Theory of solutions in energy representation (ER method) developed by Matubayasi and Nakahara provides with an approximate way of calculating solvation free energies (or, identically, the excess chemical potentials) from atomistic simulations. In this document we provide some derivation details of this, to our opinion, theoretically involved method, which will help a non-specialist to follow. There are three points which differ this document from a regular textbook on statistical mechanics or research articles:
1) Derivation is detailed and all approximations are explicitly stated;
2) Statistical mechanics derivations are performed in NPT-ensemble;
3) We perform the derivations for the case when a molecule is represented as a set of (atomic) sites interacting via spherically symmetric potentials (a classical Force Field representation).
In ER method, a new collective coordinate is introduced - the interaction energy of a solute and a solvent molecule. The excess chemical potential is expressed as a functional of the solute-solvent density distribution defined over the collective variable. The functional can be approximated by the Percus's method of functional expansion, which leads to the end-point (not dependent on the $λ$-coupling path) free energy expression.
As a side result, we prove that the solvation free energy is always equivalent to the excess (over ideal) chemical potential, and not only at infinite dilution or when internal molecule degrees of freedom are not affected by solvation as it is sometimes wrongly believed.
Lee-Yang and Fisher zeros are crucial for the study of phase transitions in the grand canonical and the canonical ensembles, respectively. However, these powerful methods do not cover the isothermal-isobaric ensemble (NPT ensemble), which reflects the conditions of many experiments. In this work we present a theory of the phase transitions in terms of the zeros of the NPT-ensemble partition functions in the complex plane. The proposed theory provides an approach to calculate all the partition function zeros in the NPT ensemble, which form certain curves in the thermodynamic limit. To verify th…
We investigate the characteristics of two dimensional melting in simple atomic systems via isobaric-isothermal ($NPT$) and isochoric-isothermal ($NVT$) molecular dynamics simulations with special focus on the effect of the range of the potential on the melting. We find that the system with interatomic potential of longer range clearly exhibits a region (in the $PT$ plane) of (thermodynamically) stable hexatic phase. On the other hand, the one with shorter range potential exhibits a first-order melting transition both in $NPT$ and $NVT$ ensembles. Melting of the system with intermediate range p…
A thermodynamic expression for the analog of the canonical ensemble for nonequilibrium systems is described based on a purely information theoretical interpretation of entropy. As an application, it is shown that this nonequilibrium canonical distribution implies some important results from nonequilibrium thermodynamics, specifically, the fluctuation theorem and the Jarzynski-equality.
We develop a regularization of the quantum microcanonical ensemble, called a Gaussian ensemble, which can be used for derivation of the canonical ensemble from microcanonical principles. The derivation differs from the usual methods by giving an explanation for the, at the first sight unreasonable, effectiveness of the canonical ensemble when applied to certain small, isolated, systems. This method also allows a direct identification between the parameters of the microcanonical and the canonical ensemble and it yields simple indicators and rigorous bounds for the effectiveness of the approxima…
Microcanonical ensemble theory of bosons is derived from quantum mechanics by making use of a hidden gauge structure. The relative phase interaction associated with this gauge structure, described by the Pegg-Barnett formalism, is shown to lead to perfect decoherence in the thermodynamics limit and the principle of equal a priori probability, simultaneously.
Starting from the quantum mechanics for $N$ particles, we show that we can directly derive the microcanonical ensemble average of the physical quantity $A$ by using only the long time average and the equal probability assumption for the equal energy states. The system is considered to be embedded in the outer world and we describe them in terms of the density matrix method.
