Both quantum bound state equilibrium and classical statistical mechanical equilibrium are characterized by d/dt partial density(x,t)=0. For a quantum particle, W(x,t)=exp(-iEt)W(x) and d(x,t)=W*W. Density is linked to fluid flow and arguments of pressure balance such that the overall average fluid flow is zero are made. This pressure-force balance is common in classical statistical mechanics and used to calculate the variation of density with x i.e. obtain a differential equation with d d(x,t) /dt partial. A similar balance equation is used in (1) as the authors try to derive the Schrodinger equation using a fluid dynamical approach. In this note, we try to argue that one may think of the two equilibria in terms of an energy quantity which remains constant throughout space. This energy quantity depends directly on the type of interactions in the system at any point x. For a classical ideal gas, balanced two body time reversal scattering represents the interaction. V(x), a potential, does not change this fundamental manner of interacting at any given point, although it does affect density. As a result the energy related constant at each x is T, related to average kinetic energy. We argue that this already points to the dominant type of interaction creating the statistical interaction i.e. one that depends only on p in interactions which conserve kinetic energy. This “happens” to be equivalent to maximizing Shannon’s entropy, but we argue this is particular to this scenario in the sense that not all interacting systems will have this equivalence. In other words, we argue that one must be careful with regards to the maximization of entropy as a fundamental rule. In particular, we consider the single particle bound quantum state. The interaction exists between the particle and the potential V(x), but one may consider a distribution of free particle momentum probabilities i.e W(x)=wavefunction = Sum over p a(p)exp(ipx). The form exp(ipx) comes from separate arguments as is discussed in the note, but the point is that there are no two body scattering reactions occurring at a given x, neither is there acceleration from on x to another (except for a vrms mathematical quantity). Nevertheless the “free particle” exp(ipx) interacts at each x with V(x). As a result of this interaction, one has free particles exp(ipx) which are no longer associated with pp/2m, but rather with an Eave which is a constant for every p. In other words the identity of exp(ipx) is unusual because it is linked to exp(ipx) and pp/2m, but also to Vk1 a(p-k1), Vk2 a(p-k2) etc where V(x)=Sum over k Vk exp(ikx). Thus each x point is associated with a constant Eave and this defines the equilibrium. (It is also equivalent to conservation of energy at each x.) In such a case, one does not maximize entropy to find a(p) values. In the two cases, the common point seems to be considering the interactions at each x and finding a constant “energy” type quantity which does not vary with x. This we argue appears to define equilibrium for both the classical statistical and quantum bound states. Instead of considering density which does not change in time at each x, there is constant energy which not only does not change in time, but has a constant value at each x which seems to be an alternative rule.
Both quantum bound state equilibrium and classical statistical mechanical equilibrium are characterized by d/dt partial density(x,t)=0. For a quantum particle, W(x,t)=exp(-iEt)W(x) and d(x,t)=W*W. Density is linked to fluid flow and arguments of pressure balance such that the overall average fluid flow is zero are made. This pressure-force balance is common in classical statistical mechanics and used to calculate the variation of density with x i.e. obtain a differential equation with d d(x,t) /dt partial. A similar balance equation is used in (1) as the authors try to derive the Schrodinger equation using a fluid dynamical approach. In this note, we try to argue that one may think of the two equilibria in terms of an energy quantity which remains constant throughout space. This energy quantity depends directly on the type of interactions in the system at any point x. For a classical ideal gas, balanced two body time reversal scattering represents the interaction. V(x), a potential, does not change this fundamental manner of interacting at any given point, although it does affect density. As a result the energy related constant at each x is T, related to average kinetic energy. We argue that this already points to the dominant type of interaction creating the statistical interaction i.e. one that depends only on p in interactions which conserve kinetic energy. This “happens” to be equivalent to maximizing Shannon’s entropy, but we argue this is particular to this scenario in the sense that not all interacting systems will have this equivalence. In other words, we argue that one must be careful with regards to the maximization of entropy as a fundamental rule. In particular, we consider the single particle bound quantum state. The interaction exists between the particle and the potential V(x), but one may consider a distribution of free particle momentum probabilities i.e W(x)=wavefunction = Sum over p a(p)exp(ipx). The form exp(ipx) comes from separate arguments as is discussed in the note, but the point is that there are no two body scattering reactions occurring at a given x, neither is there acceleration from on x to another (except for a vrms mathematical quantity). Nevertheless the “free particle” exp(ipx) interacts at each x with V(x). As a result of this interaction, one has free particles exp(ipx) which are no longer associated with pp/2m, but rather with an Eave which is a constant for every p. In other words the identity of exp(ipx) is unusual because it is linked to exp(ipx) and pp/2m, but also to Vk1 a(p-k1), Vk2 a(p-k2) etc where V(x)=Sum over k Vk exp(ikx). Thus each x point is associated with a constant Eave and this defines the equilibrium. (It is also equivalent to conservation of energy at each x.) In such a case, one does not maximize entropy to find a(p) values. In the two cases, the common point seems to be considering the interactions at each x and finding a constant “energy” type quantity which does not vary with x. This we argue appears to define equilibrium for both the classical statistical and quantum bound states. Instead of considering density which does not change in time at each x, there is constant energy which not only does not change in time, but has a constant value at each x which seems to be an alternative rule.
