New universal Lyapunov functions for nonlinear kinetics
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1 New universal Lyapunov functions for nonlinear kinetics Department of Mathematics University of Leicester, UK July 21, 2014, Leicester
2 Outline 1 2
3 Outline 1 2
4 Boltzmann Gibbs-Shannon relative entropy ( ) For a system with discrete space of states A i H BGS (P P )= ( ) ) pi p i (ln p 1 i i where P =(p i ), P =(pi ) are the positive probability distributions.
5 Kolmogorov s (master) equation q ij = q i j 0fori j (i, j = 1,...,n) dp i dt = (q ij p j q ji p i ) j, j i With a known positive equilibrium P dp i dt = q ij pj j, j i ( pj p j p i p i ) where p i and q ij are connected by the balance equation q ij pj = q ji pi for all i = 1,...,n j, j i j, j i
6 Information processing lemma (continuous time) Information does not increase (in average) due to random manipulations (Shannon 1948). For a system with positive equilibrium P d dt H BGS(P P ) 0 due to master equation
7 Mass action law A i are components, c i is concentration of A i i α ria i i β ria i elementary reactions (reversible) w r + = k r + i cα ri i, wr = kr i cβ ri i ; w r = w r + wr the reaction rate γ r =(γ ri )=(β ri α ri ) the stoichiometric vector ċ = r γ r w r kinetic equations
8 Detailed balance and H-theorem (essentially, Boltzmann, 1872) There exists a positive point of detailed balance: Then for all positive c d dt c i > 0, r w + r (c )=w r (c ) c i (ln i = r ( ci c i ) ) 1 (w + r w r )(ln w + r ln w r ) 0
9 Outline 1 2
10 f -divergences For any convex function h(x) defined on the open (x > 0) or closed x 0 semi-axis H h (p) =H h (P P )= i ( ) pi h pi pi where P =(p i ) is a probability distribution, P is an equilibrium distribution. Rényi (1960) Csiszár (1963), and Morimoto (1963) proved the information processing lemma (H-theorem) for these functions and Markov chains.
11 Rényi Csiszár Morimoto H-theorem Due to Master equation with the positive equilibrium P dh h (p) dt = l,j, j l = i,j, j i ( ) h pj q jl pl q ij p j p j [ h ( pi p i ( p l pl ) h p j p j ( pj p j ) ) ( ) ( + h pi p j pi pj p i p i )] 0
12 Outline 1 2
13 Hartley & BGS h(x) is the step function, h(x) =0ifx = 0 and h(x) = 1 if x > 0. H h (P P )= 1. i, p i >0 (the Hartley entropy); h = x 1, H h (P P )= p i pi ; i (the l 1 -distance between P and P ); h = x ln x, H h (P P )= ( ) pi p i ln p = D KL (P P ); i i (the relative Boltzmann Gibbs Shannon (BGS) entropy);
14 Burg & Fisher h = ln x, H h (P P )= i ( ) pi pi ln pi = H BGS (P P); (the relative Burg entropy); h = (x 1)2 2, H h (P P )= 1 2 i (p i p i )2 p i = H 2 (P P ); (the quadratic approximation of the relative Botzmann Gibbs-Shannon entropy);
15 Cressie Read (CR) family h = x(xλ 1) λ(λ+1) H h (P P )= 1 λ(λ + 1) (the Cressie Read (CR) family). If λ 0 then H CR λ H BGS, if λ 1 then H CR λ H Burg ; { H CR (P P pi )=max i i [ ( ) λ pi p i pi 1] ; p i { p H CR (P P )=max i i p i } 1 ; } 1.
16 Tsallis h = (xα x) α 1, α>0, H h (P P )= 1 α 1 (the Tsallis relative entropy). i [ ( ) α 1 pi p i pi 1].
17 The puzzle of nonlinear systems For the linear systems many Lyapunov functionals are known in the explicit form, On the contrary, for the nonlinear MAL systems with detailed balance we, typically, know the only Lyapunov function H BGS ; The situation looks rather intriguing and challenging: for every finite reaction mechanism with detailed balance there should be many Lyapunov functionals, but we cannot construct them. We present a general procedure for the construction of a family of new Lyapunov functionals from H BGS for nonlinear MAL kinetics and a given reaction mechanism. There is no chance to find many Lyapunov functions for all nonlinear mechanisms together.
