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In the present study, we report on the results of computations of the electronic and the vibrational contributions to the static first hyperpolarizability (β) of meta-dinitrobenzene molecule. It turned out that the electron correlation effects are much more important for reliable prediction of the electronic counterpart than for determining vibrati...
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Citations
... Units) for the TCCP-2THE and TCCP-3THE, respectively. It is now well recognized that the electron correlation may strongly influence the values of hyperpolarizability [62][63][64][65][66]. The b == and b HRS results show also that M05-2X values using aug-cc-pVDZ basis set are higher. ...
With the rapid developments of computational methods, now it is effective and efficient to predict properties and underlying reasons at different stages. In this work, we systematically investigated hexachlorocyclotriphosphazene, tris(4–hydroxyphenyl) ethane and their various inorganic–organic hybrid derivatives for dipole moment, polarizability and static first hyperpolarizability. The relation between the nonlinear optical (NLO) properties and the energy gaps were also considered. The geometries of these inorganic–organic hybrid derivatives at different substitution positions have been performed using the B3LYP functional. The ωB97X–D and B3LYP functionals give the high static first hyperpolarizability compared to the CAM–B3LYP and M05–2X levels. Inverse relation has been obtained between the HOMO–LUMO gaps and the hyper-Rayleigh scattering (HRS) first hyperpolarizability βHRS\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${\beta }_{\text{HRS}}$$\end{document}. This theoretical study reveals underlying changes in the design structures, and shift in properties will provide better understanding and may grab the attention of researchers to study cross-linkable organocyclotriphosphazenes for NLO application.
Graphical abstract
... [103] The polarizability and hyperpolarizability of NLOphoric organic materials affected by vibrational transitions can be elucidated by theoretically. [104,105] For compounds 5 and 6, the vibrational transitions in dichloromethane and methanol determined by using CAMÀ B3LYP functional at 6-31 G(d).In the above table the 'e' and 'v' coefficient used to indicate the electronic and vibrational transition contributions to polarizability (α) as well as hyperpolarizability (β). From Table 7. ...
NLOphoric D‐π‐A‐π‐D coumarin chalcone 5 and their BF2 complex 6 were designed, synthesized and characterized through Mass,¹³C‐NMR, and ¹H‐NMR analysis. Their Photophysical properties are extensively studied in solvents of different polarity. On BF2 complexation of coumarin chalcone shows highly red shift in absorption and emission spectra compared to uncomplexed coumarin chalcone. Positive solvatochromism observed which is well supported by linear and multilinear regression analysis. For BF2 complexed coumarin‐chalcone 6 the solvent dipolarity (CSdP) is the main factor responsible for slightly red shift in absorption spectra, and also for the highly red‐shift in emission spectra. Frontier molecular orbital, molecular electrostatic potential and Generalized Mulliken‐Hush analysis revealed intramolecular charge transfer in these compounds. Nonlinear optical (NLO) properties for compounds 5 and 6 were studied by solvatochromic and computational method. The linear polarizability (α), first‐order hyperpolarizability (β) and second‐order hyperpolarizability (γ) of compounds were studied by the time dependent density functional theory using three different functionals namely B3LYP, BHHLYP and CAM−B3LYP with the 6–31 G (d) basis set. BF2 complexed compound 6, show higher values for αe + αv as well as βe+βv compared to compound 5. Third order nonlinear optical susceptibility (χ⁽³⁾) of these compounds obtained by Z‐scan analysis. Third‐order (χ⁽³⁾) non‐linear optical properties of BF2 complexed coumarin‐chalcone 6 were observed to be several times higher than those of the uncomplexed coumarin‐chalcone 5 these justify the design approach.
... Significant vibrational contribution to the overall NLO response is due to the coupling between the electronic polarization and vibration [103]. In this perception, the DFT is a useful computational tool to study the vibrational contribution to polarizability and hyperpolarizabilities of NLO chromophores [104]. Table 10 gives the DFT results of the diagonal electronic and pure vibrational contributions to the linear polarizability (α) and first hyperpolarizability (β). ...
Hybrid meso BODIPY dyes are synthesized and their linear and non-linear optical properties are studied. Timeresolved
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.