A classical bound system may be said to have a spatial density proportional to the amount of time dt a particle spends in a constant dx region i.e. C/v(x) (1) We stress that in this scenario there is a well defined and constant dx so that “dt” may be linked to velocity v(x). We also note that there is no spatial representation of action-reaction here even though this exists in Newton’s theory. In a classical Maxwell-Boltzmann gas there are many particles which each act dynamically according to .5mvv+V(x) = E (where v and E are particular to the particle when it is not colliding). At the same time there is a spatial density which “represents” macroscopic static chunks of matter which are balanced through pressure differences (P=spatial density(x) RT) and -dV/dx density where V(x) is the potential. From the pressure equation, T is proportional to energy which in turn is proportional to RMS speed squared. RMS speed may then be linked to a dt if a fixed dx is understood. In the classical statistical case, however, spatial density is directly linked to the number of particles in a region. Time enters in the pressure expression through a term proportional to the average kinetic energy i.e. pv where p is like an impulse and v a flux. What happens in a single particle quantum bound state? In a sense it is like a classical bound state as the equation: prms(x)prms(x)/2m + V(x) = En holds for any energy level. Can one then take vrms(x), choose a fixed dx and argue that spatial density should be equal to dt or C/vrms(x)? We argue that one cannot due to the lack of defined “dx” quantity. Why is dx problematic to define? We argue that it is because quantum mechanics is based on action-reaction x-probaiblity distributions linked to impulse. For example, exp(ipx) for a free particle captures only p or impulse (not velocity) and cos(px) and sin(px) are its action-reaction regions.These lead ultimately to a density is given by the well-known W*(x)W(x) where W(x)=Sum over p a(p)exp(ipx), although kinetic energy with pp/2m = .5pv is used to find W(x) as well. . W*(x)W(x) has crests and troughs similar to cos(px) in exp(ipx), except that these now have varying heights and widths. We try to argue that even though each x point maps to a different KEave(x), the hump physically represents action-reaction in the system (just as the humps in cos(px) do except for a single p) while KE(x) represents an average of p’s. This action-reaction is linked with impulses. In general, if one takes d/dx of the time-independent Schrodinger equation one finds an average impulse term, -dV/dx and KE(x) dW/dx / W where dW/dx / W is the average impulse. At peaks, dW/dx =0 and so an average force through time*impulse term balances -dV/dx=Newtonian force. These peaks are also associated with W*(x at peak)W(x at peak) which is the spatial density. We interpret this as representing the average time the single particle spends near x at peak. This value, however, follows from ideas of impulse and not from speed as there is no well defined dx even though there is a well defined vrms(x). Thus the ratio of W*(x)W(x) at two peaks is not the inverse of the ratio of vrms(x) except apparently when the energy level n becomes very high. We investigate these ideas.
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.
