In a previous note, it was suggested one can use definitions of temperature and heat flow from the Boltzmann transport equation and calculate similar quantities for a bound state quantum wavefunction. It was also suggested that one could not use the “transport equations” such as the Euler equation for the quantum bound state system. In another note, however, it was shown that the quantum bound state contained important terms of the Euler equation, namely -d/dx ln(d(x)) and F(x)d(x) where d(x) is the density and F(x) the force. In this note, we consider the definition of pressure from the Boltzmann transport equation and calculate its gradient. We find the usual F(x)d(x) term in addition to an extra term. In setting F(x)=0, we find the extra term coincides with the gradient of pressure for a quantum particle in a box with no potential. Thus, it appears that a quantum particle, even without a potential, represents a pressure gradient which affects the form of the Schrodinger equation and causes quantum particles to differ from those of classical and classical statistical mechanics.
In a previous note, it was suggested one can use definitions of temperature and heat flow from the Boltzmann transport equation and calculate similar quantities for a bound state quantum wavefunction. It was also suggested that one could not use the “transport equations” such as the Euler equation for the quantum bound state system. In another note, however, it was shown that the quantum bound state contained important terms of the Euler equation, namely -d/dx ln(d(x)) and F(x)d(x) where d(x) is the density and F(x) the force. In this note, we consider the definition of pressure from the Boltzmann transport equation and calculate its gradient. We find the usual F(x)d(x) term in addition to an extra term. In setting F(x)=0, we find the extra term coincides with the gradient of pressure for a quantum particle in a box with no potential. Thus, it appears that a quantum particle, even without a potential, represents a pressure gradient which affects the form of the Schrodinger equation and causes quantum particles to differ from those of classical and classical statistical mechanics.
Quantum mechanics and classical statistical mechanics/thermodynamics are both statistical theories, but have key differences. We argue that one such key difference is nonlocality in the quantum world i.e a wavelength proportional to 1/p and a probability of exp(ipx) associated with p versus locality in the classical case. Quantum nonlocality tends to lead to spatial densities with humps even for a particle with a fixed energy in an infinite potential box. Recently it has been suggested in (1) that one may think of a quantum particle in a box with infinite walls in terms of thermodynamical properties e.g. pressure which is taken to be constant throughout the box. From this assumption, one finds that quantum entropy is ln[ Average(nxnx + nyny+nznz)]. For a single quantum state, this seems to imply that entropy is ln[nxnx+nyny+nznz] ((1a)). In a previous note (2), we suggested that quantum entropy for a wavefunction (say an eigenstate) is Integral dx W*(x)W(x) ln[W*W] + Integral dp a*(p)a(p) ln[a*(p)a(p)] ((1b)). We found this is independent of L for a particle in a box with infinite walls so that displacing the wall adiabatically should mean that dS/dL = 0 which it does as L cancels from ((1)). We argue in this note that quantum pressure should be linked to the density humps for a sin(pave x)sin(pave x) wavefunction even though pave is constant at all x points. Thus it seems that one would not consider a constant pressure for sin(pave x)=wavefunction. Furthermore ((1b)) does not yield the same entropy as ((1a)). It is noted in (1) that ((1a)) is an exact expression for entropy and that the Maxwell-Boltzmann distribution entropy approximates it. In this note, we argue that a time reversal balanced scattering reaction leads to the Fermi-Dirac and Bose-Einstein distributions and these both lead to the Maxwell-Boltzmann distribution under certain conditions. (The Maxwell-Boltzmann distribution may also be obtained from time reversal balanced scattering with looser restrictions.)
