Β0 Value Research Articles

Impact of substituents at the para position of C-Nitroso over N-Nitroso diphenylamine on static and frequency dependent nonlinear optical Properties: DFT and TD-DFT

The nonlinear optical property of N and C-nitroso diphenylamine is the focus of the current work but the D-π-A skeleton-based para substituted nitroso benzene served as the starting point for this investigation. For p-methoxy nitroso benzene, a maximum β0 of 10.47 x 10-30 esu was attained. Diphenylamine analogue was letter on chosen for further improvement. For these nitroso diphenylamines, substituent effects of electron donating groups (EDGs) at the para position have been studied for the nonlinear optical property (NLO). The NMe2 derivative of C-nitroso was found to have the highest value of hyperpolarizability (β0) of 57.46 × 10-30 esu, including 570 × 10-30 Debye.esu as molecular hyperpolarizability (µ×β0), out of these two nitroso forms with substituents Me, OMe, OEt, NH2, and NMe2 at para position. H < Me < OMe < OEt < NH2 < NMe2 is the ascending effect for the β0 in the N-nitroso whereas H < Me < OMe < NH2 < OEt < NMe2 in the C-nitroso. These β0 value shows 155.29, 73.69, 13.12 fold increment as compared to diphenylamine (DPA), urea and p-nitroaniline (PNA) respectively. Upon increasing the λmax, value of calculated βTDω also increases calculated in TD-DFT calculations (βTD1064 <βTD1340 <βTD1460 < βTD1907). These values have shown a deviation range of 7–38 % in case of N-nitroso and 11–52 % in case of C-nitroso as compared to static values. Whereas βHRSω increases with increase in the optical frequency (βHRS1064 >βHRS1340 >βHRS1460 > βHRS1907). These values have shown a deviation range of 4–91 % in case of N-nitroso and 1to > 100 in case of C-nitroso as compared to static values.

Li+(3)Mg−: A new alkaline earthide with large nonlinear optical response

Alkali metal doping has been identified as a vital step in facilitating an increase in the first hyperpolarizability(β0). To further explore this concept, we utilized Calix (Zhang et al., 2018) [3]pyrrole (3), Calix (Ma et al., 2017) [4]pyrrole (4), and Calix (Aloraini et al., 2022) [5]pyrrole (5) as our three ligands in this study. The choice of these ligands was based on their ability to undergo alkali metal doping, which ultimately led to an enhancement in the first hyperpolarizability. By doping alkali metal lithium, three new compounds Li@3, Li@4 and Li@5 were theoretically designed. Then the alkaline earthide Mg was doped onto the Li@3, and a new alkaline earthide compound Li+(3)Mg− was designed. The geometric structure and nonlinear optical properties of the molecules were studied using the CAM-B3LYP functional. The results show that Li+(3)Mg− has a considerable first-order hyperpolarizability, β0 = 21401 au, The β0 value for the 3 system is merely 37 au, whereas for the Li@3 system, it reaches a high of 12257 au Li+(3)Mg− exhibits a β0 value that is over 500 times greater than that of 3. It is evident that the electronic structure and nonlinear optical properties are significantly affected by the presence of alkali metal and alkaline earthide atoms doped in 3. The excess electron derived from alkali metal atoms and alkaline earthide atoms are significant contributors to the sudden increase in the β0 within Li+(3)Mg−. We sincerely hope that the development and production of materials with nonlinear optical properties in this study can provide new ideas and methods for the innovation of electride.

How much length of boron-nitride incorporated benzene like structures can produce efficient harmonic generation at their low-lying excited states?

