HOMO–LUMO energy interactions between endocrine disrupting chemicals and ionic liquids using the density functional theory: Evaluation and comparison

The structural and energetic properties of polyfluorene and its derivatives were investigated, using quantum chemical calculations. Conformational analysis of bifluorene was performed by using ab initio (HF/6-31G* and MP2/6-31G*) and density functional theory (B3LYP/6-31G*) calculations. The results showed that the local energy minimum of bifluorene lies between the coplanar and perpendicular conformation, and the B3LYP/6-31G* calculations led to the overestimation of the stability of the planar pi systems. The HOMO-LUMO energy differences of fluorene oligomers and its derivatives — 9,9-dihexylfluorene (DHPF), 9,9-dioctylfluorene (PFO), and bis(2-ethylhexyl)fluorene (BEHPF) — were calculated at the B3LYP/6-31G* level. Energy gaps and effective conjugation lengths of the corresponding polymers were obtained by extrapolating HOMO-LUMO energy differences and the lowest excitation energies to infinite chain length. The lowest excitation energies and the maximum absorption wavelength of polyfluorene were also performed, employing the time-dependent density functional theory (TDDFT) and ZINDO methods. The extrapolations, based on TDDFT and ZINDO calculations, agree well with experimental results. These theoretical methods can be useful for the design of new polymeric structures with a reducing energy gap.

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CH2O Adsorption on M (M = Li, Mg and Al) Atom Deposited ZnO Nano-Cage: DFT Study

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.786.384 ◽

2018 ◽

Vol 786 ◽

pp. 384-392 ◽

Cited By ~ 2

Author(s):

Hussein Y. Ammar

Keyword(s):

Density Functional Theory ◽

Bond Length ◽

Density Functional ◽

Functional Theory ◽

The Density Functional Theory ◽

Structural And Electronic Properties ◽

Formaldehyde Molecule ◽

Electronic Configurations ◽

Adsorption Energies ◽

Homo Lumo

The structural and electronic properties of Li, Mg and Al deposited ZnO nanocages and their effects on the adsorption of formaldehyde molecule have been investigated using the density functional theory (DFT) computations. To understand the behavior of the adsorbed CH2O molecule on the ZnO nanocage, results of DFT calculations of the M-deposited nanocages (M=Li, Mg and Al), as well as complex systems consisting of the adsorbed CH2O molecule on M-deposited ZnO nanocage were reported. The results presented include adsorption energies, bond lengths, electronic configurations, density of states and molecular orbitals. It was found that, the most energetically stable adsorption configurations of CH2O molecule on the bare ZnO leads to 12% dilation in C=O bond length of CH2O and 14% decrease in HOMO-LUMO gap of ZnO cluster. The most energetically stable adsorption configurations of CH2O molecule on Li, Mg and Al-deposited ZnO lead to 4%, 4% and 11% dilation in C=O bond length of CH2O and-0.66, -45 and , +66% change in HOMO-LUMO gap of ZnO nanocages, respectively. The interaction between CH2O with bare ZnO and M-deposited ZnO nanocages is attributed to charge transfer mechanism. These results may be meaningful for CH2O degradation and detection.

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SOLVENT EFFECTS ON THE ELECTRONIC STRUCTURE AND NON-LINEAR OPTICAL PROPERTIES OF PYRENE AND SOME OF ITS DERIVATIVES BASED ON DENSITY FUNCTIONAL THEORY

FUDMA Journal of Sciences ◽

10.33003/fjs-2020-0404-477 ◽

2021 ◽

Vol 4 (4) ◽

pp. 236-251

Author(s):

A. S. Gidado ◽

L. S. Taura ◽

A. Musa

Keyword(s):

