Tetrathiafulvalene derivatives as cation sensor: density functional theory investigation of the hyper-Rayleigh scattering first hyperpolarizability

RSC Advances ◽  
2015 ◽  
Vol 5 (53) ◽  
pp. 42311-42321 ◽  
Author(s):  
Chun-Guang Liu ◽  
Ming-Li Gao ◽  
Shuang Liu ◽  
Ding-Fan Zhang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Rayleigh Scattering ◽  
First Hyperpolarizability ◽  
Functional Theory ◽  
Sensor Density

The hyper-Rayleigh scattering first hyperpolarizability of a series of extended tetrathiafulvalene (TTF) and TTF derivatives have been theoretically investigated using density functional theory to explore their use as potential cation sensor.

scholarly journals Electronic And Nonlinear Optical Features of Inorganic Ga12N12 Nanocage Decorated With Alkali Metals (Li, Na and K)

2021 ◽  
Author(s):  
Azadeh Jamshidi ◽  
Zeinab Biglari
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Alkali Metals ◽  
Nonlinear Optical ◽  
Interaction Energies ◽  
First Hyperpolarizability ◽  
Negative Interaction ◽  
Functional Theory ◽  
Nlo Properties ◽  
Homo Lumo

Abstract The effect of alkali metals (Li, Na and K) interaction on the nonlinear optical response (NLO) of Ga12N12 nanocage has been performed using density functional theory (DFT) calculations. The results show that the exo-M@Ga12N12 structures are energetically favorable with negative interaction energies in the range of ‒1.50 to ‒2.28 eV. The electronic properties of decorated structures are strongly sensitive to interaction with the alkali metals. The HOMO-LUMO gap of Ga12N12 is reduced by about 70% due to the decoration with alkali metals. It is obtained that the adsorption of alkali metals over the tetragonal ring of Ga12N12 nanocage remarkably enhances the first hyperpolarizability up to 6.5×104 au. The results display that decorating Ga12N12 nanocage with alkali metals can be introduced it as a novel inorganic nanomaterial with significant NLO properties.

scholarly journals Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates

Symmetry ◽  
2021 ◽  
Vol 13 (9) ◽  
pp. 1636
Author(s):  
Emna Rtibi ◽  
Benoit Champagne
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Charge Transfer ◽  
Density Functional ◽  
Energy Charge ◽  
Substitution Effects ◽  
First Hyperpolarizability ◽  
Functional Theory ◽  
State Approximation ◽  
Donor And Acceptor

Density functional theory and time-dependent density functional theory have been enacted to investigate the effects of donor and acceptor on the first hyperpolarizability of Lindquist-type organo-imido polyoxometalates (POMs). These calculations employ a range-separated hybrid exchange-correlation functional (ωB97X-D), account for solvent effects using the implicit polarizable continuum model, and analyze the first hyperpolarizabilities by using the two-state approximation. They highlight the beneficial role of strong donors as well as of π-conjugated spacers (CH=CH rather than C≡C) on the first hyperpolarizabilities. Analysis based on the unit sphere representation confirms the one-dimensional push-pull π-conjugated character of the POMs substituted by donor groups and the corresponding value of the depolarization ratios close to 5. Furthermore, the use of the two-state approximation is demonstrated to be suitable for explaining the origin of the variations of the first hyperpolarizabilities as a function of the characteristics of a unique low-energy charge-transfer excited state and to attribute most of the first hyperpolarizability changes to the difference of dipole moment between the ground and that charge-transfer excited state.

scholarly journals Electron Donor and Acceptor Influence on the Nonlinear Optical Response of Diacetylene-Functionalized Organic Materials (DFOMs): Density Functional Theory Calculations

Molecules ◽  
2019 ◽  
Vol 24 (11) ◽  
pp. 2096 ◽  
Author(s):  
Muhammad Khalid ◽  
Riaz Hussain ◽  
Ajaz Hussain ◽  
Bakhat Ali ◽  
Farrukh Jaleel ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Gas Phase ◽  
Electron Donor ◽  
Density Functional ◽  
Nbo Analysis ◽  
Basis Set ◽  
First Hyperpolarizability ◽  
Functional Theory ◽  
Parent Molecule ◽  
Donor And Acceptor