In classical physics, a particle traveling to the right is the mirror image of one traveling to the left. In terms of a spatial density (the time spent in each constant dx), the value is the same, as is the energy. A similar notion of such a spatial invariance is in the classical conservation of energy equation for a bound particle: p(x)p(x)/2m + V(x) = E. Quantum mechanics seems to be different because exp(ipx) and exp(-ipx) are distinctly different spatial probabilities, i.e. they are dynamic. It is not just that case that a particle moves to the right for exp(ipx) and to the left for exp(-ipx). The impulse hit probabilities (represented by exp(ipx) and exp(-ipx)) are distinctly different. If one wishes to create an OR situation and write: W(x) = Sum over p a(p)exp(ipx) and use this in a conservation of energy equation, then simply including only positive or negative p values in W(x) leads to a complex average kinetic energy -1/2m d/dx dW/dx / W which cannot be used with V(x) and E. Furthermore, W_ (only negative p) and W+ (only positive p) values do not yield the same average kinetic energy. Fortunately, given that this is a statistical average for a localized object (somewhat analogous to a gas), one may combine W+ + W- and obtain a real kinetic energy. We have argued in previous notes that there exists a quantum-classical duality. For example, for a free particle one has two independent notions. One is x=vt which describes the center-of-mass of the particle. We take this to represent a state description which treats v and -v as mirror images. exp(ipx), on the other hand, represents probabilistic impulse hits and does not define the state by itself, we argue, only its interactions. Interactions are physical and define what happens in an interacting system. One may, however, measure a system, i.e interact with exp(ipx), and this should define a measurement state ( a second state ensemble average). For example, exp(ipx)exp(-ipx) = 1 which is equivalent to the constant dt in each dx associated with x=vt. Thus, the two states coincide, but exp(ipx)exp(-ipx) means that one may place the 2-slit apparatus at any x point and is not about the center-of-mass, as x=vt is. In some cases, the two states are quite different. W*(x)W(x) represents an interaction state, but vrms(x) from .5mvrms(x)vrms(x) = -1/2m d/dx dW/dx / W represents a center-of-mass state description. (Note: in these cases a state means an average state, i.e. an average over many ensemble entries.) If one takes W*(x)W(x) and integrates over x, then interference terms vanish and one obtains a classical counting of distinct p value states with their weight a*(p)a(p).This, we argue, leads to the notion of orthogonality of probabilities. In classical probability, there is no such notion, but there is the notion of AND (multiply) probabilities. Given exp(ipx) and exp(-ipx), if one multiplies one removes p, i.e. the interactions and only sees the state left. W*(x)W(x) yields a set of peaks which represent a pattern of probabilistic hits in space which define a state which one would measure in space. The interference pattern, however, must be one such that if one integrates over x, one only obtains a classical sum of probabilities a*(p)a(p)’s as mentioned above. This leads to the notion of orthogonal exp(ipx)’s (which follows mathematically anyway). If one considers different bound En states, then these two are orthogonal because W*n1(x)Wn2(x) mean n1 and n2 are associated with different energies and integrating over x cannot show a result which looks like a state result, where W*n(x)Wn(x) shows a state result. In order to achieve this orthogonality (linked directly to the notion of a state) one must have that Wn(2) usually has 0 points and is positive and negative with the possible exception of a ground state. In other words, if Wn1*(x)Wn2(x) integrated over x is not 0, one violates conservation of energy. As a result, we argue an average probability for a bound state must statistically include +p and -p contributions and must create a function which has positive and negative peaks (except possibly for the ground state), i.e. W(x) must have 0 points. This W(x) is linked to a measurement state W*(x)W(x), but this is strictly considering exp(ipx)s. We argue that there are two pieces of information for a free particle, x=vt and exp(ipx). There must also be an average state linked to x=vt and this given by KEave(x) = .5m vrms(x)vrms(x) + V(x) = E which shows that the particle may exist and have average kinetic energy even at W(x)=0 points. When measuring a system, one interacts with the exp(ipx)s and so the W*(x)W(x) state is the one which is traditionally presented, but whether one measures the center-of-mass motion or not, one also has the notion of the x=vt, i.e. vrms(x) state (average) as well, we argue.