Density Functional Theory ◽

Gas Phase ◽

Density Functional ◽

Energy Gap ◽

Chemical Reactivity ◽

Basis Set ◽

Lumo Energy ◽

Functional Theory ◽

Organic Optoelectronic ◽

Homo Lumo

Pyrene (C16H10) is an organic semiconductor which has wide applications in the field of organic electronics suitable for the development of organic light emitting diodes (OLED) and organic photovoltaic cells (OPV). In this work, Density Functional Theory (DFT) using Becke’s three and Lee Yang Parr (B3LYP) functional with basis set 6-311++G(d, p) implemented in Gaussian 03 package was used to compute total energy, bond parameters, HOMO-LUMO energy gap, electron affinity, ionization potential, chemical reactivity descriptors, dipole moment, isotropic polarizability (α), anisotropy of polarizability ( Δ∝) total first order hyper-polarizability () and second order hyperpolarizability (). The molecules used are pyrene, 1-chloropyrene and 4-chloropyrene in gas phase and in five different solvents: benzene, chloroform, acetone, DMSO and water. The results obtained show that solvents and chlorination actually influenced the properties of the molecules. The isolated pyrene in acetone has the largest value of HOMO-LUMO energy gap of and is a bit closer to a previously reported experimental value of and hence is the most stable. Thus, the pyrene molecule has more kinetic stability and can be described as low reactive molecule. The calculated dipole moments are in the order of 4-chloropyrene (1.7645 D) < 1-chloropyrene (1.9663 D) in gas phase. The anisotropy of polarizability ( for pyrene and its derivatives were found to increase with increasing polarity of the solvents. In a nutshell, the molecules will be promising for organic optoelectronic devices based on their computed properties as reported by this work.

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Meso-alkynyl corroles and their cobalt(III), manganese(III) and gallium(III) complexes

Journal of Porphyrins and Phthalocyanines ◽

10.1142/s1088424619501566 ◽

2020 ◽

Vol 24 (05n07) ◽

pp. 737-749

Author(s):

Michael Haas ◽

Sabrina Gonglach ◽

Wolfgang Schöfberger

Keyword(s):

Density Functional Theory ◽

Electronic Structure ◽

Density Functional ◽

Theoretical Study ◽

Lumo Energy ◽

Functional Theory ◽

Energy Gaps ◽

Peak Broadening ◽

Homo And Lumo ◽

Homo Lumo

We report routes towards synthesis of novel [Formula: see text]-conjugated freebase cobalt, copper, gallium and manganese meso-alkynylcorroles. UV-vis spectra show that extensive peak broadening, red shifts, and changes in the oscillator strength of absorptions increase with the extension of [Formula: see text]-conjugation. Using density functional theory (DFT), we have carried out a first theoretical study of the electronic structure of these metallocorroles. Decreased energy gaps of about 0.3–0.4 eV between the HOMO and LUMO orbitals compared to the corresponding copper, gallium and manganese meso-5,10,15 triphenylcorrole are observed. In all cases, the HOMO energies are nearly unperturbed as the [Formula: see text]-conjugation is expanded. The contraction of the HOMO–LUMO energy gaps is attributed to the lowered LUMO energies.

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Design, Synthesis, and Structural Characterization of a Bisantimony(III) Compound for Anion Binding and the Density Functional Theory Evaluation of Halide Binding through Antimony Secondary Bonding Interactions

The Journal of Physical Chemistry A ◽

10.1021/acs.jpca.6b08170 ◽

2016 ◽

Vol 120 (46) ◽

pp. 9257-9269 ◽

Cited By ~ 7

Author(s):

Jinchun Qiu ◽

Daniel K. Unruh ◽

Anthony F. Cozzolino

Keyword(s):

Density Functional Theory ◽

Structural Characterization ◽

Density Functional ◽

Anion Binding ◽

Functional Theory ◽

Design Synthesis ◽

Theory Evaluation ◽

The Density Functional Theory ◽

Secondary Bonding

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Investigation of the Effects of Solvents on the Structural, Electronic and Thermodynamic Properties of Rosiglitazone Based on Density Functional Theory

Physical Science International Journal ◽

10.9734/psij/2019/v21i230103 ◽

2019 ◽

pp. 1-18

Author(s):

R. A. Ismail ◽

A. B. Suleiman ◽

A. S. Gidado ◽

A. Lawan ◽

A. Musa

Keyword(s):

