Thermal and optical characterization of multiple hydrogen bonded liquid crystals derived from mesogenic and non-mesogenic compounds: experimental and theoretical (DFT) studies

2020 ◽  
Vol 98 (5) ◽  
pp. 413-424 ◽  
Author(s):  
S. Sundaram ◽  
P. Subhasri ◽  
R. Jayaprakasam ◽  
V.N. Vijayakumar
Keyword(s):  
Liquid Crystals ◽  
Molecular Orbital ◽  
Density Functional ◽  
Nbo Analysis ◽  
Stability Factor ◽  
Dft Studies ◽  
Scanning Calorimetry ◽  
Lowest Unoccupied Molecular Orbital ◽  
Optical Applications ◽  
Hydrogen Bonded

A set of new cyclic multiple hydrogen bonded liquid crystals (HBLCs) have been designed and synthesized from citric acid (CA) and 4-dodecyloxybenzoic acid (12OBA). The presence of intermolecular hydrogen bonds (H-bonds) between non-mesogenic and mesogenic compounds has been confirmed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) studies. The hydrogen bonding interactions were explained from natural bond orbital (NBO) analysis using B3LYP/6-311G(d,p) level of theory. Additionally, the Mulliken atomic charges reveal the nature of charge distribution in the HBLC complex. The dynamics of phase transitions and the corresponding stability factor have been evaluated using polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and electrostatic potential (ESP) analysis. Highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies of the CA+12OBA complex is theoretically calculated and experimentally verified. It is found that the variation in the mole ratio in mesogenic with non-mesogenic compound induces the stabilized nematic (N) and smectic X (Sm X) phases. Photocatalytic activity of the CA+12OBA HBLC complex reveals the usage of its optical applications.

Experimental and computational (DFT) studies on induced orthogonal smectic A∗ phase in hydrogen-bonded ferroelectric liquid crystals

2018 ◽  
Vol 32 (21) ◽  
pp. 1850223 ◽  
Author(s):  
P. Subhasri ◽  
R. Jayaprakasam ◽  
V. N. Vijayakumar
Keyword(s):  
Liquid Crystals ◽  
Molecular Orbital ◽  
Density Functional ◽  
Liquid Crystalline ◽  
Proton Acceptor ◽  
Dft Studies ◽  
Ferroelectric Liquid Crystals ◽  
Smectic A ◽  
Present Complex ◽  
Hydrogen Bonded

Hydrogen-bonded ferroelectric liquid crystals (HBFLC) are designed and synthesized from nonmesogenic chiral proton donor compound of (R)-([Formula: see text])-Methylsuccinic acid (MSA) and mesogenic proton acceptor compound of 4-undecyloxybenzoic acid (11OBA) in a different mole ratio. Intermolecular hydrogen bonds (H-bond) between the nonmesogenic and mesogenic compounds have been confirmed through experimental Fourier transform infrared spectroscopy (FTIR) and density functional theory (DFT) computational studies. The steric hindrance and inductive effects of the present complex and its influence on the structure are discussed. A rich phase polymorphism in the liquid crystalline complex has been studied using polarizing optical microscope (POM) and differential scanning calorimetry (DSC). The chiral phases observed in the present complex are due to the presence of lone pair (n) to anti-bonding ([Formula: see text]) transition symmetry which is validated by DFT studies. A noteworthy observation of induced smectic A[Formula: see text](Sm A[Formula: see text]) by quenching of traditional phase (nematic) has been identified and the reason for the same has been discussed by DFT studies. The unusual phase order of Sm A[Formula: see text], smectic C[Formula: see text](Sm C[Formula: see text]) and smectic G[Formula: see text][Formula: see text](Sm G[Formula: see text]) mesogenic phases are observed. The other liquid crystalline parameters are evaluated by experimental and theoretical calculations and the same has been compared. Increased tilt angle in liquid crystal (LC) molecules has been theoretically analyzed by natural bond orbital (NBO) studies. Stability of the HBFLC phases and its origination mechanism have been discussed with the help of highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO–LUMO) energies.

scholarly journals Spectroscopic Studies and Vibrational Assignments, Homo- Lumo, UV-VIS, NBO Analysis of Benzonitrile

2020 ◽  
Vol 13 (3) ◽  
pp. 225-239
Author(s):  
K. Rajalakshmi ◽  
S. Sharmila
Keyword(s):  
Molecular Orbital ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Spectroscopic Studies ◽  
Nbo Analysis ◽  
Functional Theory ◽  
Vibrational Assignments ◽  
Highest Occupied Molecular Orbital ◽  
Lowest Unoccupied Molecular Orbital ◽  
The Fourier Transform