In this study, exploring the nonlinear optical (NLO) responses by utilizing boron nitride (BN) units as benzene like fused ring chromophores (BTN1-BTN8) are made by correlating their planarity. The chromophore structures containing ring sizes of 3 and 4 (BTN3 and BTN4) demonstrates their significant NLO responses, while higher ring sizes show a decline as their structure become more curved. Their quantum chemical calculations are performed to optimize their molecular structures for their various chemical stability related parameters. Their dipole moments (µtot) ranges between 1.27D for BTN2 to 4.43 D for BTN8 while their average linear polarizability (<α0>) varies from 5.98–7.56 electrostatic units (e.s.u). The chromophore BTN4 exhibits its highest first order hyperpolarizability (β0) value of 9.91 e.s.u. The chromophore BTN3 has the largest second order hyperpolarizability (γ0) value of 11.98 e.s.u and it also has the highest ionization potential (IP) of 5.64 eV, while chromophore BTN4 had a remarkably low EA of −4.91 eV. Their vertical IP (VIP) values ranged from 6.21 eV for BTN1 to 7.56 eV for chromophore BTN7. The chromophore BTN1 displayed a maximum absorption (λmax) at 656 nm with an oscillator strength (f) of 0.0473 and an excitation energy (E) of 1.89 eV. The chromophore BTN4 exhibits a λmax of 366 nm, an f of 0.0012, and an E value of 3.39 eV. The chromophore BTN8 showed the highest λmax value of 1023 nm, an f of 0.0023, and an E value of 1.21 eV.

Synthesis and evaluation of antimycobacterial activity and molecular docking of 4-(benzyloxy)benzaldehyde-3,5-dinitrobenzohydrazone: A combined experimental and theoretical approaches

The 4–(Benzyloxy) benzaldehyde–3, 5–dinitrobenzohydrazone (3) has been synthesized spectroscopically, characterized and its antitubercularactivity has been evaluated. All the quantum chemical calculations have been carried out using DFT level of theory, B3LYP functional and 6-311++G(d,p) basis set. The presence of chemical shift of azomethine proton singlet at 8.246 ppm and absence of singlet at 3.1 ppm in experimental 1H NMR spectrum indicated that the molecule exits in hydrazide-hydrazone form. The N–H stretching band in the FT-IR spectrum of (3) show Davidov coupling between the neighboring units and observed in the region 3471–3226 cm–1. NBO analysis confirms the various intramolecular charge transfer from donor to acceptor and stabilize the molecule upto∼24.65 kcal/mol due to π→π* and upto∼16.60 kcal/mol due to n→π* interaction. The maximum values of the electrophilic reactivity descriptors at C14 indicate that this site is more prone to nucleophilic attack. The local reactivity descriptors for (3) favor the formation of oxadiazoline, thiadiazoline, thiazolidinones, azetidinonesetc by attack of nucleophilic part of the dipolar reagent on C14 site of C14=N15 bond. The calculated β0 (14.3915 × 10–31 esu) value indicates it's suitability for NLO application. The compound (3) was evaluated for their antitubercular potential against Mycobacterium tuberculosis H37Rv using microplate alamar blue assay (MABA). Docking study of (3) showed binding conformations and affinities with the target protein through hydrogen bonding.

Oxovanadium and copper complexes of new unsymmetrically tetradentate ligands: X- ray structure, theoretical and NLO properties, catalytic oxidation and bromoperoxidase activities

A series of mononuclear oxovanadium VOLBz, VOLT and copper CuLBz, CuLT complexes containing unsymmetrical tetradentate Schiff base ligands were synthesized and fully characterized by conventional spectroscopic techniques such as FT-IR, UV–vis, 1HNMR and mass spectrometry (MS). Crystal structure data of CuLT, solved by X-ray diffraction, shows a monoclinic system with Cc space group and Z = 4 molecules per unit cell. The central copper ion adopts a nearly ideal square planar coordination geometry. Cyclic voltammetry of oxovanadium and copper complexes revealed quasi reversible redox couples corresponding to VOIV/VOV and CuI/CuII redox processes, respectively. The quantum calculations, performed by DFT and TD-DFT theory at the M062X/6-311**G/SDD level, agree well with the experimental data. The results show that the copper and the oxovanadium compounds have larger static and dynamic hyperpolarizability values than the urea. For instance, the β0 value of H2LT is about 68 times larger than that of the urea. The results predict that the studied compounds have the ability to be excellent second and third-order NLO materials. The prepared complexes catalyzed effectively homogeneous oxidation reaction of cyclohexene in the presence of H2O2 as oxidant. Higher conversion of 98% is attained using CuLBz as catalyst. The bromoperoxidase activity is explored in the oxidative bromination of phenol red as a trap employing the studied complexes which can be considered as potential functional models of bromoperoxidase, CuLBz catalyst exhibits the better catalytic activity, the reaction rate constant k is equal to 2.203×105 (mol L-1)-2s-1.