We consider bosonic atoms with a repulsive contact interaction in a trap potential for a Bose-Einstein condensation and additionally include a random potential. The ensemble averages for two models of static and dynamic disorder are performed and investigated in parallel. The bosonic many body systems of the two disorder models are represented by coherent state path integrals on the Keldysh time contour which allow exact ensemble averages for zero and finite temperatures. These ensemble averages of coherent state path integrals therefore present alternatives to replica field theories or supers…
A pedagogical approach for deriving the statistical mechanical partition function, in a manner that emphasizes the key role of entropy in connecting the microscopic states to thermodynamics, is introduced. The connections between the combinatoric formula $S= k \ln W$ applied to the Gibbs construction, the Gibbs entropy, $S = -k \sum\limits_i p_i \ln p_i$, and the microcanonical entropy expression $S= k \ln Ω$ are clarified. The condition for microcanonical equilibrium, and the associated role of the entropy in the thermodynamic potential is shown to arise naturally from the postulate of equal …
A coherent state path integral is considered for bosons with an ensemble average of a random potential and with an additional, repulsive interaction in the context of BEC under inclusion of specially prepared disorder. The essential normalization of the coherent state path integral, as a generating function of observables, is obtained from the non-equilibrium time contour for 'forward' and 'backward' propagation so that a time contour metric has to be taken into account in the ensemble average with the random potential. Therefore, the respective symmetries for the derivation of a nonlinear sig…
Solid helium (3He and 4He) in the hcp and fcc phases has been studied by path-integral Monte Carlo. Simulations were carried out in the isothermal-isobaric (NPT) ensemble at pressures up to 52 GPa. This allows one to study the temperature and pressure dependences of isotopic effects on the crystal volume and vibrational energy in a wide parameter range. The obtained equation of state at room temperature agrees with available experimental data. The kinetic energy, E_k, of solid helium is found to be larger than the vibrational potential energy, E_p. The ratio E_k/E_p amounts to about 1.4 at low…
A comprehensive and detailed account is presented for the finite-temperature many-body perturbation theory for electrons that expands in power series all thermodynamic functions on an equal footing. Algebraic recursions in the style of the Rayleigh-Schrödinger perturbation theory are derived for the grand potential, chemical potential, internal energy, and entropy in the grand canonical ensemble and for the Helmholtz energy, internal energy, and entropy in the canonical ensemble, leading to their sum-over-states analytical formulas at any arbitrary order. For the grand canonical ensemble, thes…
We derived the equation of the density operator for generalized entropy and generalized expectation value with quantum analysis when conserved quantities exist. The derived equation is simplified when the conventional expectation value is employed. The derived equation is also simplified when the commutation relations, $[\hatρ, \hat{H}]$ and $[\hatρ, \hat{Q}^{[a]}]$, are the functions of the density operator $\hatρ$, where $\hat{H}$ is the Hamiltonian, and $\hat{Q}^{[a]}$ is the conserved quantity. We derived the density operators for the von Neumann entropy, the Tsallis entropy, and the Rényi…
All of the basic microsopic physical laws are time reversible. In contrast, the second law of thermodynamics, which is a macroscopic physical representation of the world, is able to describe irreversible processes in an isolated system through the change of entropy S larger than 0. It is the attempt of the present manuscript to bridge the microscopic physical world with its macrosocpic one with an alternative approach than the statistical mechanics theory of Gibbs and Boltzmann. It is proposed that time is discrete with constant step size. Its consequence is the presence of time irreversibilit…
The grand canonical ensemble lies at the core of quantum and classical statistical mechanics. A small system thermalizes to this ensemble while exchanging heat and particles with a bath. A quantum system may exchange quantities represented by operators that fail to commute. Whether such a system thermalizes and what form the thermal state has are questions about truly quantum thermodynamics. Here we investigate this thermal state from three perspectives. First, we introduce an approximate microcanonical ensemble. If this ensemble characterizes the system-and-bath composite, tracing out the bat…
The diffusion coefficient--a measure of dissipation, and the entropy--a measure of fluctuation are found to be intimately correlated in many physical systems. Unlike the fluctuation dissipation theorem in linear response theory, the correlation is often strongly non-linear. To understand this complex dependence, we consider the classical Brownian diffusion in this work. Under certain rational assumption, i.e. in the bi-component fluid mixture, the mass of the Brownian particle $M$ is far greater than that of the bath molecule $m$, we can adopt the weakly couple limit. Only considering the firs…
A possible quantum-mechanical origin of statistical mechanics is discussed, and microcanonical and canonical ensembles of bosons and fermions are derived from the stationary Schrödinger equation in a unified manner. The interaction Hamiltonians are constructed by the use of the discrete phase operators and the gauge-theoretical structure associated with them. It is shown how the interaction Hamiltonians stipulated by the gauge symmetry generate the specific patterns of entanglement that are desired for establishing microcanonical ensembles. A discussion is also made about the interrelation bet…
We give a simple derivation of all $n$-point densities for the eigenvalues of the real Ginibre ensemble with even dimension $N$ as quaternion determinants. A very simple symplectic kernel governs both, the real and complex correlations. 1-and-2-point correlations are discussed in more detail. Scaling forms for large dimension $N$ are derived.
