Structures and Large NLO Responses of New Electrides:  Li-Doped Fluorocarbon Chain

Abstract

An alkali-metal-doped effect on the nonlinear optical (NLO) property in new electrides is studied. The electrides are formed by doping alkali atom Li into a fluorocarbon chain H-(CF2-CH2)3-H. Six stable structures of the Lin-H-(CF2-CH2)3-H (n = 1, 2) complexes with all real frequencies are obtained at the MP2/6-31+G (d) level. Among these six structures, the largest first static hyperpolarizabilities (beta(0)) are found to be 76,978 au, which is much larger than the beta(0) value of 112 au for H-(CF2-CH2)3-H. Clearly, the Li-atom-doped effect on the first hyperpolarizability is dramatic. Three interesting relationships between the structure and beta(0) value have been observed. (1) For the one-Li-atom-doped systems as well as for the structures with two opposite Li atoms, the shorter the distance between the Li atom and difluoromethyl group, the larger the beta(0) value. (2) The beta(0) values of the two-Li-atom-doped chains are much larger than those of the one-Li-atom-doped systems, except for the case of cis-AB where the Li-Li distance (2.847 Angstrom) is close to the bond length of the Li2 molecule (2.672 Angstrom). (3) For the two-Li-atom-doped chains, the beta(0) value increases as the Li-Li distance increases. These relationships between the structure and beta(0) value may be beneficial to experimentalists for designing electrides with large NLO responses by using the alkali-metal-doped effect.

Effect of alkaline earth metal atom on the large static first hyperpolarizabilities of alkaline earth-based alkalides Be(NH3)nM (M=Be and Ca) in comparison with alkalides Li(NH3)nNa (n=1–3)

“…A great deal of work [4,[7][8][9][10][11][12][13][14][15] has been devoted to find the important influencing factors which can lead to a significant increase of the first hyperpolarizability (b 0 ) and to design a new type of NLO materials. Among them, the theoretical investigation [10][11][12][13][14][15][16][17][18][19][20][21][22][23] plays an important role for the new high-performance NLO materials' discovery. As an important strategy, doping is suggested to be a good method to enhance the NLO responses [7,[11][12][13][14][15][16][17][18][19][20][21][22][23][24].…”

The inner-induced effects of YCN in C76 on the structures and nonlinear optical properties

“…In calculating first hyperpolarizability, the second-order Møller-Plesset perturbative (MP2) method is more reliable, [8,26,63] but it has a high time cost. The Coulomb-attenuated hybrid exchange correlation functional (CAM-B3LYP), widely calculated for the first hyperpolarizabilities of π-conjugated systems, predicted the molecular NLO properties, which combines the hybrid functional (such as B3LYP), to the longrange corrected functional of Tawada et al [30,[64][65][66].…”

“…Nonlinear optical materials are of great importance for potential applications in optical computation, optical communication, second harmonic generation, and optical signal processing [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]. So far, nonlinear optical materials are mainly divided into two conventional classes: inorganic and organic materials [13,[17][18][19].…”

Superalkali atoms bonding to the phenalenyl radical: structures, intermolecular interaction and nonlinear optical properties

“…Specifically, considering precision and cost, the MP2 method has been proposed as the most suitable method to calculate first hyperpolarizabilities [33][34][35]. In the present work, the first hyperpolarizabilities were calculated at the MP2/6-31+ G(d) level.…”