arXiv subjects

James P. Finley

Publications and source records attributed to James P. Finley.

13 recordsLinked to original sources

arXiv2024

A Formulation of Quantum Fluid Mechanics and Trajectories

A formalism of classical mechanics is given for time-dependent many-body states of quantum mechanics, describing both fluid flow and point mass trajectories. The familiar equations of energy, motion, and those of Lagrangian mechanics are obtained. An energy and continuity equation is demonstrated to be equivalent to the real and imaginary parts of the time dependent Schroedinger equation, respectively, where the Schroedinger equation is in density matrix form. For certain stationary states, using Lagrangian mechanics and a Hamiltonian function for quantum mechanics, equations for point-mass trajectories are obtained. For 1-body states and fluid flows, the energy equation and equations of motion are the Bernoulli and Euler equations of fluid mechanics, respectively. Generalizations of the energy and Euler equations are derived to obtain equations that are in the same form as they are in classical mechanics. The fluid flow type is compressible, inviscid, irrotational, with the nonclassical element of local variable mass. Over all space mass is conserved. The variable mass is a necessary condition for the fluid flow to agree with the zero orbital angular momentum for s states of hydrogen. Cross flows are examined, where velocity directions are changed without changing the kinetic energy. For one-electron atoms, the velocity modification gives closed orbits for trajectories, and mass conservation, vortexes, and density stratification for fluid flows. For many body states, Under certain conditions, and by hypotheses, Euler equations of orbital-flows are obtained. One-body Schroedinger equations that are a generalization of the Hartree-Fock equations are also obtained. These equations contain a quantum Coulomb's law, involving the 2-body pair function of reduced density matrix theory that replace the charge densities.

quant-ph↗

arXiv2023

Fields and Equations of Classical Mechanics for Quantum Mechanics

A generalized Euler equation of fluid dynamics is derived for describing many-body states of quantum mechanics. The Eulerian Eq. can be viewed as representing the interaction of two substates, where each substate has its own velocity and pressure fields. These field quantities are given by maps of the wavefunction. For one-body systems, the Eulerian Eq. can model either a fluid or particle description of quantum states. The generalized Euler Eq. is shown to be the gradient of an equation representing the total-energy of the two substates, having two energy fields. This total-energy Eq. is a generalization of the Bernoulli Eq. of fluid dynamics. The total-energy Eq., along with a continuity-equation, is equivalent to the time-dependent Schroedinger Eq. An equation is also derived that is equivalent to the main equation of Bohmian mechanics with additional identifications: The quantum potential of Bohmian mechanics is given as a sum of a kinetic energy and pressure fields. Also, the time derivative of the wavefunction phase is replaced by an energy field. In the formalism, field quantities are identified from their placement in equations of classical mechanics and separately, by definitions that involve the wavefunction and operators of quantum mechanics. This approach yields, unintended, and unknown energy and pressure fields. These fields, however, are shown to satisfy a continuity Eq., an equation that is equivalent to the other equation of Bohmian mechanics. It is also demonstrated that energy conservation holds for both of these energy fields, if the wavefunction is a linear-combination of eigenvectors, where the eigenvectors can be nondegenerate. A detailed investigation is given on the possible behavior, or source, of an electron that has one of the velocity fields. Alternate formulae for this velocity fields are also considered.

quant-ph↗

arXiv2021

Developments of Bohmian Mechanics

Bohmian mechanics is a deterministic theory of quantum mechanics that is based on a set of n velocity functions for n particles, where these functions depend on the wavefunction from the n-body time-dependent Schroedinger equation. It is well know that Bohmian mechanics is not applicable to stationary states, since the velocity field for stationary states is the zero function. Recently, an alternative to Bohmian mechanics has been formulated, based on a conservation of energy equation, where the velocity fields are not the zero function, but this formalism is only applicable to stationary states with real valued wavefunctions. In this paper, Bohmian mechanics is merged with the alternative to Bohmian mechanics. This is accomplished by introducing an interpretation of the Bohm quantum potential. The final formalism gives dynamic particles for all states, including stationary states. The final main working equation contains two kinetic energy terms and a term that contains a factor that can be interpreted as a pressure. The derivation is a simple n-body generalization of the recent generalization, or refinement, of the Madelung equations.

