The previous answers do not exhaust this question, so I will add a solution to the problem as posted. The question is: what is the probability distribution for the meeting time of two diffusing spheres of radii $r_1$ and $r_2$ starting at initial separation R. By transforming to relative coordinates (as Peter Shor said), you reduce the problem to one diffusing point particle which is absorbed on a sphere of radius $A=r_1+r_2$.
The following is true in 3d
- The particles will not certainly collide. The probability of eventual collision is A/R. The probability of reaching infinity is $1-A/R$.
- If you ask the question--- do the particles collide first or reach a separation of B first, the probability of colliding first is ${ {1\over R} - {1\over B} \over {1\over A} - {1\over B} }$
- There is the usual 3d miracle of Laplacians, that there is a change of variables which normalizes the radial part to a free 1d Laplacian, which allows a closed form expression for the probability density of colliding at any finite time. This gives a complete answer to the question: the probability of not having collided at time t is given by $ P(t) = (1-{A\over R}) + {A\over R} S(\Delta,t)$, where $\Delta= R-A$, and $S(\Delta,t)$ is the probability that a 1 dimensional Brownian motion starting at position $\Delta$ has not hit the origin by time t.
$S(\Delta,t)$ is a simple function which is essentially just the error function:
$$ S(\Delta,t) = ( {2\over \sqrt{\pi}} \mathrm{erf}({\Delta \over \sqrt{2t}})) $$
It's only a function of ${\Delta \over\sqrt{t}}$ by scaling. The probability density of a collision at time t is found by differentiating the above expression, and it only involves elementary functions:
$$\rho(t) = {A\over R} {1\over 4\sqrt{\pi}}{\Delta e^{-{\Delta^2\over 2t}} \over t^{3\over 2}}$$
The answer is strange, because up to the factor of A/R which accounts for the fact that not all walks collide, it is exactly the same as the probability density for a 1d Brownian motion to collide with the origin at time t.
Image charge magnitude is collision probability
Diffusion is by the Laplacian. If you introduce a steady stream of particles at position R, they will come to a steady equilibrium where some are running off to infinity, and some are absorbed by the sphere of radius A. If you introduce these particles at a random angular position on the sphere of radius R, you get a spherically symmetric solution of Laplace's equation at steady state $\phi(r)$, which represents the steady-state density of particles.
The gradient of $\phi$ is the particle steady-state flow, it is the electric field in an electrostatic analog. The source on the sphere at R is a charge Q uniformly distributed on the sphere, which produces an outgoing electric field, an outgoing flow of particles. The particle sink on the sphere of radius A is a potential 0 surface, a metal grounded to infinity.
The solution to this places an image sphere at $A^2/R$ which has charge as required to cancel the potential. The charge is QA/R. This means that the flux into the metal is a fraction A/R of the flux introduced at R, which means that of all the outgoing flux, a fraction A/R is captured by the sphere. This gives the collision probability.
In one and two dimensions, the image charge magnitude in a sphere is always the same as the charge magnitude, and this says that 2d walks are recurrent.
Time-independent Problems are Easy
The solution to the problem of collision with an inner sphere vs. an outer sphere can be solved in the same way. The sphere at A is now is grounded on the outer sphere at a radius B, so that, matching the potentials:
$${Q \over R} - {Q_i \over A} = {Q-Q_i \over B}$$
Where $Q$ is the charge and $Q_i$ is the image charge. The image charge magnitude is
$$ Q_i = Q { {1\over R} - {1\over B} \over {1\over A} - {1\over B} }$$
This is the probability of reaching A before reaching B. It asymptotes to the correct answer for $B=\infty$, of course. This is a time-independent problem, so it has a simple answer using grounded conductors.
This gives you a qualitative indication of what the distribution for first colllsion is, By using B as a surrogate for $\sqrt{t}$. Expanding in B to leading order, and substituting $\sqrt{t}$ for B gives that the probability of surviving is
$$P(t) = {A\over R} (1 - {R-A\over \sqrt{t}})$$
Which is to be compared to the exact answer below.
Time dependent problem
The time dependent problem, the original question, also has a closed form solution. The first thing to note is that the distance between the two particles is undergoing a diffusion too. This distance prefers to go out rather than in, according to the extra phase space volume of being at a larger radius.
The form of the effective one dimensional diffusion can be worked out using a simple trick--- the uniform 3d distribution must be the Boltzmann distribution for diffusion in the effective potential on r. The resulting equation for the radial diffusion is:
$${\partial\rho\over\partial t} = {\partial \over\partial r} ( {\partial\rho\over \partial r} - {(d-1)\over r} \rho )$$
Where $d=3$ is the case of interest, and the boundary conditions you enforce are $\rho(A)=0$ and $\rho(\infty)=0$. This has a simple solution in the usual 3d way: you write $\rho(r,t) = rf(r,t)$ and then
$${\partial f\over \partial t} = {\partial^2 f\over \partial^2 r}$$
Which is the usual miracle of three dimensions, radial Laplacians become free 1d Laplacians once you extract a 1/r factor. In this case, since the distribution $\rho$ is already mutliplied by $r^2$ relative to the radially symmetric solution of Laplace's equation, you extract an r instead.
I will digress to clear up a few confusions:
- How is it possible for a 3d Laplacian, which conserves the 1d integral $r^2\rho(r)$, to be equivalent to a 1d Laplacian, which conserves the integral $f(r)$ without powers of r?
The reason is that diffusion conserves two different moments: the total probability, and the center of mass. The center of mass for f is the total probability for $\rho$. This is important, because f is not to be interpreted as a probability directly, it's first moment is the total probability.
- The location of images in 1d and in 3d are totally different! In 1d, if you have a Dirichlet condition, you always reflect at that point to find the image position. In 3d, you have to reflect in a sphere. How could the two problems be related?
There is an important note regarding this: if you just map a free diffusion in 3d to 1d, the 1d problem has absorbing boundary at the origin. The reason is that the 1d diffusion must be 0 at 0, because it comes from a 3d diffusion which has a finite density at 0 (or from a 1d radial diffusion whose density vanishes as $r^2$ near 0--- same thing). The correct images to use when there is a Dirichlet boundary condition on a sphere are the 1d images. These give the correct 1d solution. Although this is a trivial point, considering the previous section, it is confusing when you take the limits to extract the behavior at long times.
The solution for a delta function at r=R is
$$ f_D(r,t) = {1\over \sqrt{2\pi t}} (e^{-{(r-R)^2\over 2t}} - e^{-{(r-(2A-R))^2\over 2t}}) $$
Which is the image-charge method for producing a solution which is zero at $r=A$. This solution will decay, because of the negative probability coming from the image, or in real life, because of the absorption of the probability into the boundary at r=A, i.e. because of collisions. The leftover probability density is the answer to the question.
So the answer is the first moment of $f_D(r,t)$:
$$ {1\over N} \int_A^\infty r f_D(r,t) = {1\over N} \int_A (r-A) f_D(r,t) + A f_D(r,t) $$
Where the normalization constant N is so that the answer will be 1 at $t=0$.
$$ N = \int_A^\infty r f_D(r,0) = \int_A^\infty r \delta(r-R) = R$$
Using the variable $u=r-A$, the first integral is symmetric between u and -u, and becomes half the integral from minus infinity to infinity of something simple to do.
$${1\over 2R} \int_{-\infty}^\infty u f_d(u,t) = {A\over R}$$
The second integral $\int_0^\infty A f_D(r,t)$ is simply the probability of a 1d walk to avoid the origin up to time t, and it is multiplied by ${A\over R}$.