title: Construction of diabatic Hamiltonian matrix from ab initio calculated molecular symmetry adapted nonadiabatic coupling terms and nuclear dynamics for the excited states of Na3 cluster.
abstract: We present the molecular symmetry (MS) adapted treatment of nonadiabatic coupling terms (NACTs) for the excited electronic states (2(2)E' and 1(2)A1') of Na3 cluster, where the adiabatic potential energy surfaces (PESs) and the NACTs are calculated at the MRCI level by using an ab initio quantum chemistry package (MOLPRO). The signs of the NACTs at each point of the configuration space (CS) are determined by employing appropriate irreducible representations (IREPs) arising due to MS group, and such terms are incorporated into the adiabatic to diabatic transformation (ADT) equations to obtain the ADT angles. Since those sign corrected NACTs and the corresponding ADT angles demonstrate the validity of curl condition for the existence of three-state (2(2)E' and 1(2)A1') sub-Hilbert space, it becomes possible to construct the continuous, single-valued, symmetric, and smooth 3 × 3 diabatic Hamiltonian matrix. Finally, nuclear dynamics has been carried out on such diabatic surfaces to explore whether our MS-based treatment of diabatization can reproduce the pattern of the experimental spectrum for system B of Na3 cluster.
authors.affiliation: Department of Physical Chemistry and Raman Center for Atom, Molecule and Optical Sciences, Indian Association for the Cultivation of Science, Jadavpur, Kolkata 700 032, India.
authors.forename: Saikat
authors.initials: S
authors.lastname: Mukherjee
authors.forename: Sudip
authors.initials: S
authors.lastname: Bandyopadhyay
authors.forename: Amit Kumar
authors.initials: AK
authors.lastname: Paul
authors.forename: Satrajit
authors.initials: S
authors.lastname: Adhikari