Electronic Structure of Metallophthalocyanines, MPc (M = Fe, Co, Ni, Cu, Zn, Mg) and Fluorinated MPc

We compute the electronic structure and optical excitation energies of metal-free and transition metal phthalocyanines (H2Pc and MPc for M = Fe, Co, Ni, Cu, Zn, Mg) using density functionaltheory with optimally-tuned range-separated hybrid functionals (OT-RSH).We show that the OT-RSH approach provides photoemission spectra in quantitative agreement with experimentsas well as optical band gaps within 10% of their experimental values, capturing the interplay of localized d-states and delocalized pi-pi* states for these organometallic compounds. We examine the tunability of MPcs and H2Pc through fluorination, resulting in quasi-rigid shifts of the molecular orbital energies by up to about 0.7 eV. Our comprehensive dataset provides a new computational benchmark for phthalocyanines molecules, significantly improving upon other density-functional-theory-based approaches.

Can boron form coordination complexes with diffuse electrons? Evidence for linked solvated electron precursors

Electronic Structure ◽

10.1088/2516-1075/ac495c ◽

2022 ◽

Author(s):

Zachary Jordan ◽

Shahriar N. Khan ◽

Benjamin A. Jackson ◽

Evangelos Miliordos

Keyword(s):

Electronic Structure ◽

Density Functional ◽

Molecular System ◽

Hydrocarbon Chain ◽

Solvated Electron ◽

Excitation Energies ◽

Functional Theory ◽

Boron Complexes ◽

The Stability ◽

First Time

Abstract Density functional theory and ab initio multi-reference calculations are performed to examine the stability and electronic structure of boron complexes that host diffuse electrons in their periphery. Such complexes (solvated electron precursors or SEPs) have been experimentally identified and studied theoretically for several s- and d-block metals. For the first time, we demonstrate that a p-block metalloid element can form a stable SEP when appropriate ligands are chosen. We show that three ammonia and one methyl ligands can displace two of the three boron valence electrons to a peripheral 1s-type orbital. The shell model for these outer electrons is identical to previous SEP systems (1s, 1p, 1d, 2s). Further, we preformed the first examination of a molecular system consisting of two SEPs bridged by a hydrocarbon chain. The electronic structure of these dimers is very similar to that of traditional diatomic molecules forming bonding and anti-bonding σ and π orbitals. Their ground state electronic structure resembles that of two He atoms, and our results indicate that the excitation energies are nearly independent of the chain length for four carbon atoms or longer. These findings pave the way for the development of novel materials similar to expanded metals and electrides.

Atomic and Electronic Structure of LaAlO3 and LaAlO3:Mg from First-Principles Calculations

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.79-82.1257 ◽

2009 ◽

Vol 79-82 ◽

pp. 1257-1260

Author(s):

Li Guan ◽

Li Tao Jin ◽

Wei Zhang ◽

Qiang Li ◽

Jian Xin Guo ◽

...

Keyword(s):

Electronic Structure ◽

Band Structure ◽

Band Gap ◽

Density Functional ◽

Lattice Structure ◽

Cell Structure ◽

Functional Theory ◽

Super Cell ◽

Direct Band ◽

In the present paper, the lattice structure, band structure and density of state of LaAlO3 and LaAlO3:Mg are calculated by first-principle method based on density functional theory. Firstly, we select the different cutoff energy and k-point grid in the calculations, and obtain the most stable geometry structure of single crystal LaAlO3. The calculated lattice parameters are a=b=5.441 Å, c=13.266 Å, which matches with experimental values. To deeply understand the electronic structure of LaAlO3, a 2×1×1 super-cell structure is established and the doping concentration of Mg at Al sites is 25%. From the band structure and density of states, it can be seen that LaAlO3 has a direct band gap Eg=3.6 eV. However, LaAlO3:Mg has a larger band gap Eg=3.89 eV and the Fermi level enters into the valence band, which indicates the holes are introduced. The calculated results show that the conductivity of LaAlO3:Mg is better than pure LaAlO3, which is in good agreement with experimental results.

Renormalization from Density Functional Theory to Strong Coupling Models for the Electronic Structure of La2CuO4

MRS Proceedings ◽

10.1557/proc-169-19 ◽

1989 ◽

Vol 169 ◽

Cited By ~ 1

Author(s):

Mark S. Hybertsen ◽

Michael Schluter ◽

E.B. Stechel ◽

D.R. Jennison

Keyword(s):

Electronic Structure ◽

Hubbard Model ◽

Strong Coupling ◽

Density Functional ◽

Nearest Neighbor ◽

Quantitative Agreement ◽

Energy Scale ◽

Low Energy ◽

Energy Spectra ◽

Functional Theory

AbstractStrong coupling models for the electronic structure of La2CuO4 are derived in two successive stages of renormalization. First, a three-band Hubbard model is derived using a constrained density functional approach. Second, exact diagonalization studies of finite clusters within the three band Hubbard model are used to select and map the low energy spectra onto effective one-band Hamiltonians. At each stage, some observables are calculated and found to be in quantitative agreement with experiment. The final results suggest the following models to be adequate descriptions of the low energy scale dynamics: (1) a spin 1/2 Heisenberg model for the insulating case with nearest neighbor J≈130 meV; (2) a "t–t'–J" model with nearly identical parameters for the electron and hole doped cases.

