Controlling the outcome of chemical reactions by exciting specific vibrational and/or rotational modes of the reactants is one of the major goals of modern reaction dynamics studies. In the present Perspective, we focus on first-principles vibrational and rotational mode-specific dynamics computations on reactions of neutral and anionic systems beyond six atoms such as X + C2H6 [X = F, Cl, OH], HX + C2H5 [X = Br, I], OH- + CH3I, and F- + CH3CH2Cl. The dynamics simulations utilize high-level ab initio analytical potential energy surfaces and the quasi-classical trajectory method. Besides initial state specificity and the validity of the Polanyi rules, mode-specific vibrational-state assignment for polyatomic product species using normal-mode analysis and Gaussian binning is also discussed and compared with experiment.