Density Functional Theory ◽

Dipole Moment ◽

Thermodynamic Properties ◽

Gas Phase ◽

Density Functional ◽

Dielectric Constants ◽

Basis Sets ◽

Lumo Energy ◽

Functional Theory ◽

Homo Lumo

Rosiglitazone ( C18H19N3O3S ) is an anti-diabetic drug that reduces insulin resistance in patients with type 2 diabetes. The parameters (bond lengths and bond angles), HOMO, LUMO, HOMO-LUMO energy gap, dipole moment, thermodynamic properties, total energy and vibrational frequencies and intensities of the Rosiglitazone molecule in gas phase and in solvents (Water, Ethanol, DMSO and Acetonitrile) were calculated based on Density Functional Theory (DFT) using standard basis sets: B3LYP/6-31G(d,p), B3LYP/6-31+G(d,p) and B3LYP/6-31++G(d,p). Windows version of Gaussian 09 was used for all the calculations. From the results obtained, the solvents have little influence on the optimized parameters of the molecule. The highest HOMO value of -5.433 eV was found in gas phase showing that the molecule will best donate electron in the gas phase, followed by ethanol in comparison with other solvents. The values of the HOMO were observed to increase with the decrease in dielectric constants of the solvents across all the basis sets used. The lowest LUMO energy of -1.448 eV was found to be in ethanol which shows that the molecule will best accept electron in ethanol compared to the gas phase and other solvents. The largest HOMO-LUMO gap of 4.285 eV was found in water which shows its higher kinetic stability and less chemical reactivity compared to other solvents and in the gas phase. The chemical softness of the molecule was found to decrease as the dielectric constants of the solvents increased namely from ethanol to water. The chemical hardness was found to slightly increase with the increase in dielectric constants of the solvents. The highest value of the dipole moment of 4.6874 D was found in water indicating that the molecule will have the strongest intermolecular interactions in water compared to other solvents and in the gas phase. The total energy increased as the dielectric constants of the solvents decreased from water to ethanol. The vibrational frequencies and intensities increased as the dielectric constants of the solvents increased from ethanol to water. The results confirmed the effects of solvents on the structural, electronic and thermodynamic properties of the studied molecule and will be useful in the design and development of rosiglitazone as an anti-diabetic drug.

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Structure, electronic and optical properties of chalcopyrite-type nano-clusters XFeY2 (X=Cu, Ag, Au; Y=S, Se, Te): a density functional theory study

Pure and Applied Chemistry ◽

10.1515/pac-2020-1202 ◽

2021 ◽

Vol 0 (0) ◽

Author(s):

Prabhat Ranjan ◽

Praveen K. Surolia ◽

Tanmoy Chakraborty

Keyword(s):

Density Functional Theory ◽

Dielectric Constant ◽

Refractive Index ◽

Optical Properties ◽

Solar Cells ◽

Density Functional ◽

Energy Gap ◽

Lumo Energy ◽

Functional Theory ◽

Homo Lumo

Abstract Iron-based chalcopyrite materials have diverse applications in solar cells, spintronic, thermoelectric devices, LEDs and medical sciences. In this report we have studied structure, electronic and optical properties of chalcopyrite-type nano-cluster XFeY2 (X=Cu, Ag, Au; Y=S, Se, Te) systematically by using Density Functional Theory (DFT). Our computed HOMO-LUMO energy gap of XFeY2 is in the range of 1.568–3.982 eV, which endorses its potential application in optoelectronic devices and solar cells. The result shows that chalcopyrite-type material AuFeS2 having a star-type structure with point group C2v and sextet spin multiplicity, is the most stable cluster with HOMO-LUMO energy gap of 3.982 eV. The optical properties viz. optical electronegativity, refractive index, dielectric constant, IR and Raman activity of these nano-clusters are also investigated. The result exhibits that HOMO-LUMO energy gap of XFeY2 along with optical electronegativity and vibrational frequency decreases from S to Se to Te, whereas refractive index and dielectric constant increases in the reverse order.

