A new global potential energy surface (PES) is constructed for the ground state of LiHCl system based on high-quality ab initio energy points calculated using multi-reference configuration interaction calculations with the Davidson correction. The AVQZ and WCVQZ basis sets are employed for H and Li atoms, respectively. To compensate the relativistic effects of heavy element, the AWCVQZ-DK basis set is employed for Cl atom. The neural network method is used for fitting the PES, and the root mean square error is small (1.36 × 10 eV). The spectroscopic constants of the diatoms obtained from the new PES agree well with experimental data. The geometric characteristics of the transition state and the complex are examined and compared with the previous theoretical values. To study the reaction dynamics of the Li(S) + HCl(XΣ) → LiCl(XΣ) + H(S) reaction, quantum reactive scattering dynamics calculations using collection reactant-coordinate-based wave packet method are conducted based on the new PES. The results of the reaction probabilities indicate that a small barrier exists along the reaction path as observed from the PES. The integral cross section curves reveal that the product molecule LiCl is easily excited. In addition, the reaction is dominated by forward scattering, and similar pattern is observed from Becker's experiment.
The absorption spectra of dianionic tetrocyanoethylene and dicationic tetrathiafulvalene dimers have been studied theoretically with the time-dependent density functional theory and the recently proposed Coulomb-attenuated model. The nature of the excited states was further explored by means of the two-dimensional (2D) site (transition density matrix) and three-dimensional (3D) cube (transition density and charge difference density) representations. By use of the 3D transition density and charge difference density, we visualized the orientation of transition dipole moment and also explained charge-transfer characteristics occurring in the dianionic/dicationic pi-dimers system. It is found that for the dianionic/dicationic pi-dimers system there exist two kinds of charge-transfer patterns for the mainly excited states, the intermolecular charge transfer and the mixture of intramolecular charge transfer coupled with intermolecular charge transfer. Meanwhile, the coupling effect of excitation and the oscillation of electron-hole pairs between the monomers have been revealed with 2D site representation of transition density matrix, which also indicates the electron-hole coherence upon photon excitation.
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