Photoswitchable nonlinear optical properties of azobenzene-based supramolecular complexes: insights from density functional theory.

Density functional theory (DFT) calculations were performed for a series of supramolecular assemblies containing azobenzene (Azo-X where X = I, Br and H) and alkoxystilbazole subunits to evaluate their electronic, linear and nonlinear optical properties. These assemblies are derivatives of azobenzene, obtained by the substitution of electron-withdrawing and electron-donating groups onto the molecular skeleton. The interaction energies (Eint) of all the designed supramolecular complexes (IA-IF, IIA-IIF and IIIA-IIIF) range from -1.0 kcal mol-1 to -7.7 kcal mol-1. The electronic properties of these hydrogen/halogen bond driven supramolecular assemblies such as vertical ionization energies (VIE), HOMO-LUMO energy gap (GH-L), excitation energies, density of states (DOS) and natural population (NPA) analyses were also computed. The non-covalent interaction index (NCI) and quantum theory of atoms in molecules (QTAIM) analyses were also performed to validate the nature of inter- and intra-molecular interactions in these complexes. A substantial enhancement in the first hyperpolarizability (β0) values of the designed supramolecular complexes was observed, which is driven by the charge transfer from the pyridyl moiety of alkoxystilbazole to Azo-X. The highest β0 value of 1.3 × 104 au was observed for the supramolecular complex of p-nitro substituted azobenzene with alkoxystilbazole (ID complex). Moreover, the results show that the substitution of electron-withdrawing groups on Azo-X can also bring larger β0 values for such complexes. It was confirmed on a purely theoretical basis that both the types of noncovalent interactions present and the substituent group incorporated influence the nonlinear optical (NLO) response of the systems. Furthermore, the β0 values of the E (trans) and Z (cis) forms were compared to demonstrate the two-way photoinduced switching mechanism.

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

AbstractUsing density functional theory calculations, we have analyzed second‐order nonlinear optical (NLO) properties of a series of −(CH=CH)m−NH2/NO2‐modified graphynes (GY[n]) (n=1−3;m=1−6, 9, 12). This type of modification can induce evident electron transfer between the graphyne and conjugated chain and decrease the transition energy, resulting in the system exhibiting a large static first hyperpolarizability (β0). Theβ0values of the GY[n]−(CH=CH)m−NH2/NO2show a monotonously increasing trend with lengthening the −(CH=CH)m−NH2/NO2chain fromm=1 to 12. Further, the NO2‐modified system has a higherβ0value than the corresponding NH2‐modified system with the same π‐conjugated length. Compared with the single‐modified GY[1], the −(CH=CH)m−NH2/NO2co‐modified GY[1] systems exhibit better NLO responses. For GY[n]−(CH=CH)m−NO2, whenm=1−4, theβ0value increases with increasing the size of graphyne, while form=5, 6, 9, 12, the varying order is reversed. Solvent and frequency dispersion effects are also analyzed. The polarizable environment has a significant influence on hyper‐Rayleigh scattering first hyperpolarizability (βHRS).

Switching from an electride-like molecule to the molecular electride K-F6C6H6 driven by an oriented external electric field.

The exploration of innovative molecular switches has resulted in large developments in the field of molecular electronics. Focusing on a single molecular switch with different forms exhibiting different electride features, potassium-atom-doped all-cis 1,2,3,4,5,6-hexafluorocyclohexane K-F6C6H6 was studied theoretically. It was found that an oriented external electric field can drive excess electron transfer from the region outside of the K atom to that outside of F6C6H6. Subsequently, the electride-like molecule K-F6C6H6 (1) switches into the molecular electride K-F6C6H6e- (3) through another electride-like molecule K-F6C6H6 (2). The static first hyperpolarizabilities (β0) are increased over 12- and 5-fold when moving from 1 to 2 and 3, respectively. The rise of each β0 value constitutes an order of magnitude improvement. Between them, the different β0 values suggest that K-F6C6H6 is a good candidate for use as a multiple-response nonlinear optics switch. The order of the β0 values of 1-4 for M-F6C6H6 (M = Li and Na) coincide with that of K-F6C6H6, also exhibiting a switch effect.