We present a novel derivation of the constraints required to obtain the underlying principles of statistical mechanics using a maximum entropy framework. We derive the mean value constraints by use of the central limit theorem and the scaling properties of Lagrange multipliers. We then arrive at the same result using a quantum free field theory and the Ward identities. The work provides a principled footing for maximum entropy methods in statistical physics, adding the body of work aligned to Jaynes's vision of statistical mechanics as a form of inference rather than a physical theory dependen…
We derive the microcanonical ensemble from the Maximum Entropy Principle (MEP) using the phase space volume entropy of P. Hertz. Maximizing this entropy with respect to the probability distribution with the constraints of normalization and average energy, we obtain the condition of constant energy. This approach is complementary to the traditional derivation of the microcanonical ensemble from the MEP using Shannon entropy and assuming a priori that the energy is constant which results in equal probabilities.
A finite-temperature many-body perturbation theory is presented that expands in power series the electronic grand potential, chemical potential, internal energy, and entropy on an equal footing. Sum-over-states and sum-over-orbitals analytical formulas for the second-order perturbation corrections to these thermodynamic properties are obtained in a time-independent, nondiagrammatic, algebraic derivation, relying on the sum rules of the Hirschfelder-Certain degenerate perturbation energies in a degenerate subspace as well as nine algebraic identities for zeroth-order thermal averages of one- th…
In this paper, we first briefly review some recent results on the distribution of the maximal eigenvalue of a $(N\times N)$ random matrix drawn from Gaussian ensembles. Next we focus on the Gaussian Unitary Ensemble (GUE) and by suitably adapting a method of orthogonal polynomials developed by Gross and Matytsin in the context of Yang-Mills theory in two dimensions, we provide a rather simple derivation of the Tracy-Widom law for GUE. Our derivation is based on the elementary asymptotic scaling analysis of a pair of coupled nonlinear recursion relations. As an added bonus, this method also all…
The distribution function of the free energy fluctuations in one-dimensional directed polymers with free boundary conditions is derived by mapping the replicated problem to the N-particle quantum boson system with attractive interactions. It is shown that in the thermodynamic limit this function is described by the universal Tracy-Widom distribution of the Gaussian orthogonal ensemble.
It is shown that for any ensemble, whether classical or quantum, continuous or discrete, there is only one measure of the "volume" of the ensemble that is compatible with several basic geometric postulates. This volume measure is thus a preferred and universal choice for characterising the inherent spread, dispersion, localisation, etc, of the ensemble. Remarkably, this unique "ensemble volume" is a simple function of the ensemble entropy, and hence provides a new geometric characterisation of the latter quantity. Applications include unified, volume-based derivations of the Holevo and Shannon…
We show that within classical statistical mechanics without taking the thermodynamic limit, the most general Boltzmann factor for the canonical ensemble is a q-exponential function. The only assumption here is that microcanonical distributions have to be separable from of the total system energy, which is the prerequisite for any sensible measurement. We derive that all separable distributions are parametrized by a mathematical separation constant Q which can be related to the non-extensivity q-parameter in Tsallis distributions. We further demonstrate that nature fixes the separation constant…
There are several formulations of the second law, and they may, in principle, have different domains of validity. Here a simple mathematical theorem is proven which serves as the most general basis for the second law, namely the Thomson formulation (`cyclic changes cost energy'), applied to equilibrium. This formulation of the second law is a property akin to particle conservation (normalization of the wavefunction). It has been stricktly proven for a canonical ensemble, and made plausible for a micro-canonical ensemble. As the derivation does not assume time-inversion-invariance, it is applic…
The present study regards the zeroth order mean field approximation of a dipole-type interaction model, which is analytically solved in the canonical and microcanonical ensembles. After writing the canonical partition function, the free and internal energies, magnetization and the specific heat are derived and graphically represented. A crucial derivation is the calculation of the free energy, which is variationally evaluated, and it is shown that the exact result coincides with the approximate trend when $N$ tends to infinity. In the microcanonical ensemble, the entropy as other thermodynamic…
