Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2022 Mar 11;15(6):2073.
doi: 10.3390/ma15062073.

Computational and Experimental Study of Nonlinear Optical Susceptibilities of Composite Materials Based on PVK Polymer Matrix and Benzonitrile Derivatives

Lucia Mydlova  1 , Bouchta Sahraoui  2 , Karolina Waszkowska  2 , Houda El Karout  2 , Malgorzata Makowska-Janusik  1 , Anna Migalska-Zalas  1
Affiliations

Computational and Experimental Study of Nonlinear Optical Susceptibilities of Composite Materials Based on PVK Polymer Matrix and Benzonitrile Derivatives

Lucia Mydlova et al. Materials (Basel). .

Abstract

Theoretical and experimental investigations of the linear and nonlinear optical properties of composite materials based on the (Z)-4-(1-cyano-2-(5-methylfuran-2-yl)vinyl)benzonitrile molecule named as A, the (Z)-4-(2-(benzofuran-2-yl)-1-cyanovinyl)benzonitrile named as B and the (Z)-4-(2-(4-(9H-carbazol-9-yl)phenyl)-1-cyanovinyl)benzonitrile molecule named as C embedded into poly(1-vinylcarbazole) (PVK) polymer matrix were performed. The electronic and optical properties of A, B, and C molecules in a vacuum and PVK were calculated. The guest-host polymer structures for A, B, and C molecules in PVK were modeled using molecular dynamics simulations. The spatial distribution of chromophores in the polymer matrix was investigated using the intermolecular radial distribution (RDF) function. The reorientation of A, B, and C molecules under the influence of the external electric field was investigated by measuring the time-dependent arrangement of the angle between the dipole moment of the chromophore and the external electric field. The polarizabilities and hyperpolarizabilities of tested compounds have been calculated applying the DFT/B3LYP functional. The second- and third-order nonlinear optical properties of the molecule/PVK thin film guest-host systems were investigated by the Maker fringes technique in the picosecond regime at the fundamental wavelength of 1064 nm. The experimental results were confirmed and explained with theoretical simulations and were found to be in good agreement. The modeling of the composites in volumetric and thin-film form explains the poling phenomena caused by the external electric field occurring with the confinement effect.

Keywords: PVK; density functional thery (DFT); guest–host composite; hyperpolarizability; molecular dynamics; nonlinear optics; nonlinear optics (NLO).