... The cooperative interaction between the electronic polarization arising from delocalization and vibrational transitions result in a large vibrational influence to the total NLO response [78]. In such an instance, DFT is a preferred calculation means to investigate the vibrational impact on the polarizability and hyperpolarizabilities of NLOphoric molecules [79,80]. We evaluated the vibrational influences to static electronic polarizabilities and hyperpolarizabilities using the method B3LYP/6-311 + G(d,p) in two solvents. ...
Comparative study of nonlinear optical properties of red fluorescent coumarins was carried out with density functional theory based ab initio method using the popular global hybrid (GH) and range separated hybrid (RSH) functionals and correlated with the spectroscopic values. The GHs - M06 L, PBE1PBE, M06, BHHLYP, M062X and M06HF and RSHs - HISSbPBE, wB97, wB97X, HSEH1PBE, CAM-B3LYP and wB97XD in combination with the double zeta basis function 6–311 + G(d,p) were used. The computed polarizability (α0), hyperpolarizability of the first order (β0) and second order (γ) computed by the RSHs are closer to the spectroscopic values compared to GHs. Polarizabilities computed with the functionals BHHLYP and M06-2X are closer with the spectroscopic values. Incorporation of additional cyano group enhances the NLO response. An increase in electrophilic nature contributed from the reduced orbital band gap culminating an increase in α0, β0, and γ in all the cases. The NLO response was found to be highly solvent dependent that is the polarity of the micro environment created by the solvents. To understand the agreement and accuracy among the NLO parameters obtained from the selected DFT functionals and the spectroscopic values, the mean absolute error (MAE) and vibrational contribution parameters are presented. Two photon absorption (TPA) cross section depends upon the molecular structure where π-framework is an important factor rather than number of acceptors.
... Significant vibrational contribution to the overall NLO response is due to the coupling between the electronic polarization and vibration [91]. In this perception the DFT is a useful computational tool to study the vibrational contribution to polarizability and hyperpolarizabilities of NLO chromophores [92]. Table 8 gives the DFT results of the diagonal electronic and pure vibrational contributions to the linear polarizability (α) and first hyperpolarizability (β). ...
... The coupling between the electronic polarization and vibration leads to a considerable vibrational contribution to the overall NLO response [86]. In this context, DFT is a very good computational tool to study the vibrational contribution to polarizability and hyperpolarizabilities of NLO chromophores [87,88]. We have obtained the vibrational contributions to static electronic polarizability and hyperpolarizabilities using B3LYP functional with 6e311þþg(d,p) basis set in various solvents. ...
Rigid pyrazino-phenanthroline based donor-π-acceptor-π-auxiliary acceptor type compounds have been studied for their linear and non-linear optical properties. The non-linear optical (NLO) behavior of these dyes was studied by calculating the values of staticα, β and γ using solvatochromic as well as computational methods. The results obtained by solvatochromic method are correlated theoretically with Density Functional Theory (DFT) using B3LYP/6-31G (d), CAM B3LYP/6-31 G(d), B3LYP/6-31++ g(d,P) and CAM B3LYP/6-31++ g(d,P) methods. The results reveal that, among all four computational methods CAM-B3LYP/6-31++ g(d,P) performs well for the calculation of linear polarizability (α) and first order hyperpolarizability (β), while CAM-B3LYP/6-31 g(d,P) for the calculation of second order hyperpolarizability (ϒ). Overall TPA depends on the molecular structure variation with increase in complexity and molecular weight, which implies that both the number of branches and the size of π-framework are important factors for the molecular TPA in this chromophoric system. Generalized Mulliken-Hush (GMH) analysis is performed to study the effective charge transfer from donor to acceptor.
... The coupling between induced electronic polarization and vibrational motion leads to a substantial vibrational contribution to the overall NLO response for such push-pull chromophores [64]. In this circumstances the DFT computation is helpful to study the vibrational contribution to polarizability and hyperpolarizability of NLOphores [65,66]. The vibrational contributions to static electronic polarizability and hyperpolarizability are obtained by using B3LYP functional with 6-311+g(d,p) basis set in gas phase and dichloromethane. ...
