Atomic momentum distributions in polyatomic molecules in rotational–vibrational eigenstates

Abstract

We report a quantum mechanical method for calculating the momentum distributions of constituent atoms of polyatomic molecules in rotational–vibrational eigenstates. Application of the present theory to triatomic molecules in the rovibrational ground state revealed that oscillatory changes appear on the proton momentum distribution in the nonlinear H2O molecule, while no such modulation is present in the case of an oxygen atom in the linear CO2 molecule. The atomic momentum distributions were analyzed in detail by means of a rigid rotor model, and it was found that the oscillation originates from the quantum-mechanical delocalization of the target atom with respect to the other atoms.