Kumar Amit, Deval Vipin, Tandon Poonam, Gupta Archana, Deepak D'silva E
Department of Physics, University of Lucknow, Lucknow, India; Department of Applied Physics, Faculty of Engineering and Technology, M.J.P. Rohilkhand University, Bareilly, India.
Department of Applied Physics, Faculty of Engineering and Technology, M.J.P. Rohilkhand University, Bareilly, India.
Spectrochim Acta A Mol Biomol Spectrosc. 2014 Sep 15;130:41-53. doi: 10.1016/j.saa.2014.03.072. Epub 2014 Apr 8.
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.
报道了对一种查尔酮衍生物（2E）-3-[4-（甲硫基）苯基]-1-（4-硝基苯基）丙-2-烯-1-酮（4N4MSP）的傅里叶变换红外光谱（FT-IR）、傅里叶变换拉曼光谱（FT-Raman）、核磁共振光谱（NMR）、紫外可见光谱（UV-vis）进行的实验与理论相结合的研究。4N4MSP有两个通过共轭双键相连的平面环，它提供了显示非线性光学（NLO）响应的必要构型。借助基于密度泛函理论（DFT）、采用B3LYP泛函和6-311++G（d，p）基组组合进行的结构优化和正则坐标力场计算，对分子结构、基本振动频率和振动带强度进行了解释。借助势能分布（PED）对基本振动模式进行了分析。在分子几何结构上绘制了分子静电势（MEP）表面，主要用于预测亲电和亲核攻击的位点及相对反应活性。借助自然键轨道（NBO）分析讨论了分子各组成部分电子密度的离域情况。通过含时密度泛函理论（TD-DFT）计算了激发能、振子强度、波长、最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）能量等电子性质，结果与实验发现相互补充。收集了在气相和MeOD溶液中记录和计算得到的1H化学位移，用于可靠地计算磁性性质。计算了该分子在不同温度下的热力学性质，如热容（C°p,m）、熵（S°m）、焓（H°m）。基于有限场方法，计算了4N4MSP分子的非线性光学（NLO）参数，如偶极矩、平均极化率、极化率各向异性和一阶超极化率。预测的一阶超极化率表明该分子具有相当良好的非线性光学（NLO）行为。
