Classical statistical mechanics is often derived using counting methods applied to all possible configurations a system may take subject to a total volume and a total energy constraint. Given that there are numerous configurations, there should also be an average of these configurations described by f(e) for the Maxwell-Boltzmann (MB), Fermi-Dirac (FD) and Bose-Einstein (BE) distributions. In previous notes we have argued that one may apply a dynamical constraint to the average configuration. In particular, we argued that there should be a time reversal balance for two body elastic collisions. This immediately yields the various distributions with only consideration given to the average state and no counting techniques used. The counting of configurations, however, emphasizes that statistical mechanical systems contain “fluctuations” and that a specific dynamic constraint (i.e. time reversal two body scattering) applies only to the average. Quantum bound states, we argue, are very similar. They represent a statistical system which has many fluctuations (i.e. a particle may be knocked out with an momentum p with probability a*(p)a(p) where W(x)=wavefunction = Sum over p a(p)exp(ipx)). There is, however, also a dynamical constraint which applies to the average, namely KE(x)+V(x)=E which is a classical mechanical constraint. Here KE(x)= [-1/2m d/dx dW/dx /W] ((1)). If fluctuations disappear in the high energy scenario, one may assume there is an almost fixed momentum p at each x. ((1)) still applies and there is still a wavefunction which is often in the form of crests and troughs. If an almost unique p exists at each x, one expects W(x) to vary in height at peak values. This may be verified from actual W(x) solutions. Given that the constraint on the statistical average is KE(x)+V(x)=E, one would expect that as p becomes an almost unique value at each x, that the quantum expectation Integral dx WW KE(x) with KE(x) given by ((1)) should also approach a classical value in other words Integral dx WW —> integral dt. One does not need to impose the correspondence principle to arrive at this result, one only needs to consider the case in which fluctuations in a quantum system disappear allowing the average p at each x to consist of almost a single p value.
Classical statistical mechanics is often derived using counting methods applied to all possible configurations a system may take subject to a total volume and a total energy constraint. Given that there are numerous configurations, there should also be an average of these configurations described by f(e) for the Maxwell-Boltzmann (MB), Fermi-Dirac (FD) and Bose-Einstein (BE) distributions. In previous notes we have argued that one may apply a dynamical constraint to the average configuration. In particular, we argued that there should be a time reversal balance for two body elastic collisions. This immediately yields the various distributions with only consideration given to the average state and no counting techniques used. The counting of configurations, however, emphasizes that statistical mechanical systems contain “fluctuations” and that a specific dynamic constraint (i.e. time reversal two body scattering) applies only to the average. Quantum bound states, we argue, are very similar. They represent a statistical system which has many fluctuations (i.e. a particle may be knocked out with an momentum p with probability a*(p)a(p) where W(x)=wavefunction = Sum over p a(p)exp(ipx)). There is, however, also a dynamical constraint which applies to the average, namely KE(x)+V(x)=E which is a classical mechanical constraint. Here KE(x)= [-1/2m d/dx dW/dx /W] ((1)). If fluctuations disappear in the high energy scenario, one may assume there is an almost fixed momentum p at each x. ((1)) still applies and there is still a wavefunction which is often in the form of crests and troughs. If an almost unique p exists at each x, one expects W(x) to vary in height at peak values. This may be verified from actual W(x) solutions. Given that the constraint on the statistical average is KE(x)+V(x)=E, one would expect that as p becomes an almost unique value at each x, that the quantum expectation Integral dx WW KE(x) with KE(x) given by ((1)) should also approach a classical value in other words Integral dx WW —> integral dt. One does not need to impose the correspondence principle to arrive at this result, one only needs to consider the case in which fluctuations in a quantum system disappear allowing the average p at each x to consist of almost a single p value.
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.
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.
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 Part 1, we identified W*(x)W(x) (where W(x) is the spatial part of a wavefunction) as the probability to interact. In the classical limit, if one draws a curve roughly touching the peaks of W*(x)W(x), then this probability is sometimes identified in the literature as proportional to the amount of time spent in dx, i.e. dt= dx/v(x). In the classical limit, however, dt(x) is not only the amount of time interacting in dx at x, but also the amount of time spent passing through dx at x. Such is not the case in quantum mechanics. For a bound state at any energy level, there is a KEave(x) = -1/2m d/dx dW/dx / W = E-V(x) = classical KE(x). This means there exists a vrms(x) so for a fixed dx, there is a quantum average passage time through dx, which may be more related to an ensemble average passage rather than any physical passage time. In such a case, we suggest that W*(x)W(x)dx is not only the probability to interact, but may be considered proportional to an ensemble average interaction time at dx. The expression V(x) W*(x)W(x) means that one weights the potential energy by the average amount of interaction time spent in dx at x. In other words, the quantum observable reality discussed in Part 1 seems to be equivalent to the interaction experience of the particle. It is not merely the case that there is a potential energy at x, there is also a certain interaction time spent in dx at this x (even in the classical case) and this is part of the potential energy experience of the particle. Thus, the potential energy V(x) is weighted by W*(x)W(x) to describe this experience. In the classical case, this dt interaction time is also physical passage time, but in quantum mechanics it is not (as will be shown). As a result, the quantum average Integral dx W*(x) operator W(x) = Integral dx W*(x)W(x) (operator W ) / W(x) represents both a reality based on external measurement or the particle’s experience interacting. Both are interaction realities. KE(x) = -1/2m d/dx dW/dx /W is also a physical expression which should have as much meaning as V(x) or E, but it is not based on the W*(x)W(x) weighted view of the particle. In Part 1, we focused on external measurements, but here we concentrate on the interaction of the particle with V(x) and suggest that this also gives a kind of physical meaning to <W V W> = Integral dx W* V W.
