Molecular structure and electronic spectrum of MoS2under external electric field

Abstract

A variety of new materials have improved the production and life of human beings. Two-dimensional nano materials have become a research hotspot due to their unique physical and chemical properties. Molybdenum disulfide (MoS₂) is representative of transition metal sulfide, with excellent mechanical properties and chemical stability. In order to study the influence of external electrical field on the molecular structure and spectrum, here in this work, the density functional theory with the hybrid B3LYP at Def2-TZVP level is employed to calculate the geometrical parameters of the ground state of MoS₂ molecule under external electric fields ranging from 0 to 0.1 a.u. (0−5.1423 × 10¹⁰ V/m). Based on the optimized structures, the time-dependent density functional theory at the same level as the above is adopted to calculate the absorption wavelengths and the molar absorption coefficients for the first ten excited states of MoS₂ molecule under external electric fields. The results show that the most strongest absorption band is located at 483 nm with a molar absorption coefficient of 461 L·mol^–1·cm^–1 in the UV-Vis absorption spectrum. The intramolecular charge transfers as a whole with the enhancement of the external electric field. The electric dipole moment increases with the external electric field rising, while the total molecular energy decreases with external electric field increasing. With the enhancement of the external electric field, the absorption peaks show a significant redshift. When the electric field increases to 0.1 a.u., the redshift is obvious. This can be explained as follows. When the external electric field is weaker, the electron transfer in the molecule is not significant. However, with the augment of the external electric field, the electron transfer in the molecule occurs as a whole. This makes the electron interaction between Mo and S weaker, thus the electron transition is more likely to occur. The energy required for excitation is reduced, and the wavelength of the excited state becomes longer, that is, the absorption peak takes a redshift. With the enhancement of the external electric field, the molar absorption coefficient increases obviously. This is because the overall transfer of the external electric field to the electron makes the electron cloud density of the MoS₂ molecule increase and the number of electrons in transition augment. This work provides a theoretical basis for the utilization and improvement of MoS₂ photoelectric properties, and also enlightens the application research of other photoelectric materials.