18 Outline 1 2
19 Quasiequilibrium Let H(c) =H BGS (c) = i ( ) ) ci c i (ln ci 1 For every linear subspace E R n and a given concentration vector c 0 R n + the quasiequilibrium composition is the conditional minimizer of H: c E (c0 )= argmin H(c) c (c 0 +E) R n + The quasiequilibrium divergence is the value of H at the quasiequilibrium: H E (c0 )= min H(c) c (c 0 +E) R n +
20 Properties of quasiequilibria H is strongly convex and H has logarithmic singularity at c i 0. Therefore, for a positive vector c 0 R n + and a given subspace E R n the quasiequilibrium composition c E (c0 ) is also positive. H E (c0 ) H(c 0 ) and this inequality turns into the equality if and only if c 0 is the quasiequilibrium c 0 = c E (c0 ).
21 Such quasiequilibrium entropies were discussed by Jaynes (1965). He considered the quasiequilibrium H-function as the Boltzmann H-function H B in contrast to the original Gibbs H-function, H G. The Gibbs H-function is defined for the distributions on the phase space of the mechanical systems. The Boltzmann function is a conditional minimum of the Gibbs function, therefore the Jaynes inequality holds H B H G These functions are intensively used in the discussion of time arrow. In the theory of information, quasiequilibrium was studied in detail under the name information projection.
22 Consider the reversible reaction mechanism with the set of the stoichiometric vectors Υ. For each Γ Υ we can take E = Span(Γ) and define the quasiequilibrium. Let E Υ be the set of all subspaces of the form E = Span(Γ) (Γ Υ). EΥ k is the set of k-dimensional subspaces from E Υ for each k. Define H k,max Υ for each dimension k = 0,...,rank(Υ): H 0,max Υ = H, and for k > 0 H k,max Υ (c) =max HE (c) E E k Υ
23 Outline 1 2
24 H 1,max H 1,max Υ H 1,max Υ (c 0 )=max γ Υ { } min H(c) c (c 0 +γr) R n + (c) is a Lyapunov function in R n + for all MAL systems with the given equilibrium c and detailed balance on the set of stoichiometric vectors Γ Υ.
25 Simple reaction mechanism for example Consider a simple reaction mechanism: 1 A 1 A 2, 2 A 2 A 3, 3 2A 1 A 2 + A 3. The concentration triangle c 1 + c 2 + c 3 = b is split by the partial equilibria lines into six compartments.
26 Example: QE states b) γ 1 γ 3 A 2 γ 2 ǀǀγ 1 ǀǀγ 3 ǀǀγ 2 A 1 A 3
27 Example: H 1,max level set b) γ 1 γ 2 γ 3 ǀǀγ 3 A 2 level set ǀǀγ 1 ǀǀγ 2 A 1 A 3
28 Outline 1 2
29 Let U be a convex compact set of non-negative n-dimensional vectors c and for some η>min H the η-sublevel set of H belongs to U: {N H(N) η} U. Let h > min H be the maximal value of such η. Select ε>0. The ε>0-peeled set U is U ε Υ = U {N Rn + H1,max Υ (N) h ε} For sufficiently small ε>0(ε<h min H) this set is non-empty and forward invariant.
30 Illustration: forward-invariant peeling Peeling Peeling
31 Peeling Peeling Peeling The additional peeling Span{γ 1,γ 2 } makes the peeled set forward invariant with respect to the set of systems with interval reaction rate constants.
32 Main message For every reaction mechanism there exists an infinite family of Lyapunov functions for reaction kinetics that depend on the equilibrium but not in the rate constants. These functions are produced by the operations of conditional minimization and maximization from the BGS relative entropy.
33 References Just look Gorban in arxiv and references there.
arxiv: v5 [cond-mat.stat-mech] 2 Jul 2014
Entropy 2014, 16, 2408-????; doi:10.3390/e16052408 OPEN ACCESS entropy ISSN 1099-4300 www.mdpi.com/journal/entropy Article General H-theorem and Entropies that Violate the Second Law Alexander N. Gorban
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