PubMed Disclaimer

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
The location of the θ angle defines the position between the direction of the external electric field (Eext) and the electric dipole moment (μmol) of a chromophore molecule. The molecule is presented in a laboratory coordinate system.
Figure 2
Figure 2
Structures of investigated chromophores A, B, C (a), mer of the PVK polymer (b) with marked their atomic groups chosen for the RDFs calculations and the structure of the B/PVK system (c) as an example of investigated composites.
Figure 3
Figure 3
Partial RDFs calculated for distances between the center of mass of different moieties of the A molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the bulk system. The RDFs are presented for the methyl group (Me) of the A molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule A and different subunits of PVK mer (c,d); and cyanovinyl CN2 at the back of the molecule A and different subunits of PVK mer (e,f).
Figure 4
Figure 4
Partial RDFs calculated for distances between the center of mass of different moieties of the B molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the bulk system. The RDFs are presented for the benzofuran group of the B molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule B and different subunits of PVK mer (c,d), and cyanovinyl CN2 at the back of the molecule B and different subunits of PVK mer (e,f).
Figure 5
Figure 5
Partial RDFs calculated for distances between the center of mass of different moieties of the C molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the bulk system. The RDFs are presented for carbazole group of C molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule C and different subunits of PVK mer (c,d); and cyanovinyl CN2 at the back of the molecule C and different subunits of PVK mer (e,f).
Figure 6
Figure 6
Partial RDFs calculated for distances between the center of mass of different moieties of the A molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the thin film composite system. The RDFs are presented for methyl group (Me) of A molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule A and different subunits of PVK mer (c,d); and cyanovinyl CN2 at the back of the molecule A and different subunits of PVK mer (e,f).
Figure 6
Figure 6
Partial RDFs calculated for distances between the center of mass of different moieties of the A molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the thin film composite system. The RDFs are presented for methyl group (Me) of A molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule A and different subunits of PVK mer (c,d); and cyanovinyl CN2 at the back of the molecule A and different subunits of PVK mer (e,f).
Figure 7
Figure 7
Partial RDFs calculated for distances between the center of mass of different moieties of the B molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the thin-film system. The RDFs are presented for benzofuran group of B molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule B and different subunits of PVK mer (c,d); and cyanovinyl CN2 at the back of the molecule B and different subunits of PVK mer (e,f).
Figure 7
Figure 7
Partial RDFs calculated for distances between the center of mass of different moieties of the B molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the thin-film system. The RDFs are presented for benzofuran group of B molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule B and different subunits of PVK mer (c,d); and cyanovinyl CN2 at the back of the molecule B and different subunits of PVK mer (e,f).
Figure 8
Figure 8
Partial RDFs calculated for distances between the center of mass of different moieties of the C molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the thin film system. The RDFs are presented for carbazole group of C molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule C and different subunits of PVK mer (c,d); and cyanovinyl CN2 at the back of the molecule C and different subunits of PVK mer (e,f).
Figure 8
Figure 8
Partial RDFs calculated for distances between the center of mass of different moieties of the C molecule and different subunits of PVK at T = 500 K (a,c,e) and T = 300 K (b,d,f) for the thin film system. The RDFs are presented for carbazole group of C molecule and different subunits of PVK mer (a,b); for cyanovinyl CN1 at the side of the molecule C and different subunits of PVK mer (c,d); and cyanovinyl CN2 at the back of the molecule C and different subunits of PVK mer (e,f).
Figure 9
Figure 9
Changes in the value of the order parameter <cosθ(t)> versus the time of simulation and applied external electric field calculated by the MD technique for the A/PVK (a,b), B/PVK (c,d), and C/PVK (e,f) composites in the volumetric form at the temperature of 500 K (a,c,e) and glassy state (300 K) after the simulated annealing (b,d,f).
Figure 10
Figure 10
Changes in the value of the order parameter <cosθ(t)> versus the time of simulation and applied external electric field calculated by MD technique for the A/PVK (a,b), B/PVK (c,d), and C/PVK (e,f) composites in the thin film form at the temperature of 500 K (a,c,e) and glassy state (300 K) after the simulated annealing (b,d,f).
Figure 10
Figure 10
Changes in the value of the order parameter <cosθ(t)> versus the time of simulation and applied external electric field calculated by MD technique for the A/PVK (a,b), B/PVK (c,d), and C/PVK (e,f) composites in the thin film form at the temperature of 500 K (a,c,e) and glassy state (300 K) after the simulated annealing (b,d,f).
Figure 11
Figure 11
Absorption spectra measured for PVK (a) and studied A/PVK-, B/PVK-, and C/PVK-based samples (b) in the form of thin films.
Figure 12
Figure 12
SHG intensity as a function of the incident angle measured for complexes A/PVK, B/PVK, and C/PVK with 10 wt% of A, B, and C chromophores in s-p (left) and p-p (right) polarization.
Figure 13
Figure 13
Second- (a) and third-order (b) NLO susceptibilities calculated for studied A/PVK, B/PVK, and C/PVK thin films with different content of chromophores, taking into account experimentally obtained data.
Figure 14
Figure 14
THG intensity as a function of incident angle of A/PVK, B/PVK, and C/PVK composites with 10 wt% of chromophores in p-p polarization.
See this image and copyright information in PMC

Similar articles

See all similar articles

Cited by

References

    1. Dalton L., Harper A., Ren A., Wang F., Todorova G., Chen J., Zhang C., Lee M. Polymeric Electro-optic Modulators: From Chromophore Design to Integration with Semiconductor Very Large Scale Integration Electronics and Silica Fiber Optics. Ind. Eng. Chem. Res. 1999;38:8–33. doi: 10.1021/ie9705970. - DOI
    1. Alyar H. A Review on nonlinear optical properties of donor-acceptor derivatives of naphthalene and azanaphthalene. Rev. Adv. Mater. Sci. 2013;34:79–87.
    1. Yan L., Chen X., He Q., Wang Y., Wang X., Guo Q., Bai F., Xia A. Localized Emitting State and Energy Transfer Properties of Quadrupolar Chromophores and (Multi)Branched Derivatives. J. Phys. Chem. A. 2012;116:8693–8705. doi: 10.1021/jp305407s. - DOI - PubMed
    1. Verbiest T., Houbrechts S., Kauranen M., Clays K., Persoons A. Second-order nonlinear optical materials: Recent advances in chromophore design. J. Mater. Chem. 1997;7:2175–2189. doi: 10.1039/a703434b. - DOI
    1. Dalton L.R., Sulivan P.A., Bale D.H. Electric field poled organic electro-optic materials: State of the art and future prospects. Chem. Rev. 2010;110:25–55. doi: 10.1021/cr9000429. - DOI - PubMed

LinkOut - more resources