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)

AbstractBased 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.

Exploring the optical and nonlinear optical features of heteroleptic complexes with BODIPY and amido-BODIPY substitutions; A comparative theoretical study

In this study, special attention has been paid to understanding the structural effect on electronic structure, absorption spectra and nonlinear optical (NLO) response for a series of heteroleptic diimine dithiolate complexes [M(bpy)(bdt)] (M = Ni, Pd and Pt; bpy = 2,2′-bipyridine, bdt = 1,2-benzenedithiolate) attached to BODIPY and amido-BODIPY dyes through density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods. Natural bond orbital (NBO) analyses are also performed for scrutinizing the structural properties of the considered heteroleptic complexes. The calculated energy gaps show that the substitution of BODIPY or amido-BODIPY groups on the diimine ligand (bpy) leads to reduce of HLG. In contrast, these substitutions on the dithiolate ligand (bdt) are slightly increased energy gap. Moreover, the entitled substitutions at the diimine position can be red-shifted, and the expansion of absorption range to the near-IR region. It is interesting to note that the BODIPY and amido-BODIPY substitutions dramatically increase the static first hyperpolarizability (β0) value. The results suggest that structural modifications on the diimine and dithiolate ligands using BODIPY and amido-BODIPY dyes can finely tune their linear and nonlinear optical properties.

Alkali Metal Doping for Enhancement of Nonlinear Optical Properties of Dicyclopenta[4,3,2,1-ghi:4′,3′,2′,1′-pqr]perylene: A New Bowl-Shaped Fragment of Fullerene C70

The electronic properties and the first static hyperpolarizability of a new bowl-shaped of C70 fullerene, the dicyclopenta[4,3,2,1-ghi:4′,3′,2′,1′-pqr]perylene (2CP-Per = C22H10) doped with alkali metals (Li, Na and K) have been investigated employing the density functional theory. Six stable conformations are obtained for Li@2CP-Per, whereas five and four stable structures are formed for Na@2CP-Per and K@2CP-Per, respectively. The nonlinear optical properties of these structures are remarkably to interaction with the type of alkali metals and their relative location at the curved surface of 2CP-Per. The adsorption of Li, Na and K atoms on the surfaces of 2CP-Per narrows the HOMO–LUMO gap of the considered structures. Moreover it is observed that the doping with alkali metals enhances the first hyperpolarizability (β0) of 2CP-Per nanobowl. The β0 value of several doped-structures increases to 40 times of pristine 2CP-Per structure.

Theoretical research on nonlinear optical properties of sandwich compounds M3-NO3-M'3 (M, M' = Li, Na, K)

Six sandwich compounds metal-nonmetal-metal have been designed, which are composed of superalkali metal (Li3, Na3, K3) and superion (NO3–). The compounds were optimized by MP2/6-311g (2D) method to obtain the stable geometry. The analysis of NBO charge shows that in M3-NO3-M'3 the charge of M and M' are about +1, and the charge of NO3– is about −2. Therefore, it is a charge separation system, which can be recorded as M3+–NO32−-M'3+. In this special structure, the superions in the center repel the valence electrons on the two metal rings above and below to form additional electrons, so they have the characteristics of electron compounds and it may produce a good nonlinear optical response. The static first hyperpolarizability (β0) of M3+–NO32−-M'3+ was calculated. The results show that the β0 value of Na3-NO3-Na3 is the largest (79067 × 10−30 esu.), which is 1163 times larger than that in the literature.

