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The ''' | The '''Maxwell velocity distribution''' <ref>J. C. Maxwell "", British Association for the Advancement of Science '''29''' Notices and Abstracts 9 (1859)</ref> | ||
<ref>[http://dx.doi.org/10.1080/14786446008642818 J. C. Maxwell "V. Illustrations of the dynamical theory of gases.—Part I. On the motions and collisions of perfectly elastic spheres", Philosophical Magazine '''19''' pp. 19-32 (1860)]</ref> | |||
<ref>[http://dx.doi.org/10.1080/14786446008642902 J. C. Maxwell "II. Illustrations of the dynamical theory of gases", Philosophical Magazine '''20''' pp. 21-37 (1860)]</ref> | |||
<ref>[http://dx.doi.org/10.1098/rstl.1867.0004 J. Clerk Maxwell "On the Dynamical Theory of Gases", Philosophical Transactions of the Royal Society of London '''157''' pp. 49-88 (1867)]</ref> provides probability that the speed of a molecule of mass ''m'' lies in the range ''v'' to ''v+dv'' is given by | |||
:<math>P(v)dv = 4 \pi v^2 dv \left( \frac{m}{2 \pi k_B T} \right)^{3/2} \exp (-mv^2/2k_B T) </math> | :<math>P(v)dv = 4 \pi v^2 dv \left( \frac{m}{2 \pi k_B T} \right)^{3/2} \exp (-mv^2/2k_B T) </math> | ||
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and the root-mean-square speed by | and the root-mean-square speed by | ||
:<math>\sqrt{\overline{v^2}} = \sqrt | :<math>\sqrt{\overline{v^2}} = \sqrt \frac{3}{2} v_{\rm max}</math> | ||
==Derivation== | |||
Consider an ideal gas with particles of unity mass in the three-dimensional (<math>3D</math>) space. As long as there is not a privileged direction in the equilibrium, we can take any direction | |||
in the space and to study the discrete time evolution of the velocity distribution in that direction. Let us call this axis <math>U</math>. We can complete a Cartesian system with two additional orthogonal axis <math>V,W</math>. If <math>p_n(u){\mathrm d}u</math> represents the probability of finding a particle of the gas with velocity component in the direction <math>U</math> comprised between <math>u</math> and <math>u + {\mathrm d}u</math> at time <math>n</math>, then the probability to have at this time <math>n</math> a particle with a <math>3D</math> velocity <math>(u,v,w)</math> will be <math>p_n(u)p_n(v)p_n(w)</math>. The particles of the gas collide between them, and after a number of interactions of the order of system size, a new velocity distribution is attained at time <math>n+1</math>. Concerning the interaction of particles with the bulk of the gas, we make two simplistic and realistic assumptions in order to obtain the probability of having a velocity <math>x</math> in the direction <math>U</math> at time <math>n+1</math>: (1) Only those particles with an energy bigger than <math>x^2</math> at time <math>n</math> can contribute to this velocity <math>x</math> in the direction <math>U</math>, that is, all those particles whose velocities <math>(u,v,w)</math> verify <math> u^2+v^2+w^2\ge x^2</math>; (2) The new velocities after collisions are equally | |||
distributed in their permitted ranges, that is, particles with velocity <math>(u,v,w)</math> can generate maximal velocities <math>\pm U_{max}=\pm\sqrt{u^2+v^2+w^2}</math>, then the allowed range of velocities <math>[-U_{max},U_{max}]</math> measures <math>2|U_{max}|</math>, and the contributing probability of these particles to the velocity <math>x</math> will be <math>p_n(u)p_n(v)p_n(w)/(2|U_{max}|)</math>. Taking all together we finally get the expression | |||
for the evolution operator <math>T</math>. This is: | |||
<math> | |||
p_{n+1}(x)= | p_{n+1}(x)=Tp_n(x) = \int\int\int_{u^2+v^2+w^2\ge x^2}\,{p_n(u)p_n(v)p_n(w)\over 2\sqrt{u^2+v^2+w^2}} \; {\mathrm d}u{\mathrm d}v{\mathrm d}w\,. | ||
</math> | </math> | ||
Let us remark that we have not made any supposition about the type of interactions or collisions | Let us remark that we have not made any supposition about the type of interactions or collisions | ||
between the particles and, in some way, the equivalent of the Boltzmann hypothesis of ''molecular chaos'' would be the two simplistic assumptions we have stated on the interaction of particles with the bulk of the gas. In fact, the operator <math> | between the particles and, in some way, the equivalent of the Boltzmann hypothesis of ''molecular chaos'' would be the two simplistic assumptions we have stated on the interaction of particles with | ||
the bulk of the gas. In fact, the operator <math>T</math> conserves in time the energy and the null momentum of the gas. Moreover, for any initial velocity distribution, the system tends towards its equilibrium, i.e. towards the Maxwellian Velocity Distribution (MVD). This means that | |||
<math> | |||
\lim_{n\rightarrow\infty} T^n \left(p_0(x)\right) \rightarrow p_f(x)=MVD\;(1D\;case)\,. | |||
\lim_{n\rightarrow\infty} | |||
</math> | </math> | ||
Let us sketch now all these properties. | |||
