Choice Of Projection Operator Research Articles

A Road Map to Various Pathways for Calculating the Memory Kernel of the Generalized Quantum Master Equation.

The generalized quantum master equation (GQME) provides a powerful framework for simulating electronic energy, charge, and coherence transfer dynamics in molecular systems. Within this framework, the effect of the nuclear degrees of freedom on the time evolution of the electronic reduced density matrix is fully captured by a memory kernel superoperator. However, the actual memory kernel depends on the choice of projection operator and is therefore not unique. Furthermore, calculating the memory kernel can be done in multiple ways that use different forms of projection-free inputs. Although the electronic dynamics is invariant to those choices when quantum-mechanically exact projection-free inputs are used, this is not the case when they are obtained via more feasible semiclassical or mixed quantum-classical approximate methods. Furthermore, the accuracy and numerical stability of the resulting electronic dynamics has been observed to be sensitive to the above-mentioned choices when approximate methods are used to calculate the projection-free inputs. In this article, we provide a systematic road map to 30 possible pathways for calculating the memory kernel and highlight how they are related as well as the ways in which they differ. We also compare the performance of different pathways in the context of the spin-boson benchmark model, with the projection-free inputs obtained via a mapping Hamiltonian linearized semiclassical method. In this case, we find that expressing the memory kernel with an exponential operator where the projection operator precedes the Liouvillian yields the most accurate and most numerically stable results.

Nitsche’s method as a variational multiscale formulation and a resulting boundary layer fine-scale model

We show that in the variational multiscale framework, the weak enforcement of essential boundary conditions via Nitsche’s method corresponds directly to a particular choice of projection operator. The consistency, symmetry and penalty terms of Nitsche’s method all originate from the fine-scale closure dictated by the corresponding scale decomposition. As a result of this formalism, we are able to determine the exact fine-scale contributions in Nitsche-type formulations. In the context of the advection–diffusion equation, we develop a residual-based model that incorporates the non-vanishing fine scales at the Dirichlet boundaries. This results in an additional boundary term with a new model parameter. We then propose a parameter estimation strategy for all parameters involved that is also consistent for higher-order basis functions. We illustrate with numerical experiments that our new augmented model mitigates the overly diffusive behavior that the classical residual-based fine-scale model exhibits in boundary layers at boundaries with weakly enforced essential conditions. • Nitsche’s method corresponds directly to a scale decomposition in the VMS framework. • This interpretation reveals the exact fine-scale terms in the finite element formulation. • The (SUPG type) fine-scale model requires an additional boundary term. • We provide parameter estimations based on fine-scale Green’s functions. • These parameter estimations are suitable for higher-order discretizations.

Microscopic derivation of particle-based coarse-grained dynamics

In this paper we revisit the derivation of equations of motion for coarse-grained (CG) particles from the microscopic Hamiltonian dynamics of the underlying atomistic system in equilibrium. The derivation is based on the projection operator method and time-convolution equation. We demonstrate that due to the energy exchange between CG and intraparticle phase space coordinates in the microscopic system, the choice of projection operator is not unique, leading to different CG equations of motion that have the form of the nonlinear generalized Langevin equation (GLE). We derive the idempotence properties for the projection operators along the system trajectories and show that these properties result in streaming terms of the respective GLEs that are conservative forces and allow the expression of the non-conservative forces explicitly through thermodynamic averages, which can be measured from the microscopic simulations. The difference between GLEs that are presented herein lies in how the non-conservative forces are partitioned into dissipative and projected contributions. We compute the projected force and analyze conditions under which the projected (stochastic) force is orthogonal to (uncorrelated with) the momenta of CG particles, therefore justifying a transition to a framework of stochastic differential equations. We show that a position- and momentum-independent memory function appears only if the projected force is fully decoupled from the past CG positions and momenta, respectively. In the case of non-vanishing correlations between the projected force and the CG coordinates in past times, we derive explicitly the position- and momentum-dependent memory function in a form of projection onto a space spanned by N-order Hermite polynomials. The expressions presented herein can be used to construct a hierarchy of thermodynamically consistent CG models with momentum-dependent memory functions. They can also be used to design computational schemes for obtaining the parameters for GLEs and their variants such as dissipative particle dynamics equations from the microscopic data. We illustrate these applications by presenting the GLE with a memory function that is quadratic in the particle momenta.

Basis set study of classical rotor lattice dynamics.

The reorientational relaxation of molecular systems is important in many phenomenon and applications. In this paper, we explore the reorientational relaxation of a model Brownian rotor lattice system with short range interactions in both the high and low temperature regimes. In this study, we use a basis set expansion to capture collective motions of the system. The single particle basis set is used in the high temperature regime, while the spin wave basis is used in the low temperature regime. The equations of motion derived in this approach are analogous to the generalized Langevin equation, but the equations render flexibility by allowing nonequilibrium initial conditions. This calculation shows that the choice of projection operators in the generalized Langevin equation (GLE) approach corresponds to defining a specific inner-product space, and this inner-product space should be chosen to reveal the important physics of the problem. The basis set approach corresponds to an inner-product and projection operator that maintain the orthogonality of the spherical harmonics and provide a convenient platform for analyzing GLE expansions. The results compare favorably with numerical simulations, and the formalism is easily extended to more complex systems.

Many-body approach to proton emission and the role of spectroscopic factors

The process of proton emission from nuclei is studied by utilizing the two-potential approach of Gurvitz and Kalbermann in the context of the full many-body problem. A time-dependent approach is used for calculating the decay width. Starting from an initial many-body quasistationary state, we employ the Feshbach projection operator approach and reduce the formalism to an effective one-body problem. We show that the decay width can be expressed in terms of a one-body matrix element multiplied by a normalization factor. We demonstrate that the traditional interpretation of this normalization as the square root of a spectroscopic factor is only valid for one particular choice of projection operator. This causes no problem for the calculation of the decay width in a consistent microscopic approach, but it leads to ambiguities in the interpretation of experimental results. In particular, spectroscopic factors extracted from a comparison of the measured decay width with a calculated single-particle width may be affected.