The Fourier transform infrared and FT-Raman spectra of Benzonitrile have been recorded in region of 4000-400 and 4000-100 cm -1 respectively. A complete assignments and analysis of fundamental vibrational modes of the molecule have been carried out. The observed fundamental modes have been compared with harmonic vibrational frequencies computed using ab initio and density functional theory calculations by employing B3LYP functional at 6-311G(d, p) level and HF/6-311G(d, p).UV-Vis spectrum of the compound has been recorded, the natural bond orbital (NBO) electronic properties, such as highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies have been calculated with B3LYP/6-311G(d, p) level. These calculated energies show that charge transfer occurs within molecule. NBO analysis, thermodynamics properties and Mulliken charges of the title molecule are also calculated and interpreted

Observation of Induced Luminescence and Thermochromism in Achiral Hydrogen Bonded Liquid Crystal Complexes

2020 ◽  
Vol 234 (10) ◽  
pp. 1709-1733
Author(s):  
A. Ramya ◽  
V. Balasubramanian ◽  
R. Jayaprakasam ◽  
V. N. Vijayakumar
Keyword(s):  
Liquid Crystal ◽  
Nematic Phase ◽  
Density Functional ◽  
Atomic Charge ◽  
Optical Microscope ◽  
Band Gap Energy ◽  
Stability Factor ◽  
Scanning Calorimetry ◽  
Interesting Phenomenon ◽  
Hydrogen Bonded

AbstractA novel hydrogen bonded liquid crystal (HBLC) complexes are obtained from the non-mesogenic (benzylmalonic acid) and mesogenic (p-n-alkyloxybenzoic acid, where n = 6, 7 and 8) compound via intermolecular hydrogen bonds (H-bond). H-bonds are experimentally confirmed by the Fourier transform infrared spectroscopic (FT-IR) studies and the same is validated using density functional theory (DFT). Induced thermochromism is observed by the polarizing optical microscope (POM) and its possible applications are reported. Phase transition temperature and their analogous enthalpy values, stability factor and span width are determined by the differential scanning calorimetry (DSC) studies. Band gap energy is calculated using UV-visible and photoluminescence spectrum. Hyper conjugative stabilization energy and atomic charge distribution is studied by the natural bond orbital (NBO) studies. Mulliken analysis clearly reveals the intermolecular interaction and steric effect of the HBLC complexes. An interesting phenomenon is that the observation of luminescence and thermochromism in the highly fluidity nematic phase. This peculiar behavior is attributed due to the intermolecular H-bonding interaction between the BMA and nOBA compounds and the effect of rotatory motion of the molecules in nematic phase. Luminescence increases when the spacer moiety decreases in the present complexes is also reported. In nematic phase, the molecules are in different degrees of the excited state which is correlated with the hyper conjugative energy through NBO studies.

Supramolecular arrangement and photophysical properties of a dinuclear cyanophenylboronic acid ester

2018 ◽  
Vol 74 (4) ◽  
pp. 452-459 ◽  
Author(s):  
A. Jaquelin Cárdenas-Valenzuela ◽  
Jesús Baldenebro-López ◽  
Jorge A. Guerrero-Álvarez ◽  
Herbert Höpfl ◽  
Daniel Glossman-Mitnik ◽  
...  
Keyword(s):  
Solid State ◽  
Molecular Orbital ◽  
Crystal Engineering ◽  
Density Functional ◽  
Photophysical Properties ◽  
Three Dimensional ◽  
Building Blocks ◽  
Scanning Calorimetry ◽  
Supramolecular Architectures ◽  
Lowest Unoccupied Molecular Orbital

Boronic esters are useful building blocks for crystal engineering and the generation of supramolecular architectures, including macrocycles, cages and polymers (one-, two- and three-dimensional), with potential utility in diverse fields such as separation, storage and luminescent materials. The novel dinuclear cyanophenylboronic ester described herein, namely 4,4′-(2,4,8,10-tetraoxa-3,9-diboraspiro[5.5]undecane-3,9-diyl)dibenzonitrile, C19H16B2N2O4, was prepared by condensation of 4-cyanophenylboronic acid and pentaerythritol and fully characterized by elemental analysis, IR and NMR (1H and 11B) spectroscopy, single-crystal X-ray diffraction analysis and TG-DSC (thermogravimetry–differential scanning calorimetry) studies. In addition, the photophysical properties were examined in solution and in the solid state by UV–Vis and fluorescence spectroscopies. Density functional theory (DFT) calculations with ethanol as solvent reproduced reasonably well the HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) of the title compound. Hirshfeld surface and fingerprint plot analyses are presented to illustrate the supramolecular connectivity in the solid state.

