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Assessing the quantum mechanical level of theory for prediction of linear and nonlinear optical properties of push-pull organic molecules

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Abstract

In this paper, we assessed the quantum mechanical level of theory for prediction of linear and nonlinear optical (NLO) properties of push-pull organic molecules. The electric dipole moment (μ), mean polarizability (〈α〉) and total static first hyperpolarizability (βt) were calculated for a set of benzene, styrene, biphenyl and stilbene derivatives using HF, MP2 and DFT (31 different functionals) levels and over 71 distinct basis sets. In addition, we propose two new basis sets, NLO-V and aNLO-V, for NLO properties calculations. As the main outcomes it is shown that long-range corrected DFT functionals such as M062X, ωB97, cam-B3LYP, LC-BLYP and LC-ωPBE work satisfactorily for NLO properties when appropriate basis sets such as those proposed here (NLO-V or aNLO-V) are used. For most molecules with β ranging from 0 to 190 esu, the average absolute deviation was 13.2 esu for NLO-V basis sets, compared to 27.2 esu for the standard 6-31 G(2d) basis set. Therefore, we conclude that the new basis sets proposed here (NLO-V and aNLO-V), together with the cam-B3LYP functional, make an affordable calculation scheme to predict NLO properties of large organic molecules.

Calculated values for total static first hyperpolarizability (βt) for 4-amino-4′-nitrostilbene at cam-B3LYP/basis set level. Experimental from Cheng et al. [1, 2].

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Acknowledgments

The authors would like to thank the Brazilian agencies CNPq, CAPES, and FAPEMIG for financial support.

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Authors and Affiliations

  1. Núcleo de Estudos em Química Computacional (NEQC), Departamento de Química, ICE, Universidade Federal de Juiz de Fora, Campus Universitário, 36.036-330, Juiz de Fora, MG, Brazil

    Diego Paschoal & Hélio F. Dos Santos

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  1. Diego Paschoal
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Correspondence to Diego Paschoal.

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Table S1 includes the electric dipole of polarizability (α, a.u.) for all atoms at Hartree-Fock level. Tables S2, S3, S4 and S5 include the calculated values for electric dipole moment (μ), average polarizability (〈α〉) and total static first hyperpolarizability (βt) at LEVEL OF THEORY/6-31 G(d) for para-nitroaniline, 4-amino-β-nitrostyrene, 4-amino-4′-nitrobiphenyl and 4-amino-4′-nitrostilbene. Tables S6, S7, S8 and S9 include the calculated values for electric dipole moment (μ), average polarizability (〈α〉) and total static first hyperpolarizability (βt) at cam-B3LYP/BASIS SET for para-nitroaniline, 4-amino-β-nitrostyrene, 4-amino-4′-nitrobiphenyl and 4-amino-4′-nitrostilbene. Tables S10 to S15 include the calculated values for para-disubstituted benzenes, 4-β-disubstituted styrenes, 4-4′-disubstituted biphenyls, 4-4′-disubstituted stilbenes, 4-β-disubstituted α-phenylpolyenes oligomers and disubstituted α,ω-diphenylpolyenes oligomers, respectively, at cam-B3LYP/NLO-V, cam-B3LYP/6-31 G(2d) and cam-B3LYP/Def2-SVP levels. Table S16 include the NLO-V basis set for H, B, C, N, O, F, Si, P, S and Cl atoms.

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Paschoal, D., Dos Santos, H.F. Assessing the quantum mechanical level of theory for prediction of linear and nonlinear optical properties of push-pull organic molecules. J Mol Model 19, 2079–2090 (2013). https://doi.org/10.1007/s00894-012-1644-4

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