Giant first hyperpolarizabilities of donor–acceptor substituted graphyne: An ab initio study

Int J of Quantum Chemistry

Feng

et al. 2020

Based on the combination of novel carbon material graphynes (GYs) and superalkalis (OM3), a class of GY superalkali complexes, OM3+@(GY/GDY/GTY)− (M = Li, Na, and K), has been designed and investigated using the density functional theory method. Computational results reveal that these complexes with high stability can be regarded as novel superalkali salts of GYs due to electron transfer from OM3 to GYs. For second‐order nonlinear optical response, these superalkali salts exhibit large first hyperpolarizabilities (β0). Two essential effects on β0 values are found, namely, the atomic number of alkali atom in superalkali and the pore size of GY. Integrating the two effects, the selected combination of OLi3 with large pore size graphtrigne (GTY) can lead to a considerable β0 value (6.5 × 105 au), which is a new record for superatom‐doped GYs. In the resulting complex, the OLi3 unit is located at the center of the pore of GTY, forming a planar structure with the highest stability among these salts. Besides large β0 values, these superalkali salts of GYs have a deep‐ultraviolet working region; hence, they can be considered a kind of high‐performance deep‐ultraviolet NLO molecule.

Section: Introductionmentioning

confidence: 99%

Effects of the atomic number of alkali atom and pore size of graphyne on the second‐order nonlinear optical response of superalkali salts of graphynes OM₃⁺@GYs⁻ (M = Li, Na, and K)

Int J of Quantum Chemistry

Feng

et al. 2020

“…22,23,[25][26][27][28][29] More interestingly, the graphyne molecules have recently aroused extensive attention of theoretical researchers in the field of nonlinear optics. In 2016, Chakraborti 30 theoretically investigated the NLO properties of donor-acceptor substituted graphyne structures. In the same year, the hyperpolarizabilities of graphdiyne functionalized by the alkali metal atom etc .…”

Section: Introductionmentioning

confidence: 99%

Effects of the Atomic Number of Alkali Atom and Pore Size of Graphyne on the Second Order Nonlinear Optical Response of Superalkali Salts of Graphynes OM3+@GYs– (M = Li, Na, and K)

Feng

et al. 2020

Preprint

Based on the combination of novel carbon material graphynes (GYs) and superalkalis (OM 3), a class of graphyne superalkali complexes, OM 3 + @(GY/GDY/GTY)-(M = Li, Na, and K), have been designed and investigated by density functional theory method. Computational results reveal that these complexes with high stability can be regarded as novel superalkali salts of graphynes due to electron transfer from OM 3 to GYs. For second order nonlinear optical response, these superalkali salts exhibit large first hyperpolarizabilities (β 0). Two important effects on β 0 values are found, namely the atomic number of alkali atom in superalkali and the pore size of graphyne. Integrating the two effects, the selected combination of OLi3 with large pore size GTY can bring the considerable β 0 value (6.5×10 5 au), which is a new record for superatom-doped graphynes. In the resulting complex, the OLi 3 molecule is located at the center of the pore of GTY, forming a planar structure with the highest stability among these salts. Besides large β 0 values, these superalkali salts of graphynes have deep-ultraviolet working region, hence can be considered as a new kind of high-performance deep-ultraviolet NLO molecules.

“…In recent decades, significant attention has been paid to the nonlinear optical (NLO) materials because of their potential applications in laser devices, optical communication, optical computing, and optical data storage. Till date, a large number of strategies have been proposed for the design and efficient synthesis of several types of NLO materials, for instance, the organic molecules with extended π‐electrons systems, introduction of donor/acceptor groups, and doping alkali metal atoms into different molecules . Li and coworkers demonstrated that the molecules with loosely bound excess electrons (such as electride and alkalide molecules) exhibited large NLO response.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies on structures and nonlinear optical properties of alkali doped electrides B₁₂N₁₂-M (M = Li, Na, K)

Liu

2016

Int. J. Quantum Chem.

The structures and nonlinear optical properties of a novel class of alkali metals doped electrides B 12 N 12 -M (M 5 Li, Na, K) were investigated by ab initio quantum chemistry method. The doping of alkali atoms was found to narrow the energy gap values of B 12 N 12 in the range 3.96-6.70 eV. Furthermore, these alkali metals doped compounds with diffuse excess electron exhibited significantly large first hyperpolarizabilities (b 0 ) as follows: 5571-9157 au for B 12 N 12 -Li, 1537-18,889 au for B 12 N 12 -Na, and 2803-11,396 au for B 12 N 12 -K. Clearly, doping of the alkali atoms could dramatically increase the b 0 value of B 12 N 12 (b 0 5 0). Furthermore, their transition energies (DE) were also calculated. The results showed that these compounds had low DE values in the range 1.407-2.363 eV, which was attributed to large b 0 values of alkali metals doped B 12 N 12 nanocage.