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Extremization of Entropy, Central Limit Theorem and Classical Statistical and Quantum Mechanics

Francesco R. Ruggeri

Published Aug 21, 2023• 0 citations
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Abstract

Extremization of entropy, usually subject to an average energy constraint,(Maxwell-Boltzmann gas) is often associated with maximization of the number of microstates N gas particles may represent. The math procedure of extremization (variational calculus) is then associated with the ln of a factorial expression which reduces to n(ei)ln(n(ei)) using Stirling’s approximation. The central limit theorem, on the other hand, states that the distribution of sample means of a random variable approaches a Gaussian, i.e exp(-pp/(2sig sig)). Here sig sig is the standard deviation. For a random variable, the important or characteristic information is the standard deviation associated with the average of the square pp. We suggest here that an alternative way of looking at maximization of entropy (which is a stability statement we argue) other than ln of permutations is to consider the stability of the variation of the variance of pp subject to a change in the probability, with pp written in terms of P(p). Average kinetic energy in a statistical problem represents such a variance and should be invariant under changes of the probability subject to an average kinetic energy constraint, we suggest. How does this idea apply to quantum mechanics? In quantum mechanics, one has a statistical function exp(ipx) and for bound states creates W(x)=wavefunction = Sum over p a(p)exp(ipx). a(p)a(p) is formally the probability for p, but this does not mean that a(p)a(p) is a random variable because one has the constraint: Sum over p a(p)a(p) pp2/m + Integral dx V(x) W(x)W(x) = En. In the case of a harmonic oscillator, however, one knows a priori that the two summands are each equal to En/2. Furthermore there are a set of En values, starting at a ground state and increasing. All En values, except the ground state, are metastable. Thus the ground state is a special state. Given that Sum over p a(p)a(p)pp2/m = Eo/2, a priori, one may consider that all of the information of a(p)a(p) is associated with Eo. This is exactly the case for a Gaussian from the central limit theorem. Alternatively, from information theory, information = ln(probability) which yields the same result. If this is the case, then pp/2m a(p)a(p) written strictly in terms of P(p)=a(p)a(p) should be stationary upon changing P(p) subject to the E/2 constraint. This special situation, however, only holds for the ground state oscillator. What about average potential energy for the ground state oscillator? If the probability for p (momentum) is a Gaussian due to the Central Limit theorem, this means that the standard deviation is the information (and is linked with randomness). Taking a Fourier transform of a(p) cannot add more information to the picture, we argue. W(x)W(x) should also be a Gaussian, as it is. As a result, xxW(x)W(x), written in terms of P(x)=W(x)W(x) subject to the same Eo/2 constraint should represent a maximization or stationary situation, we argue.

DOI
10.5281/zenodo.8270474

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Extremization of entropy, usually subject to an average energy constraint,(Maxwell-Boltzmann gas) is often associated with maximization of the number of microstates N gas particles may represent. The math procedure of extremization (variational calculus) is then associated with the ln of a factorial expression which reduces to n(ei)ln(n(ei)) using Stirling’s approximation. The central limit theorem, on the other hand, states that the distribution of sample means of a random variable approaches a Gaussian, i.e exp(-pp/(2sig sig)). Here sig sig is the standard deviation. For a random variable, the important or characteristic information is the standard deviation associated with the average of the square pp. We suggest here that an alternative way of looking at maximization of entropy (which is a stability statement we argue) other than ln of permutations is to consider the stability of the variation of the variance of pp subject to a change in the probability, with pp written in terms of P(p). Average kinetic energy in a statistical problem represents such a variance and should be invariant under changes of the probability subject to an average kinetic energy constraint, we suggest. How does this idea apply to quantum mechanics? In quantum mechanics, one has a statistical function exp(ipx) and for bound states creates W(x)=wavefunction = Sum over p a(p)exp(ipx). a(p)a(p) is formally the probability for p, but this does not mean that a(p)a(p) is a random variable because one has the constraint: Sum over p a(p)a(p) pp2/m + Integral dx V(x) W(x)W(x) = En. In the case of a harmonic oscillator, however, one knows a priori that the two summands are each equal to En/2. Furthermore there are a set of En values, starting at a ground state and increasing. All En values, except the ground state, are metastable. Thus the ground state is a special state. Given that Sum over p a(p)a(p)pp2/m = Eo/2, a priori, one may consider that all of the information of a(p)a(p) is associated with Eo. This is exactly the case for a Gaussian from the central limit theorem. Alternatively, from information theory, information = ln(probability) which yields the same result. If this is the case, then pp/2m a(p)a(p) written strictly in terms of P(p)=a(p)a(p) should be stationary upon changing P(p) subject to the E/2 constraint. This special situation, however, only holds for the ground state oscillator. What about average potential energy for the ground state oscillator? If the probability for p (momentum) is a Gaussian due to the Central Limit theorem, this means that the standard deviation is the information (and is linked with randomness). Taking a Fourier transform of a(p) cannot add more information to the picture, we argue. W(x)W(x) should also be a Gaussian, as it is. As a result, xxW(x)W(x), written in terms of P(x)=W(x)W(x) subject to the same Eo/2 constraint should represent a maximization or stationary situation, we argue.