In a previous note (1), it was shown that for a ground state oscillator wavefunction, one could analyse the problem in momentum space as a free gas of momentum particles and obtain exp(-p*p/2mT) as fp*fp, fp being the momentum wavefunction. A free energy equal to zero was obtained, with kinetic energy being the energy term in E-TS. This suggests quantum particles scatter (with conservation of momentum) like classical point particles in momentum space, but differ from classical point particles in position space. In particular, one takes a Fourier transform of fp as it seems that each momentum wave carries an exp(ipx) function which is a sort of “baggage” term, possibly due to zitterbewegung. This seems to explain why a free gas in momentum space for the ground state oscillator yields a Gaussian density with W(x)=exp(-ax*x) (W(x)=wavefunction). An oscillator potential is then needed to keep this density with its momentum space pressure in balance. Thus, quantum mechanics and classical statistical mechanics become very similar for this scenario. This begs the question: What about other potentials or oscillator states higher than the ground state? In such a case, it still seems that one may consider “particles colliding in momentum space” with each carrying an exp(ipx) “baggage” term, but one does not have a “classical statistical mechanical” equilibrium scenario any longer. Rather, it seems that one has a net force created by -dV/dx (V(x)=potential) and a difference in pressure d/dx [Average(p*p)d(x)] where d(x) is density. There also seems to be an average velocity (1/W)dW/dx. In momentum space such a velocity would not exist for f(p)=f(-p), but because of the baggage of exp(ipx) it is present i.e. p exp(ipx) - p exp(-ipx). Newton’s law, with force acting on this velocity appears in the equation d/dx [Average(p*p)d(x)]=F(x) d(x). This same equation is equivalent to the gradient of the time-independent Schrodinger equation. For quantum mechanics, one has one particle rather than many as in classical statistical mechanics. Thus, it seems that this “Newton’s law” balance is based on a long term time average. It seems, however, that there should be a period T during which the average can establish itself. After this, one would have periodic time motion where the system keeps scattering back into itself in this characteristic time. This period can be deduced, it seems, from the time-independent Schrodinger equation and is found to be E, the energy.
It is interesting to note that d/dx [ln(d(x))] where d(x) is the spatial density, plays a central role in the time-independent Schrodinger equation, classical mechanics, the Euler equation, equilibrium statistical mechanics and Brownian motion and in all cases, even the quantum one, is related to force as -d/dx V(x), where V(x) is the potential. In this note, we try to examine the role of d/dx [ln(d(x))], and in particular try to see how quantum mechanics is related to classical and fluid mechanics and how it differs.
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.
In the literature (e.g. (1)) the Schrodinger equation is sometimes derived using classical fluid equations which follow from Boltzmann’s transport equations. In particular a continuity equation and a conservation of momentum equation involving the potential dV(x)/dx are used. We have argued in Part I that the continuity equation leads to 0+0=0 for a free particle wavefunction exp(-iEt+ipx) because density is 1. Furthermore a bound quantum state also leads to 0+0=0 partly because d/dt partial density(x) =0. Following the analysis of (1) for which a new field S(x,t) is introduced through u(x,t) =velocity field = d/dx partial S(x,t) one may see that the solution S(x,t)= f(t) for any function f yields u(x,t)=0 for a bound state. In fact, for a bound state, the continuity equation contributes nothing to the derivation of the Schrodinger equation except for the result density(x) (no t present) which is known already. The Schrodinger equation for the bound state follows completely from the fluid transport equation containing dV/dx. For this to occur, however, one must use S(x,t)=-Et. It seems, however, that for a bound state with u(x,t) the natural approach is to have S(x,t) =0 Setting S(x,t)= -Et is equivalent to having exp(-iEt) appear in the wavefunction and we argue in this note that this is an independent assumption which does not follow from fluid mechanics. In particular, we link -Et for the bound state to A(x,t)=classical action = -Et+px. For a bound state there is an average energy value, but overall p average is 0. For the free particle quantum system we argued that two flow flux equations d/dx partial A = p ((1a)) and d/dt partial A = -E ((1b)) govern the system. These may be written separately as eigenvalue equations yielding: id/dt partial exp(iA) = E exp(iA) ((2a)) and -id/dx partial exp(iA) = p exp(iA) ((2b)). We show that exp(-iEt) for the bound state is a built-in assumption needed to make the fluid mechanical equation approach to the Schrodinger equation work. As a result, this assumption id/dt exp(iA)=E exp(iA) needs to be presented together with the two fluid equations, otherwise one does not derive the Schrodinger equation. In fact, one may use ((1a)) and ((1b)), the two flux/flow equations we propose for a free particle and create a momentum distribution P(x/p) = a(p) exp(ipx)/W(x) where W(x)=wavefunction = Sum over p a(p) exp(ipx). Using conservation of energy at each x point: [Sum over p a(p)pp/2m exp(ipx)] / W + V(x) = E leads to the Schrodinger equation without the use of fluid equations.
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.