A theoretical study of the MgNC/MgCN isomerization in the electronic ground stateq

This paper reports the first theoretical treatment of the MgNC $ MgCN isomerization in the ~X2Sþ electronic ground state. Based on ab initio data, a global potential energy surface encompassing the MgNC and MgCN minima (which both correspond to linear geometries) has been constructed, and this surface has been used, together with global dipole moment surfaces, for calculating 24MgNC/24MgCN rotation– vibration energies and transition moments for states up to about 2150 cm21 above the vibrational ground state of 24MgNC. The vibrational ground state of 24MgCN is found to be 651 cm21above that of 24MgNC. The first delocalized state occurs at 2111.9 cm21. The prospect of implementing the successive stimulated Raman adiabatic passage (STIRAP) method for optically controlling the MgNC $ MgCN isomerization is discussed. q 2003 Elsevier B.V. All rights reserved.