Difference between revisions of "Capillary waves"

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(Stuff added from my contribution to wikipedia -- still to be rewritten a bit)
m (Tidy up (still work to do))
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===Derivation===
 
===Derivation===
This is a sketch of the derivation of the general dispersion relation, see Ref.
+
This is a sketch of the derivation of the general dispersion relation, see Ref. 4 for a more detailed description.
<ref> Samuel Safran "Statistical thermodynamics of surfaces, interfaces, and membranes" Addison-Wesley 1994.</ref> for a more detailed description.
+
 
 +
====Defining the problem====
  
 
Three contributions to the energy are involved: the [[surface tension]], gravity, and hydrodynamics. The part due to gravity is the simplest: integrating the potential energy density due to gravity, <math>\rho g z</math> from a reference height to the position of the surface, <math>z=h(x,y)</math>:
 
Three contributions to the energy are involved: the [[surface tension]], gravity, and hydrodynamics. The part due to gravity is the simplest: integrating the potential energy density due to gravity, <math>\rho g z</math> from a reference height to the position of the surface, <math>z=h(x,y)</math>:
:<math>E_\mathrm{g}=  \int dx\, dy\, \int_0^h dz \rho g z = \rho g /2 \int dx\, dy\, h^2.</math>
+
:<math>E_\mathrm{g}=  \int dx\, dy\, \int_0^h dz \rho g z = \frac{\rho g}{2} \int dx\, dy\, h^2.</math>
 
(For simplicity, we are neglecting the density of the fluid above, which is often acceptable.)
 
(For simplicity, we are neglecting the density of the fluid above, which is often acceptable.)
  
 
An increase in area of the surface causes a proportional increase of energy:
 
An increase in area of the surface causes a proportional increase of energy:
:<math>E_\mathrm{st}= \sigma \int dx\, dy\  \sqrt{(dh/dx)^2+(dh/dy)^2} \approx \sigma/2 \int dx\, dy\  [(dh/dx)^2+(dh/dy)^2],</math>
+
:<math>E_\mathrm{st}= \sigma \int dx\, dy\  \sqrt{\left( \frac{dh}{dx} \right)^2+\left( \frac{dh}{dy} \right)^2} \approx \frac{\sigma}{2\int dx\, dy\  \left[ \left( \frac{dh}{dx} \right)^2+\left( \frac{dh}{dy} \right)^2 \right],</math>
 
where the fist equality is the area in this ([[de Monge]]) representation, and the second
 
where the fist equality is the area in this ([[de Monge]]) representation, and the second
 
applies for small values of the derivatives (surfaces not too rough).
 
applies for small values of the derivatives (surfaces not too rough).
  
 
The last contribution involves the [[kinetic energy]] of the fluid:
 
The last contribution involves the [[kinetic energy]] of the fluid:
:<math>T= \rho/2  \int dx\, dy\, \int_{-\infty}^h dz v^2,</math>
+
:<math>T= \frac{\rho}{2} \int dx\, dy\, \int_{-\infty}^h dz v^2,</math>
where <math>v</math> is the module of the velocity field <math>\vec{v}</math>. If the fluid is
+
where <math>v</math> is the module of the velocity field <math>\vec{v}</math>.
 +
 
 +
 
 +
====Wave solutions====
 +
 
 +
Let us try separation of variables:
 +
:<math>h(x,y,t)=\eta(t)e^{i\vec{q}\vec{r}},</math>
 +
where <math>\vec{q}=(q_x,q_y)</math> is a two dimensional wave number vector, and <math>\vec{r}=(x,y)</math> the position. In this case,
 +
:<math>E_\mathrm{g} \propto \frac{\rho g}{2} \eta^2,</math>
 +
:<math>E_\mathrm{st} \propto \frac{\sigma}{2} q^2 \eta^2,</math>
 +
where a factor of <math>A/4</math> that will appear every
 +
<math>\int dx\, dy\ </math> integration is dropped for convenience.
 +
 
 +
If the fluid is
 
incompressible and its flow is irrotational (often, sensible approximations), its
 
incompressible and its flow is irrotational (often, sensible approximations), its
 
flow will be [[potential flow|potential]]: <math>\vec{v}=\nabla\psi</math>, and <math>\psi</math>
 
flow will be [[potential flow|potential]]: <math>\vec{v}=\nabla\psi</math>, and <math>\psi</math>
Line 66: Line 80:
 
#J. S. Rowlinson and B. Widom "Molecular Theory of Capillarity". Dover 2002 (originally: Oxford University Press 1982) ISBN 0486425444
 
#J. S. Rowlinson and B. Widom "Molecular Theory of Capillarity". Dover 2002 (originally: Oxford University Press 1982) ISBN 0486425444
 
#[http://dx.doi.org/10.1103/PhysRevLett.91.166103 E. Chacón and P. Tarazona  "Intrinsic profiles beyond the capillary wave theory: A Monte Carlo study", Physical Review Letters '''91'''  166103 (2003)]
 
#[http://dx.doi.org/10.1103/PhysRevLett.91.166103 E. Chacón and P. Tarazona  "Intrinsic profiles beyond the capillary wave theory: A Monte Carlo study", Physical Review Letters '''91'''  166103 (2003)]
 +
#Samuel Safran "Statistical thermodynamics of surfaces, interfaces, and membranes" Addison-Wesley 1994
 
#[http://dx.doi.org/10.1103/PhysRevLett.99.196101 P. Tarazona, R. Checa, and E. Chacón "Critical Analysis of the Density Functional Theory Prediction of Enhanced Capillary Waves", Physical Review Letters '''99''' 196101 (2007)]
 
#[http://dx.doi.org/10.1103/PhysRevLett.99.196101 P. Tarazona, R. Checa, and E. Chacón "Critical Analysis of the Density Functional Theory Prediction of Enhanced Capillary Waves", Physical Review Letters '''99''' 196101 (2007)]
 
[[Category: Classical thermodynamics ]]
 
[[Category: Classical thermodynamics ]]

Revision as of 17:12, 10 April 2008

Thermal capillary waves

Thermal capillary waves are oscillations of an interface which are thermal in origin. These take place at the molecular level, where only the surface tension contribution is relevant.

