Derivations of statistical mechanical distributions often involve the maximization of some type of uncertainty (i.e. the number of spatial arrangements or arrangements in degenerate cells of phase space) subject to a global constraint on energy (and also particle number). Interactions within statistical systems (particles colliding with each other or with a wall), introducing conservation of energy at a particle collision level is a way to achieve global energy conservation. Quantum mechanics is a statistical theory, so one may ask whether it too is based on the conservation of a particle property and whether it makes use of the maximization of some type of uncertainty. In this note, we argue that momentum is the conserved particle quantity (kinetic and potential energy are conserved on average) and that for a momentum state, one maximizes the uncertainty of x in a particular way.
Derivations of statistical mechanical distributions often involve the maximization of some type of uncertainty (i.e. the number of spatial arrangements or arrangements in degenerate cells of phase space) subject to a global constraint on energy (and also particle number). Interactions within statistical systems (particles colliding with each other or with a wall), introducing conservation of energy at a particle collision level is a way to achieve global energy conservation. Quantum mechanics is a statistical theory, so one may ask whether it too is based on the conservation of a particle property and whether it makes use of the maximization of some type of uncertainty. In this note, we argue that momentum is the conserved particle quantity (kinetic and potential energy are conserved on average) and that for a momentum state, one maximizes the uncertainty of x in a particular way.
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)
Classical statistical mechanics/thermodynamics is sometimes portrayed as an approximate approach to describing the classical mechanical motion of very large numbers of particles. Equilibrium statistical mechanics/thermodynamics, however, is a special situation in which thermodynamic averages such as temperature, pressure etc do not change in time. We argue in this note that this is due to constraints imposed on such equilibrium scenarios namely time reversal reaction balance. It is this (approximate) constraint which yields the Maxwell-Boltzmann distribution which in turn defines average values of classical values e.g. pressure resulting from an average of bvv (b=constant) and temperature being related to average kinetic energy. Interestingly, average values such as average energy and pressure may yield a classical mechanical relationship for adiabatic processes, otherwise the more complicated dE=TdS - PdV applies to these averages. (To be more accurate one may use the constraints of microcanonical theory.) Quantum mechanics is also a statistical theory because a single particle with a fixed momentum is characterized by a physical wavelength region and a probability distribution exp(ipx). If interactions occur with potential regions a superposition of these distributions (i.e. a momentum superposition) occurs i.e. W(x)= Sum over p a(p)exp(ipx). This represents one constraint in quantum mechanics), but there is a second, namely that averages for a bound system match classical values. Thus, like classical statistical mechanics one may imagine a system characterized by a parameter say L (box length) which changes such that the particle stays in the same quantum state (i.e. an adiabatic change). Given that bound quantum mechanics is constrained to behave on average as a classical system it is not surprising that a dE=PdV which is essentially a Newton’s second law statement dE=Fdx and is not necessarily linked to a usual statistical system. If a quantum state has its parameter changed nonadiabatically it should be able to have it change into a superposition of new quantum states (new L) which is very different from the classical statistical mechanical scenario. Furthermore the ideal gas relationship PV=NRT and E=3/2NRT (3 degrees of freedom) or PV=(⅔)E matches a classical mechanical result because a particle with p may bounce from a wall yielding an impulse. In this note we try to examine some of these underlying constraints and argue that even dE=PdV for average E and P values (i.e. no entropy change) one must be aware of the specific constraints involved. In other words because dE=PdV for both adiabatic classical statistical mechanical systems and a quantum eigenstate, these do not necessarily represent the same statistical type of physics. We further argue that quantum mechanical bound states are constrained to have some average and rms values such as KE(x) and p rms behave as classical values and so these should not be taken to represent “intrinsic” quantum behaviour while average spatial density on the other hand does. (It is linked to the constraint of wavelength.)
It is sometimes stated in the literature (1) that quantum mechanics is based on conditional probabilities. If this is the case, one would expect such conditional probabilities to appear in a single particle bound state. A free quantum particle is associated with a probability to interact of exp(ipx) (linked to 2-slit interference, 1-D reflection-refraction at an n1-n2 junction etc), but the kinetic energy and momentum are pp/2m (nonrelativistic) and p at all x even though each x has a different phase according to exp(ipx). The momentum is p at x, but the probability for an impulse hit at x is not the same even though its modulus is. When different probabilities exp(ipx) add in an OR situation, this leads to a spatial pattern which no longer has a modulus of 1, i.e. translational invariance is broken. Such a pattern also occurs for a single particle bound state W(x)=Sum over p a(p)exp(ipx). W(x) can have 0 points, but the average kinetic energy -1/2m d/dx dW/dx / W is not 0 at such a point. One has, on average (a statistical calculation), no average interaction at such an x point. One might ask why this should have anything to do with average kinetic energy? If one writes a conservation law: KEave(x) + V(x) = 0, then one considers kinetic energy interacting with potential energy. If there is no interaction at some x point for a given p (not W(x) on average), then it should not be part of the conservation of energy at this point. One is only interested in kinetic energy which interacts with potential energy at each x point. Thus, a(p) exp(ipx) + a(-p) exp(-ipx) (with a(p)=a(-p)) may have a 0 point at some x and so it does not have an average interaction at such a point, i.e. pp/2m (a(p)exp(ipx) + a(-p)exp(-ipx)) = 0. As a result, in a bound state, one considers kinetic energy per p, -p multiplied by the average probability (p, -p). Different a(p)exp(ipx) + a(-p)exp(-ipx) (a(p)=a(-p)) weights in this average picture indicate the extent to which the particle interacts. This idea holds for a single p,-p pair, but one must normalize over all such pairs, leading to the idea of a conditional probability. Given that hbar/p must be “created physically” in space so to speak, one must have interaction probability which creates this physical situation even in cos(px)+ i sin(px). This leads to the idea of interaction probability being 0, positive, but <1, or even negative and it is the interaction which allows one to consider conservation of energy with a potential V(x) in the first place. As a result, one cannot include a full pp/2m if there is negative, 0 or only particle interaction. Thus, pp/2m is multiplied by 2 a(p)cos(px) /W(x) for a(p)=a(-p).
We argue that classical statistical mechanics (say of an ideal gas) is based on a single equilibration scheme characterized by a temperature T (even in the presence of a potential V(x)). This single scheme is based on the maximization of entropy (subject to an average energy constraint) in order to determine probabilities for p,v and x. Quantum mechanics, on the other hand, is based on two equilibration schemes, we argue. The first is due to a built-in probability of exp(ipx) for a free particle. In this case, a potential V(x) interacts with momentum (impulse hits) to create a potential energy. No velocity appears in the creation of potential energy, but does appear in the creation of average kinetic energy. Like with a classical mechanical bound state, energy becomes a system variable. This is the first equilibration. We argue that it should have its own entropy. The probability form exp(ipx) together with conservation of energy and boundary conditions fix allowable single particle energy values (which are discrete) unlike in the classical statistical mechanical case. The second equilibration occurs if there exists a mechanism for moving from one discrete E to another, e.g. photon emission/absorption. This equilibration is based on maximization of entropy (a second entropy), but the effects of the first equilibration remain because it is this first scheme which controls allowable E values. We also argue that exp(-i Et) from the first equilibration scheme may affect the usual entropy based on exp(-E/T) used in the second scheme.
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 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.