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.)
In a classical bound state, conservation of energy: p(x)p(x)/2m + V(x) = E holds for all x. Examined in a statistical sense, one may consider each constant dx to have a probability density proportional to dt(x) where v(x)=velocity =dx/ dt(x). Thus the particle is followed in time. In quantum mechanics, even for a free particle exp(ipx), there exists a wavelength hbar/p. Within this region one cannot follow the particle in time. In fact, there are two probability distributions cos(px) and the shifted sin(px). The two dimensional nature of exp(ipx) is required to describe the direction of motion. There exists a mathematical abstraction or average which holds for any x within the wavelength and yields the classical x= p/m t. Thus there is a duality, but within a wavelength one cannot follow the particle exactly using x=p/m t. Rather there is no time and one thinks of probabilities to be at one x or another. The operator -id/dx yields the abstracted or average momentum at any x and (-id/dx)(-id/dx) average pp if one divides by probability. In other words: (-id/dx) exp(ipx)/ exp(ipx) = p and (-id/dx) (-id/dx) exp(ipx) / exp(ipx) = pp. These then apply to any x point. For a bound state, exp(ipx) is replaced with W(x)= Sum over p a(p)exp(ipx). Thus p and -p are included together. From a statistical point of view this is fine because a quantum bound state is described in terms of energy conservation (time-independent Schrodinger equation). Unlike the classical case, the probabilities of p and -p differ, i.e. exp(ipx) and exp(-ipx). The sum exp(ipx)+exp(-ipx) yields cos(px) which is the resolution probability distribution. Taking -d/dx d/dx of W(x) and then dividing by W(x) yields the average kinetic energy at any x within the wavelength. In other words this is the average kinetic energy which matches the classical result for any energy level. As a result, prms(x)prms(x)/2m + V(x) = En holds for any quantum level, but prms(x) is an rms average value which bypasses wave structure. That is why the exp(ipx) for p,-p and -id/dx must be used to calculate average quantities within a wavelength. Many different p,-p combinations are needed so that at each x within a wavelength the correct average kinetic energy value appears. Now consider a high energy level and choose a fixed dx length to represent a tiny region in the system, a cutoff for which there is no further resolution. p(x) is constant within this region. If hbar/ prms(x) <= dx, the wave structure of quantum mechanics does not play a role. (Note that for an oscillator, W(x) is a set of crests and troughs with different heights and widths.) As a result, there is no need for d/dx acting on W(x) to describe average kinetic energy within dx. The average kinetic energy is prms(x)prms(x)/2m and dx is treated like a point. Only if exp(ipx) is used does -id/dx yield the proper classical result. (An alternative scenario is that d/dx acting on a function divided by the function yields the same result as acting on exp(ipx) divided by exp(ipx) e.g. -d/dx d/dx cos(px)/cos(px) = -d/dx d/dx exp(ipx) / exp(ipx). If one has the quantum kinetic energy expression -1/2m d/dx dW/dx / W ((1)) and considers one momentum, namely prms(x), and uses W(x)= cos( prms(x) x), then with prms(x) constant at x, ((1)) yields prms(x) prms(x)/ 2m. Thus d/dx has not broken down even though it does not describe motion within dx which is now a point. A problem arises, however, if one considers Wn(x)= Wn1(x)Wn2(x) as this yields an equation containing dW1/dx dW2/dx/ (W1W2). Then the above procedure yields: dW1/dx/W1 (prms(x) sin(prms(x) x) / cos(prms(x) x). This does not match the classical value. Furthermore, dW2/dx/ W2 contains +prms(x) and -prms(x) with different weights while a classical scenario is -pP(-p,x) + pP(p,x) = 0 because P(-p,x)=P(p,x) while quantum mechanically it doesn’t. We analyze this situation and conclude that d/dx breaks down/ does not apply in the classical limit because it is used to calculate average values within a wavelength only. It only “works” if the effect of the derivative(s) on a function divided by the function is the same as the effect on exp(ipx) divided by exp(ipx). If a wavelength fits within dx, there is no need to calculate values at any lower x level and d/dx is not needed. In fact, there is a single prms(x) value in dx and the average time links different dx’s so that one follows the particle (on average in the sense that one ignores structure within each x) by x(t). As a practical consequence, using -id/dx together with the wavefunction W(x) can lead to problems in the classical limit because d/dx does apply. In short, using -id/dx operating on Wn(x) divided by Wn(x) leads to issues unless it produces the same effect as acting on exp(ipx) divided by exp(ipx).