Capillary wave theory (CWT) is a classic account of how thermal fluctuations distort an interface (Ref. 1). It starts from some intrinsic surface that is distorted. By performing a Fourier analysis treatment, normal modes are easily found. Each contributes a energy proportional to the square of its amplitude; therefore, according to classical statistical mechanics, equipartition holds, and the mean energy of each mode will be kT/2. Surprisingly, this result leads to a divergent surface (the width of the interface is bound to diverge with its area) (Ref 2). This divergence is nevertheless very mild: even for displacements on the order of meters the deviation of the surface is comparable to the size of the molecules. Moreover, the introduction of an external field removes the divergence: the action of gravity is sufficient to keep the width fluctuation on the order of one molecular diameter for areas larger than about 1 mm2 (Ref. 2).

Recently, a procedure has been proposed to obtain a molecular intrinsic surface from simulation data (Ref. 3). The density profiles obtained from this surface are, in general, quite different from the usual mean density profiles.


Gravity-capillary waves

These are ordinary waves excited in an interface, such as ripples on a water surface. Their dispersion relation reads, for waves on the interface between two fluids of infinite depth:


\omega^2=\frac{\rho-\rho'}{\rho+\rho'}gk+\frac{\sigma}{\rho+\rho'}k^3,

where ω is the angular frequency, g the acceleration due to gravity, σ the surface tension, ρ and ρ‘ the mass density of the two fluids (ρ > ρ‘) and k the wavenumber.


Derivation

This is a sketch of the derivation of the general dispersion relation, see Ref. 4 for a more detailed description.

Defining the problem

Three contributions to the energy are involved: the surface tension, gravity, and hydrodynamics. The part due to gravity is the simplest: integrating the potential energy density due to gravity, \rho g z from a reference height to the position of the surface, z=h(x,y):

E_\mathrm{g}=  \int dx\, dy\, \int_0^h dz \rho g z = \frac{\rho g}{2} \int dx\, dy\, h^2.

(For simplicity, we are neglecting the density of the fluid above, which is often acceptable.)

An increase in area of the surface causes a proportional increase of energy:

E_\mathrm{st}= \sigma \int dx\, dy\  \sqrt{\left( \frac{dh}{dx} \right)^2+\left( \frac{dh}{dy} \right)^2} \approx \frac{\sigma}{2}  \int dx\, dy\  \left[ \left( \frac{dh}{dx} \right)^2+\left( \frac{dh}{dy} \right)^2 \right],

where the fist equality is the area in this (de Monge) representation, and the second applies for small values of the derivatives (surfaces not too rough).

The last contribution involves the kinetic energy of the fluid:

T= \frac{\rho}{2}  \int dx\, dy\, \int_{-\infty}^h dz v^2,

where v is the module of the velocity field \vec{v}.


Wave solutions

Let us try separation of variables:

h(x,y,t)=\eta(t)e^{i\vec{q}\vec{r}},

where \vec{q}=(q_x,q_y) is a two dimensional wave number vector, and \vec{r}=(x,y) the position. In this case,

E_\mathrm{g} \propto \frac{\rho g}{2} \eta^2,
E_\mathrm{st} \propto \frac{\sigma}{2} q^2 \eta^2,

where a factor of A/4 that will appear every \int dx\, dy\ integration is dropped for convenience.

If the fluid is incompressible and its flow is irrotational (often, sensible approximations), its flow will be potential: \vec{v}=\nabla\psi, and \psi must satisfy Laplace equation \nabla^2\psi=0. This equation can be solved with the proper boundary conditions: \vec{v} must vanish well below the surface (in the "deep water" case, which is the one we consider), and it vertical component must match the motion of the surface: v_z=dh/dt at z=h. Performing the \int_{-\infty} dz integration one is left with a surface integral for the kinetic energy. One is then left with two contribution to the potential energy involving h, dh/dx, and dh/dy, and one for the kinetic energy involving dh/dt, all three being surface integrals. Constructing the Lagrangian of this system one readily finds a wave-like equation, whose oscillatory solutions satisfy


\omega^2=g k+\frac{\sigma}{\rho}k^3,

the same dispersion as above if \rho' is neglected.



References

  1. F. P. Buff, R. A. Lovett, and F. H. Stillinger, Jr. "Interfacial density profile for fluids in the critical region" Physical Review Letters 15 pp. 621-623 (1965)
  2. J. S. Rowlinson and B. Widom "Molecular Theory of Capillarity". Dover 2002 (originally: Oxford University Press 1982) ISBN 0486425444
  3. E. Chacón and P. Tarazona "Intrinsic profiles beyond the capillary wave theory: A Monte Carlo study", Physical Review Letters 91 166103 (2003)
  4. Samuel Safran "Statistical thermodynamics of surfaces, interfaces, and membranes" Addison-Wesley 1994
  5. P. Tarazona, R. Checa, and E. Chacón "Critical Analysis of the Density Functional Theory Prediction of Enhanced Capillary Waves", Physical Review Letters 99 196101 (2007)