quant-ph↗

arXiv2021

Refined Madelung Equations

The Madelung equations are two equations that are equivalent to the one-body time-dependent Schroedinger equation. In this paper, the Madelung equation, whose gradient is an Euler equation, is refined by introducing interpretations of functions that are shown to depend only on the real-part of the complex-valued wavefunction. These interpretations are extensions of functions from the recently derived generalized Bernoulli equation, applicable to real-valued quantum-mechanical stationary states. In particular, the velocity and pressure definitions are extended so that they depend on the real-part of a time-dependent complex-valued wavefunction. The Bohn quantum potential is then interpreted as the sum of two terms, one involving the kinetic energy and the other involving the pressure. Substituting the interpreted quantum-potential into the Madelung equation gives a refined equation containing two kinetic energy terms, a pressure term, and the external potential. It is easily demonstrated that the refined Madelung equation, applied to the hydrogen atom states with a nonzero magnetic quantum number, gives a fluid velocity that contains both a radial component and a free vortex. Hence, the fluid particles have angular momentum and move on streamlines that terminate at infinity. It is also demonstrated that the two velocities from the refined Madelung equation are related: One is the real component and the other is the imaginary component of a complex velocity. Furthermore, an Euler equation for quantum mechanical systems is derived by taking the gradient of the refined Madelung equation.

physics.flu-dyn↗

arXiv2021

A Quantum Mechanics Conservation of Energy Equation for Stationary States with Real Valued Wave Functions

Many-body quantum-mechanical stationary states that have real valued wavefunctions are shown to satisfy a classical conservation of energy equation with a kinetic energy function. The terms in the equation depend on the probability distribution, and, in addition, pressure and velocity functions, but these functions also depend on the probability distribution. There are two possible directions of the velocity that satisfy the energy equation. A linear momentum function is defined that integrates to zero, and this property is consistent with the expectation value of the linear momentum for stationary states with real-valued wave functions. The energy equation is integrated to obtain a version of the well known energy equation involving reduced density matrices, where the kinetic energy functional of the one-particle density matrix is replaced by a function of the electron density and a velocity function. Also, the noninteracting kinetic energy functional from the Hohenberg--Kohn theorem is given as an explicit functional of the orbital densities. For the purpose of describing the behavior of particles in a stationary state, a model based on the energy equation is constructed. The model is evaluated for the two different velocity directions using the grounds state of the particle in a one-dimensional box and the hydrogen atom. For one velocity direction, equations of motions with contradictory properties are obtained, and, in the other, an unstable system is found. A discussion is given with suggestions of additional elements that might improve the model.

physics.atom-ph↗

arXiv2021

The Fluid Dynamics of the One-Body Stationary States of Quantum Mechanics with Real Valued Wavefunctions

It is demonstrated that the probability density function, given by the square of a quantum mechanical wavefunction that is a real-valued eigenvector of a time-independent, one-body Schroedinger equation, satisfies a compressible-flow generalization of the Bernoulli equation, where the mass density is the probability density times the mass of the system; the pressure and velocity fields are defined by functions depending on the probability density, and the gradient and the Laplacian of the probability density, where there are two possible directions of the velocity on a streamline. The velocity given definition implies a generalization of the steady-flow continuity equation where mass is not locally conserved. The gradient of the Bernoullian equation is demonstrated to be equivalent to the steady flow Euler equation for variable mass and irrotational flow. A speed of sound quadratic equation is obtained from a spherical wave-pulse. One of the solutions indicates that the wave-pulse velocity on a streamline is equal in magnitude but opposite in direction of the fluid velocity on the streamline. The other solution is the focus of attention from that point on. It is proven that the extremums of the momentum per volume on a streamline occur at points that are Mach 1 speed. The developed formalism is applied to a particle in a one-dimensional box, the ground and first excited-states of the one-dimensional harmonic oscillator, and the hydrogen 1s and 2s states. Some behavior is repeated in all the applications examined. For example, an antinode, a point of local-maximum density, has zero velocity and zero Mach speed on the streamline, while a node, a point of minimum density, has infinite velocity and Mach 2. In between the node and antinode is an extremum of the momentum, and Mach 1. (This is a short version of the abstract.)

