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

Abstract

On 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.

DFT studies of electronic and nonlinear optical properties of a novel class of excess electron compounds based on multi-alkali metal atoms-doped Janus face C13H10F12

“…2, the common feature of equilibrium geometry on the M F -1-nLi (M F = Li, Na and K; n = 0, 1, 2) system is that the alkali-metal atom M F is located above the central C atom of the fluorocarbon face. The distances (d MF-F ) between M F and F are in the range of 1.85-2.54 Å (see Table 1), which are in excellent agreement with the corresponding results in M-F 6 C 6 H 6 16 and M + -F 6 C 6 H 6 -M À . 18 From the hydrocarbon face, the 67 As shown in Fig.…”

“…Among the studied compounds, the largest b 0 value is up to 7 Â 10 5 a.u., which is 3030 times larger than that of F 6 C 6 H 6 . 16 It follows that this value can be notably enhanced by doping alkali-metal atoms, and a number of studies have confirmed it. 18,[36][37][38][39] However, up to now, the research and calculation of this work mainly focus on the single-ring Janus face system F 6 C 6 H 6 .…”

“…We have obtained virtual frequency free and stable geometric structures of the designed compounds, mM F -1-nLi (M F = Li, Na and K; m = 1, 2; n = 0, 1, 2), using the hybrid meta exchange correlation functional (M062X) DFT method [45][46][47] at the 6-31++G(d,p) level, which has been confirmed to be accurate enough. 16,18,20 Meanwhile, the natural bond orbital (NBO) charges, the HOMO-LUMO gaps (E gaps ), and the vertical ionization energies (VIEs) of the compounds were calculated at the same level. The VIE is defined as follows:…”

Effective Enhancement of the Second‐Order Nonlinear Optical Responses of Graphynes by Introducing π‐Conjugated Chains with Donor/Acceptor Groups

“…The dipole moment is generally associated with the projection of β on dipole moment vector (β vec ). [55][56] The definition of β vec is b vec ¼ P i¼x;y;z…”

Theoretical study of a novel organic electride with large nonlinear optical responses

“…Recently, the definition of electride has been extended from solids [7] to liquids [21,22] and even to molecular electrides in gas (theoretical model) [23] . Although many organic molecular electrides have been theoretically designed, [24–31] unfortunately, they have not been successfully synthesized yet. Formally, an organic molecular electride may be viewed as a subunit of organic crystal electrides.…”