The inverse Henderson problem refers to the determination of the pair potential which specifies the interactions in an ensemble of classical particles in continuous space, given the density and the equilibrium pair correlation function of these particles as data. For a canonical ensemble in a bounded domain it has been observed that this pair potential minimizes a corresponding convex relative entropy functional, and that the Newton iteration for minimizing this functional coincides with the so-called inverse Monte Carlo (IMC) iterative scheme. In this paper we show that in the thermodynamic limit analogous connections exist between the specific relative entropy introduced by Georgii and Zessin and a proper formulation of the IMC iteration in the full space. This provides a rigorous variational framework for the inverse Henderson problem, valid within a large class of pair potentials, including, for example, Lennard-Jones type potentials.
It is further shown that the pressure is strictly convex as a function of the pair potential and the chemical potential, and that the specific relative entropy at fixed density is a strictly convex function of the pair potential. At a given reference potential and a corresponding density in the gas phase we determine the gradient and the Hessian of the specific relative entropy, and we prove that the Hessian extends to a symmetric positive semidefinite quadratic functional in the space of square integrable perturbations of this potential.
The inverse Henderson problem of statistical mechanics concerns classical particles in continuous space which interact according to a pair potential depending on the distance of the particles. Roughly stated, it asks for the interaction potential given the equilibrium pair correlation function of the system. In 1974 Henderson proved that this potential is uniquely determined in a canonical ensemble and he claimed the same result for the thermodynamical limit of the physical system. Here we provide a rigorous proof of a slightly more general version of the latter statement using Georgii's versi…
In this paper, we survey our recent results on the variational formulation of nonequilibrium thermodynamics for the finite dimensional case of discrete systems as well as for the infinite dimensional case of continuum systems. Starting with the fundamental variational principle of classical mechanics, namely, Hamilton's principle, we show, with the help of thermodynamic systems with gradually increasing level complexity, how to systematically extend it to include irreversible processes. In the finite dimensional cases, we treat systems experiencing the irreversible processes of mechanical fric…
An application of variational principle to bifurcation of periodic solution in Lagrangian mechanics is shown. A few higher derivatives of the action integral at a periodic solution reveals the behaviour of the action in function space near the solution. Then the variational principle gives a method to find bifurcations from the solution. The second derivative (Hessian) of the action has an important role. At a bifurcation point, an eigenvalue of Hessian tends to zero. Inversely, if an eigenvalue tends to zero, the zero point is a bifurcation point. The third and higher derivatives of the actio…
Employing a phase space which includes the (Riemann-Liouville) fractional derivative of curves evolving on real space, we develop a restricted variational principle for Lagrangian systems yielding the so-called restricted fractional Euler-Lagrange equations (both in the continuous and discrete settings), which, as we show, are invariant under linear change of variables. This principle relies on a particular restriction upon the admissible variation of the curves. In the case of the half-derivative and mechanical Lagrangians, i.e. kinetic minus potential energy, the restricted fractional Euler-…
Hartree--Fock theory in quantum mechanics is reviewed, from the proposal of the Hartree--Fock approximation right after quantum mechanics was formulated to its applications in modern physics. This includes the description of traditional Hartree--Fock theory in quantum chemistry, its generalizations of various kinds, and its importance for predicting the presence of symmetry breaking, or the absence thereof.
Variational approach to nonholonomic and inequality-constrained mechanics
Department of Mathematics and Physics, University of Stavanger（数学与物理系，斯塔万格大学）；Department of Physics, Korea University（物理系，韩国大学）；Department of Physics, University of Cape Town（物理系，开普敦大学）；Department of Physics, New Mexico State University（物理系，新墨西哥州立大学）；Theoretical Sciences Visiting Program, Okinawa Institute of Science and Technology Graduate University（理论科学访问计划，冲绳科学技术大学院大学）
The mechanics of a flexible membrane decorated with a nematic liquid-crystal texture is considered in a variational framework. The variations on the splay, twist and the bend energy of the nematics are obtained from the local deformations leading to changes in the shape membrane. The Euler-Lagrange derivatives and the Noether charges are identified from the variational equations. The nematic stress tensor is obtained as a consequence of translational invariance. Likewise, the rotational invariance implies the torque nematic tensor. The corresponding boundary conditions are obtained for free ed…
In this paper we combine two main topics in mechanics and optimal control theory: contact Hamiltonian systems and Pontryagin Maximum Principle. As an important result, among others, we develop a contact Pontryagin Maximum Principle that permits to deal with optimal control problems with dissipation. We also consider the Herglotz optimal control problem, which is simultaneously a generalization of the Herglotz variational principle and an optimal control problem. An application to the study of a thermodynamic system is provided.
In this paper, high-order numerical integrators on homogeneous spaces will be presented as an application of nonholonomic partitioned Runge-Kutta Munthe-Kaas (RKMK) methods on Lie groups. A homogeneous space $M$ is a manifold where a group $G$ acts transitively. Such a space can be understood as a quotient $M \cong G/H$, where $H$ a closed Lie subgroup, is the isotropy group of each point of $M$. The Lie algebra of $G$ may be decomposed into $\mathfrak{g} = \mathfrak{m} \oplus \mathfrak{h}$, where $\mathfrak{h}$ is the subalgebra that generates $H$ and $\mathfrak{m}$ is a subspace. Thus, varia…
We are describing relations between Schrödinger's variational problem and Onsager's approach to nonequilibrium statistical mechanics. Although the second work on reciprocal relations and detailed balance has been published in the same year (1931) as the first one, the impact of Schrödinger's idea has not yet been considered in the classical context of Onsager.
