Investigation on the electronic structures and nonlinear optical properties of alkali metal atom doped all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane

Abstract

AbstractOn the basis of stable all‐cis 1,2,3,4,5,6‐hexafluorocyclohexane, a series of alkali metal atom doped MF6C6H6 (M = Li, Na, and K) compounds were theoretically constructed and studied by using ab initio quantum chemistry method. The calculated results show that the HOMO–LUMO gap of the MF6C6H6 conspicuously narrowed from 10.41 eV of pure F6C6H6 to about 2.00 eV of MF6C6H6. The electride characteristics of MF6C6H6 are verified by their electronic structures, HOMOs, and small VIE values. As expected, these electrides possess considerable static first hyperpolarizabilities (β0). Among the studied electrides, the largest β0 of the LiF6C6H6 is 7.00 × 105 au, which is about 3030 times larger than pure F6C6H6. TD‐M06‐2X calculations show that these larger β0 values are attributed to lower transition energies for the crucial excited states of MF6C6H6 systems. Further, the vibrational contributions to the static first hyperpolarizabilities of these molecules are also estimated. Moreover, Li atom doped dimer and trimer of F6C6H6 also present unusual electride's features and exhibit dramatically large β0. Thus, the F6C6H6 interacting with the alkali metal atoms may be a potential promising NLO nanomaterial.