scholarly journals Computational Aspects of (E)-O-Carbomethoxy Methyl Oxime Ether of 1,3-Dimethyl-2,6-Diphenylpiperidin-4-One

2019 ◽  
Vol 9 (2S2) ◽  
pp. 701-706
Keyword(s):  
Molecular Orbital ◽  
Density Functional ◽  
Atomic Charge ◽  
Molecular Geometry ◽  
Biologically Active ◽  
Oxime Ether ◽  
Structure And Property ◽  
Highest Occupied Molecular Orbital ◽  
Computational Aspects ◽  
Lowest Unoccupied Molecular Orbital

Density Functional Theoretical (DFT) studies on the biologically active oxime ether derived from 1,3-dimethyl-2,6-diphenylpiperidin-4-one has been carried out. Various quantum chemical parameters of the molecule viz. molecular geometry, Highest Occupied Molecular Orbital – Lowest Unoccupied Molecular Orbital (HOMO–LUMO) energies, Non-Linear Optical (NLO) properties, Mulliken atomic charge distribution were obtained theoretically and compared with the single crystal data. An insight into the structure and property correlation revealed the probable behavior of the molecule studied

scholarly journals Molecular-level architectural design using benzothiadiazole-based polymers for photovoltaic applications

2017 ◽  
Vol 13 ◽  
pp. 863-873 ◽  
Author(s):  
Vinila N Viswanathan ◽  
Arun D Rao ◽  
Upendra K Pandey ◽  
Arul Varman Kesavan ◽  
Praveen C Ramamurthy
Keyword(s):  
Molecular Orbital ◽  
Architectural Design ◽  
Density Functional ◽  
Short Circuit ◽  
Energy Levels ◽  
Photovoltaic Performance ◽  
Hole Mobility ◽  
Short Circuit Current ◽  
Open Circuit ◽  
Lowest Unoccupied Molecular Orbital

A series of low band gap, planar conjugated polymers, P1 (PFDTBT), P2 (PFDTDFBT) and P3 (PFDTTBT), based on fluorene and benzothiadiazole, was synthesized. The effect of fluorine substitution and fused aromatic spacers on the optoelectronic and photovoltaic performance was studied. The polymer, derived from dithienylated benzothiodiazole and fluorene, P1, exhibited a highest occupied molecular orbital (HOMO) energy level at −5.48 eV. Density functional theory (DFT) studies as well as experimental measurements suggested that upon substitution of the acceptor with fluorine, both the HOMO and lowest unoccupied molecular orbital (LUMO) energy levels of the resulting polymer, P2, were lowered, leading to a higher open circuit voltage and short circuit current with an overall improvement of more than 110% for the photovoltaic devices. Moreover, a decrease in the torsion angle between the units was also observed for the fluorinated polymer P2 due to the enhanced electrostatic interaction between the fluorine substituents and sulfur atoms, leading to a high hole mobility. The use of a fused π-bridge in polymer P3 for the enhancement of the planarity as compared to the P1 backbone was also studied. This enhanced planarity led to the highest observed mobility among the reported three polymers as well as to an improvement in the device efficiency by more than 40% for P3.

Computational and Experimental Study onthe Adsorption and Inhibition Effects of 1,3-Benzothiazol-6-ol on the Corrosion ofSteel X80 in Acidic Solution

2019 ◽  
Vol 0 (0) ◽  
Author(s):  
Iman Danaee ◽  
Paria Nikparsa ◽  
Mohammad Reza Khosravi-Nikou
Keyword(s):  
Molecular Orbital ◽  
Density Functional ◽  
Acidic Solution ◽  
Energy Gap ◽  
Force Microscopy ◽  
Highest Occupied Molecular Orbital ◽  
Low Concentrations ◽  
Noise Data ◽  
Chemical Factors ◽  
Lowest Unoccupied Molecular Orbital

Abstract In this work, the adsorption and inhibition behavior of 1,3-benzothiazol-6-ol were investigated by computational and experimental techniques for steel X80 corrosion in acidic solution. The density functional theory was carried out and quantum chemical factors like the energy gap, energy of highest occupied molecular orbital, the energy of lowest unoccupied molecular orbital, the fraction of electron transferred, and Mulliken charges have been calculated. In addition, according to quantum calculation, S atom in 1,3-benzothiazol-6-ol indicated more tendency for electrophilic attack in adsorption. The main reason for high inhibition efficiencies in very low concentrations is the planar and simplicity of inhibitor structure which leads to increasing the efficiency of adsorption by functional group especially sulfur. Electrochemical frequency modulation and potentiodynamic polarization indicated that this material has excellent inhibiting features in very low concentrations. The influence of DC trend on the explanation of electrochemical noise data was evaluated by polynomial fitting and the optimum polynomial order m = 5 was obtained. Noise resistance and the inhibition efficiency was calculated and compared in different methods. The theory of shot noise in frequency domain was used to obtain the electrochemical event charge. The corroded surface of steel in the absence and existence of thiazole compound was studied by Atomic force microscopy.

