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

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.

scholarly journals Structural Properties and Nonlinear Optical Responses of Halogenated Compounds: A DFT Investigation on Molecular Modelling

2018 ◽  
Vol 16 (1) ◽  
pp. 978-985 ◽  
Author(s):  
Muhammad Ramzan Saeed Ashraf Janjua
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Computational Study ◽  
Visible Region ◽  
Second Order ◽  
Computational Method ◽  
Lumo Energy ◽  
Functional Theory ◽  
Energy Gaps ◽  
Homo Lumo

AbstractComputational chemistry is used to evaluate structures of different compounds by using principles of theoretical and quantum chemistry integrated into useful computer programs. It is used to determine energies, dipole moments and thermodynamic properties of different compounds. The present work reports the computational study of six donor-acceptor dyes. The computational method CAM-B3LYP with 6-31G(d,p) was used in this research to determine the effect of halogens on non-linear optical compounds. HOMO-LUMO energy gaps, dipole polarizabilities, first hyperpolarizabilities, and absorption spectra of six studied compounds (dye 1: 4-(2-(4-fluorophenyl)ethynyl)benzenamine; dye 2: 4-(2-(4-chlorophenyl)ethynyl)benzenamine; dye 3: 4-(2-(4-bromophenyl)ethynyl)benzenamine; dye 4: 5-(2-(4-fluorophenyl)ethynyl)benzene-1,2,3-triamine; dye 5: 5-(2-(4-chlorophenyl)ethynyl)benzene-1,2,3-triamine; dye 6: 5-(2-(4-bromophenyl)ethynyl)benzene-1,2,3-triamine) with aniline and halo phenyl segments were computed by using density functional theory (DFT) and time-dependent density functional theory (TDDFT). Results indicate that all dyes showed wavelengths of maximum absorbance in the visible region. Small HOMO-LUMO energy gaps were observed in all investigated dyes. The present calculations on these dyes (1-6) offer an understanding of the direction of charge transfer (CT) and how NLO behavior can be explained. The aniline-to-halo phenyl CT, caused by the combination of the donor amino group and the acceptor halo group, could be a reason for NLO behavior of these sorts of compounds. These compounds exhibit significant molecular second-order NLO responses, especially dyes (6) and (5), with second-order polarizability determined to be approximately 4600 a.u.

STRUCTURES, ABSORPTION SPECTRA, AND ELECTRONIC PROPERTIES OF POLYFLUORENE AND ITS DERIVATIVES: A THEORETICAL STUDY

2006 ◽  
Vol 05 (03) ◽  
pp. 595-608 ◽  
Author(s):  
KRIENGSAK SRIWICHITKAMOL ◽  
SONGWUT SURAMITR ◽  
POTJAMAN POOLMEE ◽  
SUPA HANNONGBUA
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Energy Gap ◽  
Level Energy ◽  
Excitation Energies ◽  
Lumo Energy ◽  
Functional Theory ◽  
Local Energy Minimum ◽  
Pi Systems ◽  
Homo Lumo

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.

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

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.

Density Functional Study of H2S Adsorption on Small Agn (n = 1–5)

2013 ◽  
Vol 634-638 ◽  
pp. 47-51 ◽  
Author(s):  
Jun Qing Wen ◽  
A Ping Yang ◽  
Guo Xiang Chen ◽  
Chen Jun Zhang
Keyword(s):  
Density Functional Theory ◽  
Binding Energy ◽  
Density Functional ◽  
Global Minimum ◽  
Electronic States ◽  
Functional Study ◽  
Functional Theory ◽  
Energy Gaps ◽  
Single Fold ◽  
Homo And Lumo

The global-minimum geometries and electronic states of AgnH2S (n=1-5) clusters have been calculated using density-functional theory. Our calculations predicate that the stable geometries of AgnH2S clusters can be got by directly adding the H2S molecule on different site of Agn clusters, Agn (n=1-5) clusters would like to bond with sulfur atom and the H2S molecule is partial to hold the top location and single fold coordination site in the clusters. After adsorption, the structures of Agn clusters and H2S molecule keep the original structures and are only distorted slightly. The averaged binding energy reveals that adsorption of H2S molecule can strengthen the stabilities of AgnH2S clusters. The second difference in energy and the energy gaps between the HOMO and LUMO of Agn and AgnH2S have been studied.

scholarly journals Theoretical study on crystal polymorphism and electronic structure of lead(ii) phthalocyanine using model dimers

RSC Advances ◽  
2017 ◽  
Vol 7 (14) ◽  
pp. 8646-8653 ◽  
Author(s):  
Nobutsugu Hamamoto ◽  
Hiromitsu Sonoda ◽  
Michinori Sumimoto ◽  
Kenji Hori ◽  
Hitoshi Fujimoto
Keyword(s):  
Density Functional Theory ◽  
Electronic Structure ◽  
Density Functional ◽  
Theoretical Study ◽  
Density Functional Theory Calculations ◽  
Functional Theory ◽  
Crystal Polymorphism ◽  
Small Models

The polymorphism in lead(ii) phthalocyanine solids was discussed with the results of density functional theory calculations using small models.

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

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.

scholarly journals Theoretical study on temperature effect of electronic structure and spin state in LaCoO3 by using density functional theory

2016 ◽  
Vol 285 ◽  
pp. 195-201 ◽  
Author(s):  
Takayoshi Ishimoto ◽  
Yumi Ito ◽  
Tomofumi Tada ◽  
Ryo Oike ◽  
Takashi Nakamura ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Electronic Structure ◽  
Temperature Effect ◽  
Spin State ◽  
Density Functional ◽  
Theoretical Study ◽  
Functional Theory

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

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.

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

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.

scholarly journals Boron Nitride Nanotubes for Curcumin Delivery as an Anticancer Drug: A DFT Investigation

2022 ◽  
Vol 12 (2) ◽  
pp. 879
Author(s):  
Suleiman Nafiu ◽  
Vitus Atanga Apalangya ◽  
Abu Yaya ◽  
Edward Benjamin Sabi
Keyword(s):  
Boron Nitride ◽  
Anticancer Drug ◽  
Density Functional ◽  
Adsorption Process ◽  
Drug Carrier ◽  
Boron Nitride Nanotubes ◽  
Functional Theory ◽  
Energy Gaps ◽  
Homo And Lumo ◽  
Homo Lumo

The electrical properties and characteristics of the armchair boron nitride nanotube (BNNT) that interacts with the curcumin molecule as an anticancer drug were studied using ab initio calculations based on density functional theory (DFT). In this study, a (5,5) armchair BNNT was employed, and two different interactions were investigated, including the interaction of the curcumin molecule with the outer and inner surfaces of the BNNT. The adsorption of curcumin molecules on the investigated BNNT inside the surface is a more favorable process than adsorption on the outside surface, and the more persistent and stronger connection correlates with curcumin molecule adsorption in this case. Furthermore, analysis of the HOMO–LUMO gap after the adsorption process showed that the HOMO value increased marginally while the LUMO value decreased dramatically in the curcumin-BNNT complexes. As a result, the energy gaps between HOMO and LUMO (Eg) are narrowed, emphasizing the stronger intermolecular bonds. As a result, BNNTs can be employed as a drug carrier in biological systems to transport curcumin, an anticancer medication, and thereby improve its bioavailability.

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