Beyond Born–Oppenheimer based diabatic surfaces of 1,3,5-C6H3F3+ to generate the photoelectron spectra using time-dependent discrete variable representation approach

Abstract

In this article, Beyond Born–Oppenheimer (BBO) treatment is implemented to construct diabatic potential energy surfaces (PESs) of 1,3,5-C₆H₃F₃⁺ over a series [eighteen (18)] of two-dimensional (2D) nuclear planes constituted with eleven normal modes (Q₂, Q_9x, Q_9y, Q_13x, Q_13y, Q_18x, Q_18y, Q_10x, Q_10y, Q_12x and Q_12y) to include all possible nonadiabatic interactions among six coupled electronic states (²E′′, , ²E′ and ). We had formulated explicit expressions of adiabatic to diabatic transformation (ADT) equations [S. Mukherjee, J. Dutta, B. Mukherjee, S. Sardar and S. Adhikari, J. Chem. Phys., 2019, 150, 064308] for the same system forming six state sub-Hilbert space and at present, these ADT equations are solved by incorporating MRCI level ab initio adiabatic PESs and CP-MCSCF calculated nonadiabatic coupling terms (NACTs) to derive diabatic PESs and couplings. Such single-valued, smooth, symmetric and continuous diabatic surface matrices are utilized to carry out multi-state multi-mode nuclear dynamics with the help of time-dependent discrete variable representation (TDDVR) methodology to compute the photoelectron (PE) spectra of 1,3,5-C₆H₃F₃. Our theoretically calculated spectra for ²E′′, and states using BBO treatment and TDDVR dynamics show peak by peak correspondence with the experimental results as well as better than the findings of the multi-configuration time-dependent Hartree (MCTDH) method.