Classical statistical mechanical density maximizes entropy subject to constraints i.e. one has the Maxwell-Boltzmann (MB) distribution P(x)P(p) proportional to exp(- pp/2mT - V(x)/T). Quantum mechanics is also a statistical theory, but it is not based on the maximization of entropy. Rather it is based on a conditional probability P(p/x) = a(p)exp(ipx)/W(x) where W(x) =wavefunction = Sum over p a(p)exp(ipx) such that: Sum over p pp/2m P(p/x) + V(x) = E (bound states). As a result, it has classical densities P(x)=W(x)W(x) and P(p)=a(p)a(p), but these in general do not maximize entropy and so do not match the MB distribution. There is a special case, however, namely the ground state oscillator for which the quantum mechanical results P(x) and P(p) are both Gaussians. It is shown in (1) that for a fixed variance, a Gaussian maximizes entropy. Thus, the MB scenario must be a Gaussian for an oscillator as it is, but the quantum result is also a Gaussian and so matches the classical statistical mechanical result. In this note, we show that the time-independent Schrodinger equation collapses to the equality situation in Heisenberg’s uncertainty principle, suggesting that the solution also represents maximum entropy.
In (1), we noted that a Gaussian wavefunction may be a solution to the time-independent Schrodinger equation (e.g. the ground state solution of the quantum oscillator) and simultaneously a solution of maximizing spatial Shannon’s entropy - density(x) ln(density(x)) subject to the constraint V(x) xx constant, where density(x) =W*(x)W(x) with W(x) being the wavefunction. In (2), which deals strictly with classical probabilities and the Maxwell-Boltzmann factor n(ei) = exp(-ei/T), we argued that this function is equivalent to: ln(n(ei)) = -ei/T. This in turn is equivalent to the maximization of ln(n(ei)!) with the constraint ei n(ei) which is part of: ln( N!/ Product over i n(ei)!) with the full constraint Sum over i ei n(ei)=Eave. Here n(ei)=N p(ei) where p(ei) is a probability and N a very large number. Thus a function of exp( something) may indicate that “something” * density(x) is a constraint with -density ln(density) being Shannon’s entropy. Quantum mechanics for a bound system yields a real wavefunction W(x) such that density(x)=W(x)W(x)=probability(x). Thus maximization of Shannon’s entropy - density(x) ln (density) subject to a constraint: density(x)B(x) should correspond to a solution for density of exp( B(x)). B(x) as part of the constraint, however, should represent a physical constraint. Thus if there is a solution to the Schrodinger equation of the form exp(.5B(x)) and B(x)density(x) represents the physical constraint in the system, classical maximization of probability solves the quantum problem in such a case. The above ideas may be applied to the quantum oscillator ground state and essentially repeat what is done in (1). We, however, try to generalize them to see if they may apply to a free quantum particle. In this case the probability used is exp(ipx) which is complex. It corresponds to P(x)=exp(ipx)exp(-ipx)=1 which is a uniform distribution which has maximum lack of information.
Classical statistical mechanics often utilizes the idea of maximizing entropy subject to a physical constraint For example, for a Maxwell-Boltzmann gas, this constraint is Sum over i ei p(ei) where ei=pp/2m (no V(x)). We have argued previously that there may be many possible constraints, i.e. an average of any power of ei could be a physical constraint. We stated that a conserved quantity associated with interactions present (creating equilibrium) should be used. Here we examine the constraint in terms of mechanical resistance i.e. pressure. We further consider the free particle quantum wavefunction exp(-iEt+ipx) in terms of resistances in time and space. We argue that the form exp(-ipx)exp(ipx) = 1 removes the stochasticity associated with motion due to the resistance (impulse) p Thus 1 or 1/L (L=length) seems to be a smoothed over picture associated with a constant flux and overlooks the inherent stochasticity associated with motion. This stochasticity is crucial when describing impulse hit reactions (n-slits, index of refraction interfaces, interactions with V(x)), but if a particle does not interact in space, then the W*(x)W(x) picture seems to be used to describe the v(average)=x/t scenario. The issue is that for a quantum bound state, there is also an rms velocity based on a wavefunction and one may create an average W(x)W(x) (W(x) is real for a bound state), but like exp(-ipx)exp(ipx), this bypasses some of the stochasticity in the problem, we argue. It only demonstrates stochasticity associated with differences in momentum.
