Abstract The control of chemical reaction pathways has been of great interest in chemistry. One way of controlling the course of a chemical reaction is through manipulation of its transition state. In this work, we suggest the possibility of bond selective dissociation of the collinear BrHBr transition state complex by the use of an infrared linear chirped laser pulse to drive vibrational states of the BrHBr. The initial vibrational state of the BrHBr is prepared as a linear combination of two quasi‐bound vibrational states of the BrBr degree of freedom. We employ state of the art potential energy and dipole moment surfaces for the BrHBr to simulate the interaction of the initially prepared BrHBr with an optimized linear chirp laser pulse. The results of these quantum simulations show (i) that the bond selective dissociation depends on the initial preparation of the vibrational state of the BrHBr, (ii) the feasibility of manipulating the quasi‐bound vibrational states of a XHX type complex (X halogen atom) to enhance its rate of dissociation, and (iii) the possibility of controlling the branching ratio of the product channels (Br + HBr and BrH + Br) with a relatively broad range of values to choose.