Experimental and theoretical (FT-IR, FT-Raman, UV-vis, NMR) spectroscopic analysis and first order hyperpolarizability studies of non-linear optical material: (2E)-3-[4-(methylsulfanyl) phenyl]-1-(4-nitrophenyl) prop-2-en-1-one using density functional theory.
A combined experimental and theoretical investigation on FT-IR, FT-Raman, NMR, UV-vis spectra of a chalcone derivative (2E)-3-[4-(methylsulfanyl) phenyl]-1-(4-nitrophenyl) prop-2-en-1-one (4N4MSP) has been reported. 4N4MSP has two planar rings connected through conjugated double bond and it provides a necessary configuration to show non-linear optical (NLO) response. The molecular structure, fundamental vibrational frequencies and intensity of the vibrational bands are interpreted with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) with B3LYP functional and 6-311++G(d,p) basis set combination. The analysis of the fundamental modes was made with the help of potential energy distribution (PED). Molecular electrostatic potential (MEP) surface was plotted over the geometry primarily for predicting sites and relative reactivities towards electrophilic and nucleophilic attack. The delocalization of electron density of various constituents of the molecule has been discussed with the aid of NBO analysis. The electronic properties, such as excitation energies, oscillator strength, wavelengths, HOMO and LUMO energies, were calculated by time-dependent density functional theory (TD-DFT) and the results complement the experimental findings. The recorded and calculated 1H chemical shifts in gas phase and MeOD solution are gathered for reliable calculations of magnetic properties. Thermodynamic properties like heat capacity (C°p,m), entropy (S°m), enthalpy (H°m) have been calculated for the molecule at the different temperatures. Based on the finite-field approach, the non-linear optical (NLO) parameters such as dipole moment, mean polarizability, anisotropy of polarizability and first order hyperpolarizability of 4N4MSP molecule are calculated. The predicted first hyperpolarizability shows that the molecule has a reasonably good nonlinear optical (NLO) behavior.
Department of Physics, University of Lucknow, Lucknow, India; Department of Applied Physics, Faculty of Engineering and Technology, M.J.P. Rohilkhand University, Bareilly, India.
Amit
A
Kumar
Department of Applied Physics, Faculty of Engineering and Technology, M.J.P. Rohilkhand University, Bareilly, India.
Vipin
V
Deval
Department of Physics, University of Lucknow, Lucknow, India.
Poonam
P
Tandon
Department of Applied Physics, Faculty of Engineering and Technology, M.J.P. Rohilkhand University, Bareilly, India. Electronic address: drarchana.physics@gmail.com.
Archana
A
Gupta
Department of Physics, Center for Post Graduate Studies and Research, St. Philomena College, Puttur, India.
E
E
Deepak D'silva
D002244:Carbon / Q000737:chemistry; D047188:Chalcones / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008280:Magnetics; D008968:Molecular Conformation; D009585:Nitrogen Dioxide / Q000737:chemistry; D009596:Nitrophenols / Q000737:chemistry; D055095:Optics and Photonics; D010100:Oxygen / Q000737:chemistry; D011312:Pressure; D013056:Spectrophotometry, Ultraviolet; D017550:Spectroscopy, Fourier Transform Infrared; D013059:Spectrum Analysis, Raman; D055672:Static Electricity; D013696:Temperature; D013816:Thermodynamics; D013997:Time Factors; D014961:X-Ray Diffraction
D047188:Chalcones; D009596:Nitrophenols; C024719:4-nitrophenyl; D002244:Carbon; D009585:Nitrogen Dioxide; D010100:Oxygen
(2E)-3-[4-(methylsulfanyl) phenyl]-1-(4-nitrophenyl) prop-2-en-1-one; Density functional theory; Hyperpolarizability; NMR; UV–vis analysis; Vibrational analysis