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Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.17.162 ◽

2021 ◽

Vol 17 ◽

pp. 2450-2461

Author(s):

Najeh Tka ◽

Mohamed Adnene Hadj Ayed ◽

Mourad Ben Braiek ◽

Mahjoub Jabli ◽

Peter Langer

Keyword(s):

Density Functional Theory ◽

Cyclic Voltammetry ◽

Density Functional ◽

Energy Levels ◽

Cross Coupling ◽

Density Functional Theory Calculations ◽

Facile Synthesis ◽

Lumo Energy ◽

Functional Theory ◽

Homo Lumo

A facile synthesis of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridine derivatives is reported which is based on POCl3-mediated cyclodehydration followed by double Suzuki–Miyaura cross-coupling. The absorption and fluorescence properties of the obtained products were investigated and their HOMO/LUMO energy levels were estimated by cyclic voltammetry measurements. Besides, density functional theory calculations were carried out for further exploration of their electronic properties.

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Synthesis, DFT calculations, photophysical, photochemical properties of peripherally metallophthalocyanines bearing (2-(benzo[d] [1,3] dioxol-5-ylmethoxy) phenoxy) substituents

10.21203/rs.3.rs-393739/v1 ◽

2021 ◽

Author(s):

Derya Güngördü Solğun ◽

Ümit Yıldıko ◽

Mehmet Salih Ağırtaş

Keyword(s):

Dft Calculations ◽

Density Functional ◽

Fluorescence Emission ◽

Docking Studies ◽

Lumo Energy ◽

Functional Theory ◽

The Density Functional Theory ◽

Homo Lumo ◽

Electronic Surface ◽

Absorption Measurements

Abstract 4-(2-(benzo[d] [1, 3] dioxol-5-ylmethoxy) phenoxy) phthalonitrile was first prepared as a starting material. Then, this new phthalonitrile derivative was reacted with Zn and Co salts to obtain new phthalocyanine complexes. Phthalocyanine complexes were evaluated by fluorescence emission, extinction, and absorption measurements. Aggregation studies show the compliance with the lambert-beer law in the concentration range studied for peripheral phthalocyanine compounds. The density functional theory (DFT) calculations of the metallophthalocyanines compounds were performed using B3LYP / 6-31G in Zn-Pc and B3LYP / LanL2DZ in Co-Pc to derive structural optimization, HOMO-LUMO energy parameters, and NLO properties. The calculated values of M-Pcs with different center atoms were obtained close to each other. Molecular electronic surface (MEP) maps of the studied compounds are mapped and discussed. The HOMO-LUMO energy gaps of our compounds studied are around 2.1 eV. The docking studies were performed with the phthalonitrile.

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Density functional theory study on CO adsorption on the PdnAl (n = 1–5) clusters

International Journal of Modern Physics B ◽

10.1142/s0217979218501874 ◽

2018 ◽

Vol 32 (15) ◽

pp. 1850187 ◽

Cited By ~ 4

Author(s):

Zhi Li ◽

Zhonghao Zhou ◽

Zhen Zhao ◽

Qi Wang

Keyword(s):

Density Functional Theory ◽

Ground State ◽

Density Functional ◽

Co Adsorption ◽

Binding Energies ◽

Density Functional Theory Study ◽

Functional Theory ◽

The Density Functional Theory ◽

Energy Configurations ◽

Homo Lumo

The configurations, stability, electronic properties and CO adsorption of the ground state Pd[Formula: see text]Al (n = 1–5) clusters are calculated by the density functional theory (DFT). The results reveal that the lowest-energy configurations of Pd[Formula: see text]Al clusters inherit the geometries of the host Pd[Formula: see text] clusters to a larger extent. The C atom in CO molecule prefers to approach more Pd atoms rather than Al atoms in small Pd[Formula: see text]Al clusters. Pd[Formula: see text]AlCO clusters have higher average binding energies than the corresponding small Pd[Formula: see text]CO clusters except for PdCO. AlCO and Pd3AlCO clusters possess better kinetic stability than their neighbors by the HOMO–LUMO gaps. Except for Pd6 clusters, CO molecule prefers to adsorb on small Pd[Formula: see text] clusters rather than Pd[Formula: see text]Al clusters. Both the Al–Pd bonding in Pd[Formula: see text]Al clusters and C–Pd bonding in Pd[Formula: see text]AlCO clusters have certain covalent characters.

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