Stereomutation in vibrationally excited NHD2

The stereomutation at the pyramidal nitrogen atom induced by intense infrared radiation is a prototype, photo-induced chemical reaction. This reaction is addressed here theoretically. We investigate the coherent excitation quantum dynamics as well as of the rearrangement process of atoms with the help of realistic potential energy and dipole moment surfaces. The “Multi-configurational Time-dependent Hartree” (MCTDH) program package is used. We discuss convergence issues related to the choice of basis sets used in this program. A simple control mechanism is proposed to control the rate of the reaction by an appropriate choice of the carrier frequency and duration of the laser pulse.