The Maxwell-Boltzmann MB distribution is often derived by maximizing the number of possible arrangements of particles with different energies subject to the constraint of a fixed number of particles and fixed energy. Using the canonical approximation that only average energy is conserved and using Stirling’s approximation for large number factorials leads to the Maxwell-Boltzmann distribution. The ln of total number of arrangements using Stirling’s approximation is linked to a math form called Shannon’s entropy i.e. - Sum over i f(ei) ln(f(ei)). Interestingly this same MB result may be obtained through reaction balance which makes no use of the idea of arrangements or entropy or maximization. It is concerned with including all possible physical reactions (for example two body reactions between all energy particles) subject to conservation of energy. In this sense it deals directly with the dynamics of the problem while the arrangement approach does not. The dynamical approach considers all possible reactions with notions of independence or lack of information and ensures the system remains unchanged. Why are they the same? We argue that it is because the “recipe” for the probability of two body reactions namely n(e1)n(e2) is of the same form as the leading factor of n(e1)! n(e2)!. In the case of quantum mechanics one may apply the dynamical approach to obtain the time-independent Schrodinger equation. In such a case one does not need to think in terms of “maximizing” any quantity although one considers all possible reactions with a potential V(x). a(p) factors in W(x) = wavefunction = Sum over p a(p)exp(ipx) are interrelated, but retain their identity after all possible interactions occur. This we argue is the idea for the eigenvalue equation. At the same time, Shannon’s entropy, which is directly linked to the notion of arrangements, is applied to a bound state and possibly linked to thermodynamics i.e. dE = TdS -PdV which may be applied to an adiabatic expansion. Shannon’s entropy is created from existing probabilities in this case which do not arise from explicitly maximizing entropy subject to constraints as the probabilities follow directly from the Schrodinger equation. One might ask why Shannon’s entropy has any relevance if it is the dynamics which determines the value of W(x) and a(p). It seems, however, that one may knock out a particle in a state p with probability P(p)= a*(p)a(p) or find a particle at x with probability P(x)=W*(x)W(x). These are classical type probabilities linked to the quantum dynamical probabilities a(p) and W(x). It seems Shannon’s entropy is only applied to P(x) and P(p) or a product P(x)P(p) which may give it physical meaning in a quantum bound state. We examine these ideas in this note.
Historically, thermodynamics was formulated for macroscopic systems followed by the development of statistical mechanics which provided microscopic formulations for quantities such as entropy. Entropy is traditionally linked to the ln of the number states available or to the Shannon’s form -k Sum over i P(ei) ln(P(ei)) where P(ei) is the probability for the quantity ei. In addition a variable T (linked to average kinetic energy) appears in both theories. Later the Schrodinger equation was developed to describe bound electron states in an atom etc. These states were characterized by a math object W(x) called the wavefunction and a set of discrete energy levels was calculated which matched data of emitted photons. In a previous note (1) we argued that the average energy En for a quantum bound state plays the same role of characterizing equilibrium as T in classical thermodynamics/statistical mechanics. We further argued that En is linked to parameters in the system. For example, for a particle in a box with infinite potential walls, En is linked to L as well as to n the energy level. One may change En by either changing n or L separately (or both). Holding L constant and changing n leads to a certain type of energy change. We argue this is similar to holding the volume of a gas constant and increasing T. Alternatively, one may leave n unchanged (a quantum adiabatic process) and change L i.e. a mechanical change or work. We argue that one may already consider the concept of the first law of thermodynamics at the quantum bound state level i.e. dE = dQ - dWork where Work is linked to a change in a physical parameter, such as L the length of the box, whereas dQ is linked to energy changes not involving a physical parameter e.g. a change in n the energy level. The Schrodinger equation yields solutions for W(x)=Sum over p a(p)exp(ipx) the wavefunction as well as En’s. We have argued in previous notes that W(x) is part of a conditional probability P(p/x)= a(p)exp(ipx)/W(x) and that En is constant at each point x just as T is constant at each x for classical statistical equilibrium (1). Thus a kind of statistical mechanics exists at the wavefunction level we argue. This statistical mechanics makes use of a free particle wavefunction exp(ipx) and weights a(p), but does not contain the usual P(x), P(p) picture of the classical world. We have shown