Herein, we report the quantum chemical results based on density functional theory for the polarizability (α) and first hyperpolarizability (β) values of diacetylene-functionalized organic molecules (DFOM) containing an electron acceptor (A) unit in the form of nitro group and electron donor (D) unit in the form of amino group. Six DFOM 1–6 have been designed by structural tailoring of the synthesized chromophore 4,4′-(buta-1,3-diyne-1,4-diyl) dianiline (R) and the influence of the D and A moieties on α and β was explored. Ground state geometries, HOMO-LUMO energies, and natural bond orbital (NBO) analysis of all DFOM (R and 1–6) were explored through B3LYP level of DFT and 6-31G(d,p) basis set. The polarizability (α), first hyperpolarizability (β) values were computed using B3LYP (gas phase), CAM-B3LYP (gas phase), CAM-B3LYP (solvent DMSO) methods and 6-31G(d,p) basis set combination. UV-Visible analysis was performed at CAM-B3LYP/6-31G(d,p) level of theory. Results illustrated that much reduced energy gap in the range of 2.212–2.809 eV was observed in designed DFOM 1–6 as compared to parent molecule R (4.405 eV). Designed DFOM (except for 2 and 4) were found red shifted compared to parent molecule R. An absorption at longer wavelength was observed for 6 with 371.46 nm. NBO analysis confirmed the involvement of extended conjugation and as well as charge transfer character towards the promising NLO response and red shift of molecules under study. Overall, compound 6 displayed large <α> and βtot, computed to be 333.40 (a.u.) (B3LYP gas), 302.38 (a.u.) (CAM-B3LYP gas), 380.46 (a.u.) (CAM-B3LYP solvent) and 24708.79 (a.u.), 11841.93 (a.u.), 25053.32 (a.u.) measured from B3LYP (gas), CAM-B3LYP (gas) and CAM-B3LYP (DMSO) methods respectively. This investigation provides a theoretical framework for conversion of centrosymmetric molecules into non-centrosymmetric architectures to discover NLO candidates for modern hi-tech applications.

Density functional theory prediction for the second-order nonlinear optical responses of phenanthroline-fused phthalocyanine derivatives

2014 ◽  
Vol 18 (01n02) ◽  
pp. 58-66 ◽  
Author(s):  
Chao Chen ◽  
Lijuan Zhang ◽  
Luyang Zhao ◽  
Dongdong Qi ◽  
Jianzhuang Jiang
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Rayleigh Scattering ◽  
Electronic Absorption Spectra ◽  
Density Functional Theory Calculations ◽  
Dft Method ◽  
Second Order ◽  
Absorption Region ◽  
Functional Theory ◽  
Optical Responses

A series of unsymmetrical phenanthroline-fused phthalocyanine derivatives including Zn [ Pc ( Phen )], Zn [ Pc ( Phen )2], Zn [ Pc ( Phen )3], Zn [ Pc ( NH 2)6( Phen )], Zn [ Pc ( NH 2)4( Phen )2], Zn [ Pc ( NH 2)2( Phen )3], Zn [ PcF 6( Phen )], Zn [ PcF 4( Phen )2], and Zn [ PcF 2( Phen )3] were designed to explore their properties of geometric and electronic structures, electronic absorption spectra, and second-order nonlinear responses under density functional theory and time-dependent density functional theory calculations. The computational results show that the peripheral substituents with push-pull effect could obviously change the π–π* transitions, leading to a tunable absorption region in the range between 300–800 nm. The hyperpolarizabilities were carefully investigated using CP-DFT method, revealing the size effect and clarifying the limit when expanding the conjugated system is employed to improve the hyper-Rayleigh scattering response coefficient (βHRS). According to the results, the NH 2-substitued phenanthroline-fused phthalocyanines are considered as ideal NLO blocking materials with large βHRS.

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