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P. 1

N. Theodorakopoulos- Nonlinear physics (solitons, chaos, discrete breathers)|Views: 92|Likes: 1

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https://www.scribd.com/doc/81403690/N-Theodorakopoulos-Nonlinear-physics-solitons-chaos-discrete-breathers

02/28/2012

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At any ﬁnite temperature, we will have to consider the competition of the two possible

structures: the one corresponding to the ﬁxed point, and the corresponding to the DW with

the least energy. Strictly speaking, in the latter case we are considering the totality of all

possible values of L.

**Free energy associated with a given minimum
**

For small displacements around any given local minimum** {**¯yn

yn = ¯yn +un

the total potential energy will be given, to quadratic order in the displacements, by

Φ(u)** ≈**E(¯y) + 1

2

i,j

hijuiuj ,

where E(¯y) is the energy of the local minimum.

The associated conﬁgurational part of the partition function will be

Z(¯y) = e−βE(¯y)

∞

−∞

N

m=1

dum

e−*β
*

2

*i,j
*

h*ij*u*i*u*j
*

= e−βE(¯y)

N

ν=1

2π

βΛν

1/2

(14.35)

where the product runs over all eigenvalues of the Hessian. Note that the eigenvalues must be

strictly positive, not just nonnegative. The free energy associated with any given minimum

will then be

F(¯y) =** −**T lnZ(¯y) = E(¯y)

2

N

ν=1

ln

2π

βΛν

(14.36)

**Comparison of free energies
**

The spectra of (i) the ﬁxed point and (ii) the stable DW with the minimal energy at some

ﬁnite L are shown in Fig. 14.2.2.

142

14 Unbinding the double helix

Now consider the diﬀerence in free energies between the DW with the minimal energy at

some ﬁnite L and the ﬁxed point

∆F(L) = E∗(L)** −** T

2

N

ν=1

ln

Λ0

ν

Λ∗ν

(14.37)

where the star in the superscript denotes the DW and the 0 the ﬁxed point.

The second term represents the diﬀerence in entropies. Formation of the DW generates a

gain in entropy. The quantity

1

2

N

ν=1

ln

Λ0

ν

Λ∗ν

** ≡** L

p∗σ(R)

is generally proportional to the number L/p∗ of unbound sites. The extra entropy comes

exclusively from the unbound part. It is due to the fact that the acoustic phonons which

live in the unbound region have lower frequencies than the optical phonons which live in the

bound state deﬁned by ﬁxed point.

Combining terms, the diﬀerence in free energy can be written as

∆F(L) = [2** −**Tσ(R)] L

p∗

(14.38)

which becomes zero at

Tc(R) = 2

σ(R)

(14.39)

and negative at higher temperatures. Thus, if the temperature is raised beyond Tc(R) a DW

of any length can be formed spontaneously - since it generates a net gain in free energy.

Denaturation can occur spontaneously.

Alternatively, we may look at the derivative

p = dF(L)

dL = [2** −**Tσ(R)] 1

p∗

(14.40)

which represents the unzipping force at a ﬁnite temperature T. Spontaneous thermal de-

naturation is, in this sense, equivalent to the vanishing of the unzipping force.

For not too large values of R, the proportionality constant is

σ(R) = ln

R/2 + 1 +R/2

.

(14.41)

In the continuum limit, R** ** 1, this gives a Tc = 2(2/R)1/2

, which is exactly the critical

temperature found in Section 14.1.2.

In summary, what I have presented in this lecture is an alternative picture of the DNA

instability, based on the underlying, competing nonlinear equilibrium structures (domain

walls vs. ﬁxed point). The results suggest that the domain wall, via the entropic gain it

generates, can overcome the energetic cost of its production. In other words, spontaneous

formation of a DW at the instability temperature is what really “drives” DNA denaturation.

143

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