We study the relationship between the tensor product multiplicities of a compact semisimple Lie algebra g and a special function J associated to g, called the volume function. The volume function arises in connection with the randomized Horn's problem in random matrix theory and has a related significance in symplectic geometry. Building on box spline deconvolution formulae of Dahmen-Micchelli and De Concini-Procesi-Vergne, we develop new techniques for computing the multiplicities from J , answering a question posed by Coquereaux and Zuber. In particular, we derive an explicit algebraic formula for a large class of Littlewood-Richardson coefficients in terms of J . We also give analogous results for weight multiplicities, and we show a number of further identities relating the tensor product multiplicities, the volume function and the box spline. To illustrate these ideas, we give new proofs of some known theorems.