framework is developed for the Hawkes self-excited point process with arbitrary memory kernels by embedding the original non-Markovian one-dimensional dynamics onto a Markovian infinite-dimensional one. The corresponding Langevin dynamics of the field variables is given by stochastic partial differential equations that are Markovian. This is in contrast to the Hawkes process, which is non-Markovian (in general) by construction as a result of its (long) memory kernel. We derive the exact solutions of the Lagrange-Charpit equations for the hyperbolic master equations in the Laplace representation in the steady state, close to the critical point of the Hawkes process. The critical condition of the original Hawkes process is found to correspond to a transcritical bifurcation in the Lagrange-Charpit equations. We predict a power law scaling of the PDF of the intensities in an intermediate asymptotics regime, which crosses over to an asymptotic exponential function beyond a characteristic intensity that diverges as the critical condition is approached. We also discuss the formal relationship between quantum field theories and our formulation. Our field theoretical framework provides a way to tackle complex generalisation of the Hawkes process, such as nonlinear Hawkes processes previously proposed to describe the multifractal properties of earthquake seismicity and of financial volatility.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
