Second-order nonlinear optical properties of two chalcone derivatives: insights from sum-over-states

Author(s)

Custodio, Jean M. F. ^[1] ; D'Oliveira, Giulio D. C. ^[1] ; Gotardo, Fernando ^[2] ; Cocca, Leandro H. Z. ^[2] ; de Boni, Leonardo ^[2] ; Perez, Caridad N. ^[1] ; Napolitano, Hamilton B. ^[3] ; Osorio, Francisco A. P. ^{[4, 5]} ; Valverde, Clodoaldo ^{[3, 6]}

Affiliation

^[1] Univ Fed Goias, Inst Quim, BR-74690970 Goiania, Go - Brazil

^[2] Univ Sao Paulo, Inst Fis Sao Carlos, BR-13566590 Sao Paulo, SP - Brazil

^[3] Univ Estadual Goias, Campus Ciencias Exatas & Tecnol, BR-75132903 Anapolis, Go - Brazil

^[4] Univ Fed Goias, Inst Fis, BR-74690900 Goiania, Go - Brazil

^[5] Pontificia Univ Catolica Goias, BR-13566590 Goiania, Go - Brazil

^[6] Univ Paulista, BR-74845090 Goiania, Go - Brazil

• Document type: Journal article
• Source: Physical Chemistry Chemical Physics; v. 23, n. 10, p. 6128-6140, MAR 14 2021.
• Web of Science Citations: 0

Abstract

In this study, a combined experimental and theoretical study of the nonlinear optical properties (NLO) of two chalcone derivatives, (E)-3-(2-methoxyphenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (MPSP) and (E)-3-(3-nitrophenyl)-1-(2-(phenylsulfonylamine)phenyl)prop-2-en-1-one (NPSP), in DMSO is reported. The single crystal structures of the compounds, which differ only by the type and position of one substituent, were grown using the slow evaporation technique, and the main structural differences are discussed. The two-photon absorption and first-order hyperpolarizability measurements were performed via the Z-scan technique and hyper-Rayleigh scattering experiment in DMSO. The theoretical calculations were performed using the Density Functional Theory (DFT) at the CAM-B3LYP/6-311++G(d,p) level, and the sum-over-states (SOS) approach in both static and dynamic cases. Besides the electron conjugation achieved by the aromatic rings, olefins, and carbonyl groups, both compounds have a nearly flat chalcone backbone, which is believed to contribute to the nonlinear optical properties. MPSP and NPSP have different positions, even though they have roughly the same conformation and form C-HMIDLINE HORIZONTAL ELLIPSISO interactions. For several studied frequencies, the HRS first hyperpolarizability values for MPSP are greater than those for NPSP, indicating that in most cases the NLO properties of MPSP are better. The comparison among the theoretical and experimental HRS first hyperpolarizability results showed a good agreement. In addition, the two-dimensional second order nonlinear optical spectra obtained from the sum-over-states model indicate good second-order NLO responses of the two chalcone derivatives under external fields. Our findings are important not only to show the potential nonlinear optical application of the two new compounds but also to gain an insight into how different chemical compositions might affect the crystal structures and physico-chemical properties. (AU)

• FAPESP's process: 16/20886-1 - Ultrafast nonlinear optical spectroscopy: Transient Absorption and optical Kerr Gate with polarization control
• Grantee: Leonardo De Boni
• Support Opportunities: Regular Research Grants
• FAPESP's process: 18/11283-7 - Nonlinear photonics: spectroscopy and advanced processing of materials
• Grantee: Cleber Renato Mendonça
• Support Opportunities: Research Projects - Thematic Grants