Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates
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 f...
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MDPI AG
2021-09-01
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| Online Access: | https://www.mdpi.com/2073-8994/13/9/1636 |
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| author | Emna Rtibi Benoit Champagne |
| author_facet | Emna Rtibi Benoit Champagne |
| author_sort | Emna Rtibi |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-03-10T07:10:54Z |
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| issn | 2073-8994 |
| language | English |
| last_indexed | 2024-03-10T07:10:54Z |
| publishDate | 2021-09-01 |
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| spelling | doaj.art-c06d929f341c42959731f7f0554225102023-11-22T15:27:46ZengMDPI AGSymmetry2073-89942021-09-01139163610.3390/sym13091636Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido PolyoxometalatesEmna Rtibi0Benoit Champagne1Laboratory of Materials Molecules and Applications, Preparatory Institute for Scientific and Technical Studies, Carthage University, B.P. 51 La Marsa, Tunis 2075, TunisiaLaboratory of Theoretical Chemistry, Unit of Theoretical and Structural Physical Chemistry, Namur Institute of Structured Matter, University of Namur, Rue de Bruxelles, 61, 5000 Namur, BelgiumDensity 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.https://www.mdpi.com/2073-8994/13/9/1636polyoxometalatesdonor/acceptor substituentsfirst hyperpolarizability(time-dependent) DFT |
| spellingShingle | Emna Rtibi Benoit Champagne Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates Symmetry polyoxometalates donor/acceptor substituents first hyperpolarizability (time-dependent) DFT |
| title | Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates |
| title_full | Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates |
| title_fullStr | Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates |
| title_full_unstemmed | Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates |
| title_short | Density Functional Theory Study of Substitution Effects on the Second-Order Nonlinear Optical Properties of Lindquist-Type Organo-Imido Polyoxometalates |
| title_sort | density functional theory study of substitution effects on the second order nonlinear optical properties of lindquist type organo imido polyoxometalates |
| topic | polyoxometalates donor/acceptor substituents first hyperpolarizability (time-dependent) DFT |
| url | https://www.mdpi.com/2073-8994/13/9/1636 |
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