No. The question is not whether there are radially symmetric solutions for other values of a, but whether there are any solutions. The solution could be theta-dependent (unless the fact that the BC's are radially symmetric implies that the solution is, but I don't think this is true).
In that case, you can't write down a general solution for the equation, and so you can't obtain a simple set of linear equations for a. (If I could, then, as you say, I would be able to establish conditions for the existence of solutions in terms of a). I could write down a general series solution consisting of an infinite sum of seperable solutions, and then proceed as you suggest. However, this would not be a proof, as the person above says that the seperable solutions do not form a complete set - that is, there may be solutions to the problem that cannot be written as an infinite sum of seperable solutions.