In a previous note (1) we argued that both the relativistic A= -mo t sqrt(1-vv) and nonrelativistic A=t .5mvv classical free particle actions may be written with v=x/t and x and t varied independently to yield: dA/dx partial = p and dA/dt partial = -E. Thus A is equivalent to -Et + px for a free particle with x and t being treated as independent. We argue in this note that such an assumption is equivalent to a statistical picture for a free particle even at the classical level because x and t are treated as independent. Thus a constant p may occur at any x because no time is linked to x. Given that all space points are the same for constant p one expects a constant probability at all x points. Knowing p exactly means not knowing anything about which x one has. Secondly, one may create an ensemble of free particle p classical actions for a situation containing a potential V(x). Given that x and t are independent, there cannot be any notion of single p accelerating, although a vrms from an ensemble may. At a given x (x known exactly) one does not know which p is present. Thus the ideas of uncertainty of p and x follow immediately from this picture. If one considers a single particle and an ensemble of free particles in the x-t independent scenario, then each free particle action p is linked to A=-Et+px where E=pp/2m. This ensemble would arguably be stirred up by a potential V(x). If one wishes to consider an equilibrium scenario for which there is an overall En for the bound system one would expect an overall Ent for the system and for -pp/2m t pieces to disappear. Thus we postulate that pp/2m +{p part} G(p’s k’s) = En for all p where {p part}G(p’s, k’s) is an unknown function and V(x)=Sum over k Vk exp(ikx). Next one may consider the spatial situation for which V(x) is the classical potential for a single particle. The kinetic energy follows from an ensemble of free particles with the overall -Et removed. From classical considerations one would expect to have a KE(x). Thus one expects: KE(x) = {Sum over p a(p) f(px) } / {Sum over a(p)f(px) } with f(px), an orthonormal basis set, because the action contains px. (It is orthonormal because one wishes the identity of p to exist if not at a point, then over all of x.) We try to argue in this note that f(px)=exp(ipx), the momentum eigenstate which follows from A=-Et+px. We find G(p’s, k’s) which implies entanglement or mixing of a given p state with other p and k states from the potential V(x)=Sum over k Vk exp(ikx). Thus one expects an entropy linked to this momentum entanglement. Given the form exp(ipx), finding a set of ap’s which satisfy pp/2m + G(p’s, k’s)=En leads to a spatial distribution W(x)=Sum over p a(p)exp(ipx) so there should be an entropy contribution from this spatial part as well. In classical statistical mechanics one has both momentum and spatial contributions to entropy. We argue for S=Sp+Sx, but note that even though px has x, p symmetry as does the Heisenberg uncertainty principle var x var p >= hbar/2, Sp and Sx may not be symmetric in terms of important parameters such as n, energy level. In other words, Sp the entanglement entropy with V(x) may be the driver entropy sensitive to energy level changes while Sx the resulting spatial density may not be as sensitive. Furthermore the overall entropy Sp+Sx gives information about uncertainties in x and p as is already known in the literature where bound state Sp+Sx bounds are given.
The classical limit of quantum mechanics is often considered in terms of the time dependent Schrodinger equation. In this note we consider the bound case solution i.e. a time dependence of exp(-iEt) and as in previous notes argue that time has been removed from this statistical equilibrium picture as a the quantum particle tries to establish a kind of impulse potential field based on superpositions of exp(ipx) terms. Such a potential field is linked with a bound state and does not involve following the particle about in time as it undergoes stochastic impulse hits with exp(ikx) terms from V(x)=Sum over k Vk exp(ikx). On average a classical energy balance equation KE(x)+V(x) = En holds for every energy En, but the average is created by a spread of momenta i.e. W(x)=wavefunction= Sum over p a(p)exp(ipx). In this note we consider the case of a particle in an infinite potential well and note how the spatial resolution becomes very high at the same time that the momentum spread becomes very narrow in the case of high n (energy level). Thus as n becomes approaches infinite, it is not just the vrms(x) which is linked with x, but the statistical scenario of quantum mechanics approaches a situation in which x is being resolved to a very high level and p is almost constant. Furthermore quantum entropy becomes a constant (independent of n) as n→ infinite suggesting a theory which is nonstatistical in this limit.This would represent a classical picture except for the fact that time is still removed from the quantum bound state i.e. forward and backward exp(ipx), exp(-ipx) still interfere. Given that x and p are well resolved locally for high n it seems one may follow the high n quantum particle in space and time and manually remove the forward and backward portions to create a theory of a particle moving in one direction under V(x) i.e. classical physics. This bypasses the idea of a wavepacket whose x-spread increases in time and allows one to base classical physics on a bound state solution of a quantum particle in an infinite well.