in (2) that one may obtain P(x)=W*(x)W(x) and P(p)=a*(p)a(p) from the conditional probability. The essential physics we argue, however, is at the level of the wavefunction together with its own unique statistical scenario of exp(ipx)’s interacting with exp(ikx)’s from V(x)=Sum over Vkexp(ikx) (see (1)). Given that P(x) and P(p) exist for a quantum bound state, it may be convenient to use them in formulas because they are linked to a classical statistical picture. We argue that one may use P(x) and P(p) to construct an object S such that T dS does not change when one changes L, the size of box with infinite potential walls. We argue that such an object follows from properties of the Schrodinger equation together with various assumptions. We arrive at S=Sp+Sx where Sp=-k Integral dp a(p)a(p) ln{|a(p)a(p)}| and Sx= -k Integral dx W(x)W(x) ln(W(x)W(x)) for a given energy level. We do not use arguments related to taking ln of the number of states present or Shannon’s entropy. Rather we look for a solution which does not depend on L and is additive. We note, however, that for both W(x)W(x) and a(p)a(p) the solution found is mathematically consistent with the entropy form found by considering independent probabilities. This, however, applies to P(x) and P(p), but we argue that the physical situation is based on W(x) and a(p) as solutions of the Schrodinger equation. Nevertheless P(x) and P(p) are physical observables and not simply math constructs and so may think of them in a somewhat classical manner in terms of probability. Thus we argue that thermodynamics is already present at the level of a quantum bound state and that one may obtain Shannon’s entropy at this level using P(x) and P(p), but without considering the overall probability of independent probabilities as in information theory or numbers of states. Rather obtaining a function which is additive in Sp and Sx and eliminates L is the main consideration. We also argue that S=Sp+Sx carries over into mixed quantum state wavefunctions even though it is usually ignored. Thus we try to argue that it is the bound quantum state which gives rise to the notion of thermodynamics and entropy.
Classical statistical equilibrium, for a Maxwell-Boltzmann gas for example, is based on localizing the gas to a certain volume and having no average changes in time. In other words, maximization of entropy subject to the average energy constraint sum over i ei P(ei) is linked with these two ideas. Ei (kinetic energy for no V(x)) is a conserved quantity in reactions and overall energy represents a quantity which does not change in time consistent with a center-of-mass which does not change and average values which do not change in time. This approach is associated with a specific kind of statistics, namely that of the constituents of the system. As a result, one obtains the Maxwell-Boltzmann distribution exp(-ei/T) where ei is an extensive property of a particle (or subset of the system) and T an intensive property linked with the whole system. Entire systems, however, may interact. For example, a N particle system with T1 may achieve equilibrium with a N system with T2 yielding a new average (T1+T2)/2. The probabilities exp(-ei/T), however, are for subcomponents of a system. One could argue that momentum is an additive (vector) quantity which is conserved in collisions, but the average momentum of the system is 0 which does not allow one to describe increases in average p and -p which may be described using energy, i.e. through T temperature. This begs the question whether momentum may be associated with maximization of entropy subject to a constraint. In (1), we argued that there were flow probabilities in quantum mechanics linked with exp(-iEt) and exp(ipx), which may be obtained formally through maximization of entropy. Here we argue that while an MB gas describes a localized volume with average values not changing in time, x and t state values change, even if p and pp/2m remain constant for a free particle and it may be possible to have a maximum entropy situation to describe the combination of px and -Et. In other words, we suggest localized versus nonlocalized equilibria. The latter represents a quantum free particle, but one may then try to localize such a particle in a potential. What happens in such a case? One does not switch to a localized maximization of entropy as in the MB gas case, because it is possible to have the potential leave the flow unbroken as argued in (1). In other words, the nonlocalized free particle equilibrium is akin to a particle bouncing back and forth in a box, which in classical mechanics is not considered a statistical process. Here we suggest that the underlying picture is statistical meaning that the classical mechanics approach seems to be an approximation. We consider both a quantum particle trapped in an infinite potential well and the ground state of an oscillator to examine ideas of maximizing entropy beyond exp(ipx). A key common feature of both types of equilibrium is the product rule P(ei)P(ej) = P(ei+ej) or exp(ip1x)exp(ip2x) = exp(i (p1+p2)x). We consider this feature as well.