Theoretical study on the effect of spacer groups on the nonlinear optical properties of polyvinyl carbazole molecular fragments

In this paper, polyvinyl carbazole fragments with side-hung chromogenic groups were used as the parent. The relationship between the structure and the properties of NLO was studied by changing the type of spacer groups on chromogenic groups with density functional theory (DFT). The results show that all designed systems have significant second-order NLO response. The first hyperpolarizability (β0) of the system has the following regularity (taking PBE0 algorithm as an example): the β0 value of the system is related to the type of electron-donating and electron-withdrawing spacer group (X).The β0 value of electron-donating spacer group is larger than that of electron-withdrawing spacer, and the β0 value of the molecule is independent of the size of the spacer group. When the spacer group is methyl, the value of β0 (168.1 × 10−30 esu) is the largest in tested electron-donating group. When the spacer group is an electron-withdrawing group, the value of β0 is related to electron-withdrawing ability, and the value of β0 is inversely proportional to the electron-withdrawing ability of the spacer group.

Spectroscopic behavior, FMO, NLO and substitution effect of 2-(1H-Benzo[d]imidazole-2-ylthio)-N-o-substituted-acetamides: Experimental and theoretical approach

The benzimidazole-based derivatives 2a-c were designed and synthesized via C–N coupling reaction and experimentally characterized by infrared spectroscopy (FT-IR), nuclear magnetic resonance (1H NMR) spectroscopy and mass spectrometry (MS). The observed and calculated FT-IR frequencies correspond to CO stretching of amide group are depicted at 1657, 1672 and 1682, 1689 and 1699, 1682 for 2a, 2b and 2c respectively and are in good agreement. The synthesized compounds 2a-c exhibit non-linear optical response with the first hyperpolarizability (β0) at 783, 1550 and 694 au, respectively. Due to the presence of electron withdrawing –NO2 on the primary amine of 2b, the β0value is estimated at 1550 au, which reduces the energy barrier hence increasing the β0 value, with maximum UV–vis absorption at 224 nm with TD-DFT method. The opposite behavior is demonstrated by the electron donor –OCH3 substituent. This study of NLO responses would be beneficial to the development of high-performance NLO materials.

A theoretical study of alkaline-earthides Li(NH3)4M (M = Be, Mg, Ca) with large first hyperpolarizability.

With the aid of ab initio calculations at the MP2 level of theory, a novel type of alkaline-earthides, namely Li(NH3)4M (M = Be, Mg, Ca), has been theoretically designed and investigated. These compounds possess a similar geometric structure, in which the alkali-metal cation Li+ lies near the center of the cagelike (NH3)4 complexant and the alkaline-earth anion M- is located outside. All the proposed alkaline-earthides exhibit extremely large static first hyperpolarizability (β0) up to 8.01 × 106 au, indicating that they can be considered as novel NLO molecules with high performance. The calculated results reveal that the alkaline-earth atom is more suitable to serve as excess electron acceptor in excess electron compounds for increasing the β0 value. We hope that our study can attract more research interest in alkaline-earthides and further experimental research.

Non-linear optical response of meso substituted dipyrromethene boron difluoride dyes: Synthesis, photophysical, DFT and Z scan study

2-(Naphthalen-2-yl)benzo[d]thiazole meso fused dipyrromethene boron difluoride dyes are synthesised and their linear and non-linear optical properties are studied. The third order nonlinear susceptibility (χ3) value obtained from the Z-scan experiment is 11.21 × 10−13 and 13.30 × 10−13 esu. The global hybrid (B3LYP and BHHLYP) and range-separated hybrid (CAM-B3LYP) functional with the basis set 6-311++G(d,p) performed better in computing the linear and non-linear optical properties. The computed β0 value (56.36 × 10−30 esu and 48.64 × 10−30 esu for Kr-OH-BDY and Kr-OMe-BDY respectively) of both the dyes are superior to that of urea (βo = 0.371 × 10−30 esu). Thermal and reorientational study display the dominating electronic contribution to the linear polarizability (α) whereas for first-order hyperpolarizability (β), pure vibrational contributions found to be more operative in both the dyes. The geometries of the dyes were optimized by using B3LYP/6-311++ G(d,p) level of theory.

