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We extend and deepen the theory of functional calculus for semigroup generators, based on the algebra of analytic Besov functions, which we initiated in a previous paper. In particular, we show that our construction of the calculus is optimal in several natural senses. Moreover, we clarify the structure of and identify several important subspaces in practical terms. This leads to new spectral mapping theorems for operator semigroups and to wide generalisations of a number of basic results from semigroup theory.

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