The dynamics of the S(D-1) + CD4 --> SD + CD3 reaction has been studied in a photolysis-probe experiment. S(1D) reagent was prepared by laser photolysis of CS2, and the SD(X(2)Pi) product was detected by laser fluorescence excitation. The nascent rotational/ fine-structure state distribution of the SD(X(2)Pi) product was determined. The experimentally determined rotational state distribution within each fine-structure manifold agrees well with the predictions of a statistical 'prior' distribution, while the F-1 to F-2 fine-structure branching ratio is higher than predicted statistically. The product state distribution is consistent with reaction through the formation and decay of an energized CD3SD complex. (C) 2004 Elsevier B.V. All rights reserved.