Effects of Li doping and B3N3 substitution on the static first hyperpolarizabilities of biphenylene nanosheets: A computational and comparative study

Abstract Based on the density functional theory calculations, the BP-(B3N3)n and Li@BP-(B3N3)n (BP = biphenylene, n = 1–4) systems, were designed for the first time and explored the effects of Li doping and B3N3 substitution on their nonlinear optical (NLO) properties. We find that, when the carbon rings are replaced by B3N3 units in the biphenylene, systems of enhanced static hyperpolarizabilities (β0) are delivered. And the position and the number of B3N3 unit have an important effect on the β0 value. Moreover, when one Li atom is adsorbed on the surface of B3N3-substituted BP, the β0 values of these systems are further dramatically enhanced to 2.24 × 104–1.42 × 106 au. The further investigations show that small transition energy is the decisive factor for their large β0 values. Specially, these Li-doped compounds exhibits high stability and excellent infrared (IR) transparency. These findings might provide valuable insights into the design of novel high-performance NLO materials based on BP flake.

Theoretical study of substituent effects on electride characteristics and the nonlinear optical properties of Li@calix[4]pyrrole

Electrides, a novel kind of ionic compound in which electrons serve as anions, have been proposed as potential second-order nonlinear optical (NLO) materials. In this work, the substituent effects on the electride characteristics and the NLO behaviour of Li@calix[4]pyrrole with an electride-like structure were studied theoretically. The results show that electron-donating and electron-withdrawing groups can effectively increase and decrease the first hyperpolarizability (β0), respectively, without affecting the electride characteristics (electron population). More interestingly, lithiation in which four H atoms bonded to N atoms are substituted by four Li atoms within the core structure of Li@calix[4]pyrrole remarkably improves the electride characteristics, with a large electron population of 0.74 e (1.02 e) at the NNA (ELF) basins, making this structure perhaps the first formal molecular electride with almost one electron isolated from the rest of the molecules. Furthermore, a relationship between the electride characteristics and the NLO properties is found: the more delocalization the excess electron of the electride experiences, the larger the β0 value is. The present investigation may provide useful information for exploring high-performance second-order nonlinear optical materials based on organic electrides.

Non-linear optical response of meso hybrid BODIPY: Synthesis, photophysical, DFT and Z scan study.

Hybrid meso BODIPY dyes are synthesized and their linear and non-linear optical properties are studied. Time-resolved fluorescence lifetime decay is found to be identical for all dyes irrespective of meso substituents. The Z-scan experiment performed to calculate the nonlinear absorption coefficient (β) and third-order nonlinear susceptibility (χ3). Global hybrid (B3LYP and BHHLYP) and range-separated hybrid (CAM-B3LYP) functional with the basis set 6-311++G(d,p) was employed to determine the theoretical linear and non-linear optical properties. The computed β0 value of all the three dyes was found to be superior to that of urea (βo = 0.371 × 10-30 esu). Introduction of meso substituent directly affects the polarizability and second-order hyperpolarizability of the dyes. Thermal and reorientational effect of the investigated NLOphoric dyes were studied.

Influences of adsorptions of some inorganic molecules on electronic, optical, and thermodynamic properties of Mg12O12 nanocage: A computational approach

According to density functional theory, we investigate the effects of BF3, BF4, BCl3, AlF3, AlCl3, AlBr3, BeF3, GaF3, GaCl3, GaBr3, NO3, BS2, BSO, BO2, F2, PF5, PCl5, and ASF5 molecules on the geometric, electronic, linear, and nonlinear optical properties of an Mg12O12 nanocage. The thermodynamic stability and feasibility of the adsorption process are investigated by analyzing the free energy. It is shown that the adsorptions of almost all molecules on the Mg12O12 surface are exothermic. The calculations of the polarizability of these nanoclusters show that among the studied molecules, BeF3 has the largest influence on the polarizability value (α ≈ 315 a.u., the unit a.u. is short for atomic unit). The static first hyperpolarizability (β0) value is increased in the presence of these superhalogens. This increase is greatest for BeF3 and BF4 of which the highest value of the first hyperpolarizability (β0 ≈ 5775 a.u.) is related to a BeF3c(e@Mg12O12) nanocluster. The adsorption position is a key to estimating the value of increasing the first hyperpolarizability.