First, we introduce the norm <math>||\cdot||</math> of positive functions (one-dimensional velocity distributions) in the real axis as | |||
<math> | |||
\vert\vert p\vert\vert=\int_{-\infty}^{+\infty} p(x) dx. | \vert\vert p\vert\vert=\int_{-\infty}^{+\infty} p(x) dx. | ||
</math> | </math> | ||
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===Theorem 1=== | ===Theorem 1=== | ||
For any <math>p</math> with <math>||p||=1</math>, we have <math>|| | For any <math>p</math> with <math>||p||=1</math>, we have <math>||Tp||=||p||</math>. | ||
This can be interpreted as the conservation of the number of particles | This can be interpreted as the conservation of the number of particles or in an equivalet way of the total mass of the gas. | ||
===Theorem 2=== | ===Theorem 2=== | ||
The mean value of the velocity in the recursion <math>p_n= | The mean value of the velocity in the recursion <math>p_n=T^np_0</math> is conserved in time. | ||
In fact, it is null for all <math>n</math>: | In fact, it is null for all <math>n</math>: | ||
<math> | |||
<x,Tp>=<x,T^2p>=<x,T^3p>=\cdots=<x,T^np>=\cdots=0\,, | |||
</math> | </math> | ||
where | where | ||
<math> | |||
<f,g>=\int_{-\infty}^{+\infty}f(x)g(x){\mathrm d}x\,. | |||
</math> | </math> | ||
It means that the zero total momentum of the gas is conserved in its time evolution under the action of <math> | It means that the zero total momentum of the gas is conserved in its time evolution under the action of <math>T</math>. | ||
===Theorem 3=== | ===Theorem 3=== | ||
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For every <math>p</math> with <math>||p||=1</math>, we have | For every <math>p</math> with <math>||p||=1</math>, we have | ||
<math> | |||
<x^2,p>=<x^2,Tp>=<x^2,T^2p>=<x^2,T^3p>=\cdots=<x^2,T^np>=\cdots \,. | |||
</math> | </math> | ||
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===Theorem 4=== | ===Theorem 4=== | ||
The one-parametric family of normalized | The one-parametric family of normalized gaussian functions <math>p_{\alpha}(x)=\sqrt{\alpha\over\pi}e^{-\alpha x^2}</math>, <math>\alpha\ge 0</math>, <math>||p_{\alpha}||=1</math>, are fixed points of the operator <math>T</math>. In other words, <math>Tp_{\alpha}=p_{\alpha}</math>. | ||
===Conjecture=== | ===Conjecture=== | ||
As a consequence of the former theorems | As a consequence of the former theorems and by simulation of many exmaples, it can be claimed the following conjecture: | ||
For any <math>p</math> with <math>||p||=1</math>, with finite <math> | For any <math>p</math> with <math>||p||=1</math>, with finite <math><x^2,p></math> and verifying <math>\lim_{n\rightarrow\infty} ||T^np(x)-\mu(x)||=0</math>, the limit <math>\mu(x)</math> is the fixed point <math>p_{\alpha}(x)=\sqrt{\alpha\over\pi}\,e^{-\alpha x^2}</math>, with <math>\alpha=(2\,<x^2,p>)^{-1}</math>. | ||
===Conclusion=== | ===Conclusion=== | ||
In physical terms, it means that for any initial velocity distribution of the gas, it decays to the Maxwellian distribution, which is just the fixed point of the dynamics. Recalling that <math> | In physical terms, it means that for any initial velocity distribution of the gas, it decays to the Maxwellian distribution, which is just the fixed point of the dynamics. Recalling that <math><x^2,p>=k\tau</math>, with <math>k</math> the Boltzmann constant and <math>\tau</math> the temperature of the gas, and introducing the mass <math>m</math> of the particles, let us observe that the MVD (above presented) is recovered in its <math>3D</math> format: | ||
<math> | |||
MVD = p_{\alpha}(u)p_{\alpha}(v)p_{\alpha}(w)=\left({m\alpha\over\pi}\right)^{3\over 2}\,e^{-m\alpha (u^2+v^2+w^2)} \;\;\; with \;\;\; \alpha=(2k\tau)^{-1}. | |||
</math> | </math> | ||
==References== | ==References== | ||
<references/> | <references/> | ||
;Related reading | ;Related reading | ||
*[http://dx.doi.org/10.1080/002068970500044749 J. S. Rowlinson "The Maxwell-Boltzmann distribution", Molecular Physics '''103''' pp. 2821 - 2828 (2005)] | |||
*[http:// | *[http://arxiv.org/abs/1105.4813 Elyas Shivanian and Ricardo Lopez-Ruiz "A New Model for Ideal Gases. Decay to the Maxwellian Distribution", arXiv:1105.4813v1 24 May (2011)] | ||
==External resources== | ==External resources== | ||
*[ftp://ftp.dl.ac.uk/ccp5/ALLEN_TILDESLEY/F.24 Initial velocity distribution] sample FORTRAN computer code from the book [http://www.oup.com/uk/catalogue/?ci=9780198556459 M. P. Allen and D. J. Tildesley "Computer Simulation of Liquids", Oxford University Press (1989)]. | *[ftp://ftp.dl.ac.uk/ccp5/ALLEN_TILDESLEY/F.24 Initial velocity distribution] sample FORTRAN computer code from the book [http://www.oup.com/uk/catalogue/?ci=9780198556459 M. P. Allen and D. J. Tildesley "Computer Simulation of Liquids", Oxford University Press (1989)]. | ||
[[category: statistical mechanics]] | [[category: statistical mechanics]] |