The Geometric and Electronic Structures of Fen-1Si(n=2-7) Clusters

2010 ◽  
Vol 150-151 ◽  
pp. 984-987
Author(s):  
Shuai Qin Yu ◽  
Li Hua Dong ◽  
Yan Sheng Yin
Keyword(s):  
Molecular Orbital ◽  
Density Functional ◽  
Energy Gap ◽  
Energy Difference ◽  
Ground State Structure ◽  
Magic Numbers ◽  
Highest Occupied Molecular Orbital ◽  
Hybridization Intensity ◽  
Lowest Unoccupied Molecular Orbital ◽  
The Stability

The geometric structures and electronic properties of Si doped Fen (n=2-7) clusters have been systematically studied at the BPW91 level in density-functional theory (DFT). Calculated results show that an Si impurity does not change the ground-state structure of small iron clusters and prefers to occupy surface site bonding with iron atoms as many as possible. The second-order energy difference and the vertical ionization potential show that n=4 and 6 are magic numbers within the size range studied, but the maximum value occurs at n=4 for the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital(LUMO). It is found that the hybridization intensity between Si and Fe atoms is relevant to the stability of clusters.

Investigation of Carbon Monoxide Adsorption on Cationic Gold- Palladium Clusters

2013 ◽  
Vol 68 (10-11) ◽  
pp. 651-658 ◽  
Author(s):  
Yang-Mei Chen ◽  
Xiao-Yu Kuang ◽  
Xiao-Wei Sheng ◽  
Huai-Qian Wang ◽  
Peng Shao ◽  
...  
Keyword(s):  
Carbon Monoxide ◽  
Molecular Orbital ◽  
Density Functional ◽  
Co Adsorption ◽  
Vibration Strength ◽  
Au Clusters ◽  
Highest Occupied Molecular Orbital ◽  
Lowest Unoccupied Molecular Orbital ◽  
Pd Clusters ◽  
Homo Lumo

Density functional calculations have been performed for the carbon monoxide molecule adsorption on AunPd+m(n+m ≤ 6) clusters. In the process of CO adsorption, small Au clusters and Pd clusters tend to be an Au atom and three Pd atoms adsorption, respectively. For the mixed Au-Pd clusters, an Au atom, a Pd atom, two atoms consisted of an Au atom and a Pd atom, two Pd atoms, and three Pd atoms adsorption structures are displayed. The highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps and natural bond orbital charge population are calculated. Moreover, CO adsorption energy, CO stretching frequency, and CO bond length (upon adsorption) are also analysed in detail. The results predict that the adsorption strength of Au clusters with CO and the C-O vibration strength is enhanced and reduced after doping of Pd in the AunPdmCO+ complexes, respectively

Cross-conjugation as a Motif for Organic Non-Linear Optical Molecules

2014 ◽  
Vol 1698 ◽  
Author(s):  
Meghana Rawal ◽  
Kerry Garrett ◽  
Andreas F. Tillack ◽  
Werner Kaminsky ◽  
Evgheni Jucov ◽  
...  
Keyword(s):  
Molecular Orbital ◽  
Density Functional ◽  
Dipole Moments ◽  
X Ray Diffraction ◽  
Conjugated Molecules ◽  
Functional Theory ◽  
Highest Occupied Molecular Orbital ◽  
Donor And Acceptor ◽  
Vis Spectroscopy ◽  
Lowest Unoccupied Molecular Orbital

ABSTRACTWe studied the effect of a cross-conjugated bridging group (χC) on charge-transfer in a push-pull chromophore system. The hyperpolarizability of such molecules was found to be comparable to that of a fully π-conjugated molecule (πC) with the same donor and acceptor. The cross-conjugated moiety was then applied as a pendant to a fully π-conjugated chromophore containing a tricyanopyrroline acceptor (TCP). The addition of a χC moiety did not alter the intrinsic hyperpolarizability and provides an avenue for extending and aiding πC systems. The molecules were examined by X-ray diffraction (XRD), hyper-Raleigh scattering (HRS) and UV-visible (UV-vis) spectroscopy. Experimental results were compared with the predictions of density functional theory (DFT). Cross-conjugated molecules have comparable β values, relative to πC molecules, due to reduced spatial overlap between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). Thus, the χC architecture could facilitate independent modification of donor and acceptor strengths while minimizing unfavorable effects on electronic transitions and dipole moments.

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