In this thesis, steric effects in the dissociative chemisorption of quantum state-prepared methane on single crystal surfaces of nickel (Ni(100) and Ni(110)) are detected and quantified for the first time. Exploiting a new, continuous-wave, high-power, single-mode infrared optical parametric oscillator, I produced an intense, quantum state-prepared molecular beam by rapid adiabatic passage. During the infrared excitation of the antisymmetric (ν3) stretch of CH4 or the C-H (ν1) stretch of CD3H by linearly polarized radiation, the angular momentum and vibrational transition dipole moment of methane is aligned in the laboratory frame. The excited, aligned molecular beam is used to probe the stereodynamics of the chemisorption reaction of vibrationally excited methane. For the reaction on Ni(100), an increase in state-prepared methane reactivity of nearly 60% is observed when the laser polarization direction is changed from normal to parallel to the surface. The dependence of the alignment effect on the rotational branch used for excitation (P-, Q-, or R-branch) indicates that alignment of the vibrational dipole moment rather than the angular momentum is responsible for the alignment dependent reactivity. Dephasing of the initially prepared alignment due to hyperfine coupling is observed to be on the timescale of 5-15 microseconds which does not preclude the study of alignment dependent reactivity in our experimental setup. Reactivity decreased monotonically from parallel to perpendicular alignment for both methane isotopologues studied. The alignment effect is shown to be independent of incident velocity for CH4(ν3) and decreases with increasing velocity of CD3H(ν1). For the Ni(110) surface, which consists of parallel rows of closely spaced Ni atoms separated by one-layer deep troughs, I probed if the reactivity depends on the methane alignment relative to the direction of the surface rows. The CH4(ν3) reactivity increases a factor of two when the laser polarization direction is changed from normal to parallel to the surface. Alignment of the vibration perpendicular to the surface rows produced a ∼10% higher reactivity than alignment parallel to the surface rows. Steric effects in a chemical reaction reveal detailed information about the reactive potential energy surface, which makes experimental studies of stereochemistry a powerful probe of microscopic chemical dynamics. The results in this thesis demonstrate and quantify specific steric requirements for this benchmark gas-surface reaction and will serve as a stringent test of multi-dimensional dynamics calculations.