In this note, we try to develop bound state quantum mechanics directly from statistical arguments. The key idea, we argue, is that a statistical treatment of a system considers “free particles” together with a stochastic equilibrium driving mechanism. If an acceleration driving potential exists (as in classical statistical mechanics), it alters the results, but does not change the main scenario of free particles interacting through a stochastic mechanism at a point because one does not follow particles in time, noting how they accelerate as they travel. (For example, a Maxwell-Boltzmann gas distribution is based on two body elastic scattering whether there is a potential or not. The potential affects the density, but not the relative momentum probabilities at any x.) For the quantum case, the potential V(x) is the stochastic equilibrium driver, but on average kinetic energy plus potential must equal total energy. Again, one does not follow the quantum particle in time trying to see if or how it accelerates.
In this note, we try to develop bound state quantum mechanics directly from statistical arguments. The key idea, we argue, is that a statistical treatment of a system considers “free particles” together with a stochastic equilibrium driving mechanism. If an acceleration driving potential exists (as in classical statistical mechanics), it alters the results, but does not change the main scenario of free particles interacting through a stochastic mechanism at a point because one does not follow particles in time, noting how they accelerate as they travel. (For example, a Maxwell-Boltzmann gas distribution is based on two body elastic scattering whether there is a potential or not. The potential affects the density, but not the relative momentum probabilities at any x.) For the quantum case, the potential V(x) is the stochastic equilibrium driver, but on average kinetic energy plus potential must equal total energy. Again, one does not follow the quantum particle in time trying to see if or how it accelerates.
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.
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.
Quantum mechanics is often compared with classical mechanics because both may deal with a single particle subject to a potential. Classical mechanics is said to be deterministic describing x(t) and its derivatives i.e showing how a particle moves and accelerates while bound state quantum mechanics produces a real wavefunction W(x) such that W(x)W(x) yields a spatial density profile. The comparison is carried further with the correspondence principle which states that at high energy levels quantum mechanics should mimic classical mechanics. Classical mechanics does not simply describe x(t) and its derivatives i.e. deterministic motion. It also includes two body scattering, force and torque balances for a stationary object etc. In the case of the classical statistical mechanics of an equilibrium ideal gas, the Maxwell-Boltzmann (MB) distribution in the absence of a potential is C1 exp(- pp/(2mT) ). If a potential V(x) is added, one may find P(x) two different ways using Newtonian ideas. The first is to consider the gas as a collective entity like a tiny macroscopic classical object at x. Then one may argue that equilibrium means the system is stationary and apply Newtonian statics i.e. a balance of pressures and -dV/dx to obtain exp(-V(x)/T) as is often done in textbooks. Alternatively, one may consider a single particle and apply Newtonian mechanics differently, namely use a conservation of energy equation: p1p1/2m + V(x1) = p2p2/2m + V(x2). Again one obtains exp(-V(x)/T). The spatial part of probability may be based on Newtonian mechanics indicating that it is not stochastic. The stochastic function is C1 exp(-pp/2mT). Interestingly, however, the two Newtonian approaches are different with respect to a single particle. A collective nonmoving set of particles acts as a stationary object, yet within it each particle seems to be “bouncing” off of an imaginary wall creating pressure. Thus one has an impulse free particle picture yet obtains the correct result exp(-V(x)/T). Alternatively one may think of a single particle accelerating which it does if it is not colliding with other particles. This is a very different picture of the single particle than of one bouncing back and forth hitting an imaginary wall. In fact, there is usually a wall holding the gas together and pressure and bouncing particles are the real picture there, but within the gas one would normally think of a single particle accelerating. Nevertheless there are two scenarios which yield the same result. The idea of pressure balance is more in keeping with an overall statistical picture of the gas. In other words, one may actually ignore the idea of following a single particle as it accelerates. (That is not to say that single particle acceleration does not exist - it does.) Quantum mechanics we argue is a statistical theory. In the case of a single bound particle one has a momentum distribution W(x)=wavefunction = Sum over p a(p)exp(ipx). One may apply conservation of average energy at each x to obtain the time-independent Schrodinger equation. In such a picture, like with the statistical mechanical gas, we argue that one may imagine impulse hits with the potential instead of considering acceleration. The quantity vrms(x) from KEclassical= .5m vrms(x)vrms(x) = -1/2m d/dx dW/dx / W does display acceleration, but this is a mathematical average. As energy levels become higher the correspondence principle is said to apply, but a classical particle exhibits acceleration. The quantum bound state does not, but like in the case of the statistical mechanical gas it may be that two scenarios lead to the same result. In other words, the quantum bound W(x) still has crests and troughs, but with low resolution one may only see an envelope roughly touching W(x)W(x) which matches a classical C2/v(x) where v(x) is classical velocity. Given that quantum mechanics is a statistical theory it may not be necessary to have it explicitly display acceleration.