physics.atom-ph↗

arXiv2016

The Differential Virial Theorem with Gradient Formulas for the Operators

A gradient dependent formula is derived for the spinless one-particle density-matrix operator z from the differential virial theorem. A gradient dependent formula is also derived for a spinless one-particle density-matrix operator that can replace the two operators of the differential virial theorem that arise from the kinetic energy operator. Other operators are also derived that can replace the operators mentioned above in the differential virial theorem; these operators depend on the real part of spinless one-particle density-matrix.

physics.chem-ph↗

arXiv2005

Expressions for the Exchange Correlation Potential and Exchange Correlation Functional of Kohn--Sham Density Functional Theory

The State--Specific Kohn--Sham Density Functional Theory [arXiv:physics/0506037] is used to derive the Kohn-Sham exchange-correlation potential $\vxc$ and exchange-correlation energy $\Eco$ as explicit functionals of $v_s$ and $ϕ_1$, where $v_s$ is the local, one-body potential from the Kohn--Sham equations, and $ϕ_1$ is the spinless one-particle density matrix from the Kohn--Sham noninteracting state, say $|ϕ_1\ran$. In other words, $|ϕ_1\ran$ is the ground state eigenfunction of the noninteracting Schrödinger equation with the one-body potential $v_s$. For simplicity, we only consider noninteracting states that are closed-shell states and interacting states that are nondegenerate, singlet ground-states.

physics.chem-ph↗

arXiv2005

State-Specific Kohn-Sham Density Functional Theory

A generalization of the Kohn--Sham approach is derived where the correlation-energy functional depends on the one-particle density matrix of noninteracting states and on the external potential from the interacting target-state. The one-particle equations contain the exact exchange potential, a nonlocal correlation potential, and an additional operator involving the correlation density. The electronic-energy functional has multiple solutions: Any one-particle density matrix delivering the target-state density yields a solution. In order to obtain the Kohn--Sham solution, the nonlocal operators are converted into local ones using an approach developed by Sala and Gorling. Since the exact exchange-potential is used, and the N--representability problem does not arise--in contrast to the Kohn--Sham approach--errors from Coulomb self-interactions do not occur, nor the need to introduce functionals defined by a constraint search. Furthermore, the approach does not use the Hohenberg-Kohn theorem. A density functional formalism is also derived that assumes that the one-particle density matrices of interest have v-representable (non-interacting) densities and that these density matrices can be written as an explicit functional of the electron density. For simplicity, we only consider noninteracting closed-shell states and target states that are nondegenerate, singlet ground-states.

physics.chem-ph↗

arXiv2004

The conversion of nonlocal one-body operators into local ones: The Slater potential revisited

One-particle Schrodinger equations are considered, e.g., the Hartree--Fock equations, that contain a nonlocal operator, e.g., the Hartree--Fock exchange operator, where this operator depends on the one-particle density-matrix of a determinantal state. One-body nonlocal operators of this type are converted into approximate local potentials that depend on the kernel of the nonlocal operator and, also, the one-particle density matrix that, as mentioned above, the nonlocal operator also depends on. When the non-local operator is the exchange operator, the method yields the Slater potential.