BORICO dyes with N, N-diethyl as a strong donor and BF2 complexed iminocoumarin six member core as strong acceptor are investigated as an efficient non linear optical chromophores. Extended π-conjugation over iminocoumarin moiety is useful to make ICT character of BORICO dyes more significant and is established on the scale of Generalised Mulliken Hush analysis scale. Bond length alternation and bond order alternation values for three BORICO chromophores estimates the cyanine like framework for optimal non linear optical response. The frontier molecular orbital diagrams obtained from density functional theory calculations shows that there is charge transfer from donor to accepter as well as effective overlap between them making the basis for optimal NLO response of BORICO chromophores. The theoretical values of linear and non linear optical responses for three BORICO NLOphores obtained by using three different functionals B3LYP, CAMB3LYP and BHandHLYP with 6-311+g(d,p) basis set are quite consistent for the values of static dipole moment (μ), linear polarizability (α) and first hyperpolarizability (β). However in case of the γ values calculation, compare to the similar values obtained by CAMB3LYP and BHandHLYP functionals, B3LYP overestimates the same. The vibrational motions play decisive role in the overall non linear optical properties of BORICO chromophores.
... The values of the first hyperpolarisability are found to be quite large for the so-called push-pull molecules, i.e., p-conjugated molecules with the electron donating and the electron withdrawing substituents attached to a ring, compared to the mono substituted systems. 21 This type of functionalisation of organic materials is meant for the purpose of maximising NLO properties. ...
Crystals of guanidinium oxalate monohydrate (GUOM), a salt of a functional guanidine derivative, crystallising with the space group of P21/c, is synthesised and characterised by single-crystal XRD, NMR, UV-Vis and vibrational spectroscopy. The assignment of spectral bands is carried out in terms of the fundamental modes of vibration of the guanidinium cation and oxalate anion. Thermal analysis (TG/DTA) indicates that the compound is thermally robust. GUOM also exhibits antimicrobial activity against a few microorganisms.
... The coupling betweenthe electronic polarization and vibration leads to a considerable vibrational contribution to the overall NLO response[78]. In this context the DFT is a very good computational tool to study the vibrational contribution to polarizability and hyperpolarizabilities of NLO chromophores[79,80]. We have obtained the vibrational contributions to static electronic polarizability and hyperpolarizabilities using B3LYP functional with 6e311þþg(d,p) basis set in two solvents.Table 10presents the DFT results of the diagonal electronic and vibrational contributions to the linear polarizability (a) and first hyperpolarizability (b).Table 10(chloroform) andTable S1(methanol) shows that along with electronic part there is substantial contribution of vibrational part to the polarizability and hyperpolarizability. ...
The dicyanoisophorone acceptor based NLOphores with Intramolecular Charge Transfer (ICT) character are newly synthesised, characterised and explored for linear and non linear optical (NLO) property investigation. Strong ICT character of these D-π-A styryl NLOphores is established with support of emission solvatochromism, polarity functions and Generalised Mulliken Hush (GMH) analysis. First, second and third order polarizability of these NLOphores is investigated by spectroscopic and TDDFT computational approach using CAM/B3LYP-6-311 + g (d, p) method. BLA and BOA values of these chromophores are evaluated from ground and excited state optimized geometries and found that the respective structures are approaching towards cyanine limit. Third order nonlinear susceptibility (X⁽³⁾) along with nonlinear absorption coefficient (β) and nonlinear refraction (n2) are evaluated for these NLOphores using Z-scan experiment. All four chromophores exhibit large polarization anisotropy (Δα), first order hyperpolarizability (β0), second order hyperpolarizability (γ) and third order nonlinear susceptibility (X⁽³⁾). TGA analysis proved these NLOphores are stable up to 320 °C and hence can be used in device fabrication.
... While the former approach can be quite successful in predicting electronic and vibrational (hyper)polarizabilities, the latter was shown a decade ago to completely fail in determining electronic contributions to α, β and γ of π-conjugated systems [1,2,3]. An assessment of DFT to compute vibrational (hyper)polarizabilities has only recently been undertaken [14,15,16]. The traditional functionals are expected to fail for long chain molecules, as the evolution of electronic contributions to α, β and γ with system size is poorly reproduced [3]. ...
Despite undisputed success of the density functional theory (DFT) in
various branches of chemistry and physics, an application of the DFT for
reliable predictions of nonlinear optical properties of molecules has
been questioned a decade ago. As it was shown by Champagne, et al. [1,
2, 3] most conventional DFT schemes were unable to qualitatively predict
the response of conjugated oligomers to a static electric field.
Long-range corrected (LRC) functionals, like LC-BLYP or CAM-B3LYP, have
been proposed to alleviate this deficiency. The reliability of LRC
functionals for evaluating molecular (hyper)polarizabilities is studied
for various groups of organic systems, with a special focus on
vibrational corrections to the electric properties.