We argue that in a quantum bound state with one particle, the particle receives stochastic hits from a potential. As a result, if one examines a point x, the particle may be present at ti with momentum pi (in both the forward and backward directions) leading to a momentum distribution with a conditional probability P(p/x) = a(p) exp(ipx)/W(x) where W(x) is the wavefunction. Thus, one does not follow a stochastic particle in time, but rather describes it by a probability distribution at each x. One may next ask whether this conditional probability at x changes in time? This is not the actual time related to stochastic motion of the particle. To answer this question, we argue one must consider interactions which occur at x which are part of an energy equation. Even in classical physics, the energy equation at x indicates how a particle’s motion changes. Thus, we argue one does not simply take measurements at x of ti and pi, but that at each ti, a particle with pi is undergoing dynamic changes and these may be considered as well. If one describes the quantum picture by W(x) i.e. a momentum distribution, one may find a collective interaction given by -1/2m d/dx d/dx W + VW. The coupling between V(x)=Sum over k V(x)exp(ikx) and the particle conditional probabilities in W is apparent in the VW term. This energy term should describe whether the momentum distribution changes in time i.e should be proportional to dW/dt (partial derivative), but should also equal the average energy. Thus, a link exists between ensemble energy and time. In this note, we argue that these ideas may be applied to P(p/x) in a bound state resonance because the same E applies to each p.
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 appears to be based on a no-flow situation with a balance of pressure (including -dV/dx in the case of a potential present). It may be noted, however, that like quantum mechanics, a single particle has different probabilities of being at one x versus another. Furthermore, the Maxwell-Boltzmann, Fermi-Dirac and Bose-Einstein distributions may be obtained using reaction balance which is linked to conservation of energy i.e. g(f(ei))g(f(ej)) = g(f(el))g(f(ek)) where ei+ej=el+ei=e. Taking ln of the former expression and linking to the latter yields f(ei), the probability distribution. g=1 for the MB case, f(e)/(1-f(ei)) for the FD and f(e)/(1+f(ei)) for the BE. In classical mechanics, one has the conservation equation: p(x)*p(x)/2m + V(x) = E. In quantum bound systems one has: KE(ave)(x) + V(x) = E which appears to be very similar, although it is based on ensemble averages and there is a momentum distribution P(p/x) at each x. A question which arises is: What is the “conservation of energy” equation for a particular p of the P(p/x) distribution? In this note, we argue the “potential” term associated with a component p*p/2m is related to the part of the potential which contributes to the “creation” of p. In particular, we consider V(x)= Sum over k V(k) exp(ikx) where each k term renders a kick of momentum k. One may create a momentum p using k and p-k for each value of k. We further argue that: p*p/2m P(p/x) + contributing portion of V(x) = E P(p/x) ((1)) for all p. Thus, in quantum equilibrium, which involves a flow, there is a “constant E” type of equation i.e. ((1)), different in form but similar in idea, to that of classical statistical mechanical equilibrium. In previous notes, we referred to this as cycling, but in this note we wish to consider it in terms of dynamics. We further note that in both classical statistical mechanics and quantum mechanics, the energy-probability p equation makes use of the overall average energy which is bT for the classical case and E for the quantum. (b is constant)