physics.chem-ph↗

arXiv2004

Developments for Reference--State One--Particle Density--Matrix Theory

Brueckner orbitals, and the density of the Brueckner reference-state, are shown to satify the same cusp condition -- involving the nuclear charges -- as natural- and Hartree--Fock-orbitals. Using the cusp condition, the density of a determinantal state can be used to determine the external potential, if the determinantal state is from either Hartee--Fock or Brueckner-orbital theory, as well as, determinant states obtained by many other formalisms that are defined by a one-body operator, if a portion of the one-body operator -- the portion not associated with the kinetic energy or external potential -- generates a well behaved function when acting on an occupied orbital. Using this relationship involving a determinant and its external potential, a variation of Reference--State One--Particle Density--Matrix Theory (physics/0308056) is formulated, where the trial wavefunctions are universal, in the Kohn-Sham sense, since they do not depend on the external potential. The resulting correlation-energy functionals, are also, universal, except for a relatively small term involving the portion of the expectation value of the external potential with the trial wavefunctions that appears beyond the first order. The same approximate energy functionals that were shown to be valid for the previous v-dependent, Reference--State One--Particle Density--Matrix Theory (physics/0308084), are shown to be valid for the current approach, except that the use of the LYP and Colle--Salvetti functional appear more natural within the current approach, since these functionals are universal ones. And since the BLYP and B3LYP functionals contain the LYP functional, these approaches are also better suited with the current approach.

physics.chem-ph↗

arXiv2003

Using the local density approximation and the LYP, BLYP, and B3LYP functionals within Reference--State One--Particle Density--Matrix Theory

For closed-shell systems, the local density approximation (LDA) and the LYP, BLYP, and B3LYP functionals are shown to be compatible with reference-state one-particle density-matrix theory, where this recently introduced formalism is based on Brueckner-orbital theory and an energy functional that includes exact exchange and a non-universal correlation-energy functional. The method is demonstrated to reduce to a density functional theory when the exchange-correlation energy-functional has a simplified form, i.e., its integrand contains only the coordinates of two electron, say r1 and r2, and it has a Dirac delta function -- delta(r1 - r2) -- as a factor. Since Brueckner and Hartree--Fock orbitals are often very similar, any local exchange functional that works well with Hartree--Fock theory is a reasonable approximation with reference-state one-particle density-matrix theory. The LDA approximation is also a reasonable approximation. However, the Colle--Salvetti correlation-energy functional, and the LYP variant, are not ideal for the method, since these are universal functionals. Nevertheless, they appear to provide reasonable approximations. The B3LYP functional is derived using a linear combination of two functionals: One is the BLYP functional; the other uses exact exchange and a correlation-energy functional from the LDA.

physics.chem-ph↗

arXiv2003

Reference-State One-Particle Density-Matrix Theory

A density-matrix formalism is developed based on the one-particle density-matrix of a single-determinantal reference-state. The v-representable problem does not appear in the proposed method, nor the need to introduce functionals defined by a constrained search. The correlation-energy functionals are not universal; they depend on the external potential. Nevertheless, model systems can still be used to derive universal energy-functionals. In addition, the correlation-energy functionals can be partitioned into individual terms that are -- to a varying degree -- universal; yielding, for example, an electron gas approximation. Variational and non-variational energy functionals are introduced that yield the target-state energy when the reference state -- or its corresponding one-particle density matrix -- is constructed from Brueckner orbitals. Using many-body perturbation theory, diagrammatic expansions are given for the non-variational energy-functionals, where the individual diagrams explicitly depend on the one-particle density-matrix. Non-variational energy-functionals yield generalized Hartree--Fock equations involving a non-local correlation-potential and the Hartree--Fock exchange; these equations are obtained by imposing the Brillouin--Brueckner condition. The same equations -- for the most part -- are obtained from variational energy-functionals using functional minimizations, yielding the (kernel of) correlation potential as the functional derivative of correlation-energy functionals. Approximations for the correlation-energy functions are introduced, including a one-particle-density-matrix variant of the local-density approximation (LDA) and a variant of the Lee--Yang--Parr (LYP) functional.

physics.chem-ph↗