Density functional theory of transition metal phthalocyanines, I: electronic structure of NiPc and CoPc—self-interaction effects

Applied Physics A ◽

10.1007/s00339-008-5007-z ◽

2008 ◽

Vol 95 (1) ◽

pp. 159-163 ◽

Cited By ~ 98

Author(s):

Noa Marom ◽

Leeor Kronik

Keyword(s):

Electronic Structure ◽

Transition Metal ◽

Density Functional ◽

Interaction Effects ◽

Functional Theory ◽

Metal Phthalocyanines

Isolation, Identification, Molecular and Electronic Structure, Vibrational Spectroscopic Investigation, and Anti-HIV-1 Activity of Karanjin Using Density Functional Theory

Journal of Theoretical Chemistry ◽

10.1155/2014/680987 ◽

2014 ◽

Vol 2014 ◽

pp. 1-13 ◽

Cited By ~ 2

Author(s):

Anoop kumar Pandey ◽

Abhishek Kumar Bajpai ◽

Ashok Kumar ◽

Mahesh Pal ◽

Vikas Baboo ◽

...

Keyword(s):

Electronic Structure ◽

Spectroscopic Investigation ◽

Density Functional ◽

Ground State Structure ◽

Functional Theory ◽

Experimental Values ◽

Anti Hiv ◽

Molecular And Electronic Structure ◽

Hiv 1

“Karanjin” (3-methoxy furano-2,3,7,8-flavone) is an anti-HIV drug, and it is particularly effective in the treatment of gastric problems. The method of isolation of “Karanjin” followed the Principles of Green Chemistry (eco-friendly and effortless method). The optimized geometry of the “Karanjin” molecule has been determined by the method of density functional theory (DFT). Using this optimized structure, we have calculated the infrared wavenumbers and compared them with the experimental data. The calculated wavenumbers are in an excellent agreement with the experimental values. On the basis of fully optimized ground-state structure, TDDFT//B3LYP/LANL2DZ calculations have been used to determine the low-lying excited states of Karanjin. Based on these results, we have discussed the correlation between the vibrational modes and the crystalline structure of “Karanjin.” A complete assignment is provided for the observed FTIR spectra. This is the first report of the isolation, molecular and electronic structure using vibrational spectroscopic investigation, density functional theory, and anti-HIV-1 activity of “Karanjin.”

Electronic structure, first and second order physical properties of MPS4: a theoretical study

Materials Science-Poland ◽

10.1515/msp-2016-0060 ◽

2016 ◽

Vol 34 (2) ◽

pp. 275-285

Author(s):

Tahar Dahame ◽

Bachir Bentria ◽

Houda Faraoun ◽

Ali Benghia ◽

A.H. Reshak

Keyword(s):

Electronic Structure ◽

Physical Properties ◽

Density Functional ◽

Population Analysis ◽

Second Order ◽

Ionic Character ◽

Modern Theory ◽

Functional Theory ◽

Electro Optic ◽

AbstractWe have calculated the electronic structure and physical properties of metal thiophosphate compounds InPS4 and AlPS 4by means of pseudopotential density functional theory (DFT) coupled with the modern theory of polarization. The targeted physical properties are ﬁrst and second order optical properties as well as elastic, piezoelectric and electro-optic coefﬁcients. Furthermore, population analysis is presented in order to evaluate the covalent-ionic character of the constituent bonds. The calculated elastic constants, refractive indices and second order optical coefﬁcients of InPS4 are in good agreement with experimental values. With the absence of any theoretical or experimental physical properties of AlPS4, we predict that this compound has high piezoelectric coefﬁcients with d14 = − 73.82 pm/V, d25 = − 10.96 pm/V and d36 = 28.19 pm/V.

Density functional theory of transition metal phthalocyanines, II: electronic structure of MnPc and FePc—symmetry and symmetry breaking

Applied Physics A ◽

10.1007/s00339-008-5005-1 ◽

2008 ◽

Vol 95 (1) ◽

pp. 165-172 ◽

Cited By ~ 88

Author(s):

Noa Marom ◽

Leeor Kronik

Keyword(s):

Electronic Structure ◽

Transition Metal ◽

Symmetry Breaking ◽

Density Functional ◽

Functional Theory ◽

Metal Phthalocyanines

An investigation of the excitation and emission properties of fluorescence compounds using DFT and TD-DFT methods

HUE UNIVERSITY JOURNAL OF SCIENCE NATURAL SCIENCE ◽

10.26459/hueuni-jns.v127i1a.4777 ◽

2018 ◽

Vol 127 (1A) ◽

pp. 43

Author(s):

Duong Tuan Quang

Keyword(s):

Excited States ◽

Density Functional ◽

Basis Set ◽

Excitation Energies ◽

Dft Methods ◽

Functional Theory ◽

Emission Properties ◽

Experimental Values ◽

Optimized Geometries

The density functional theory and time-dependent density functional theory methods were used for investigation of the excitation and emission properties of some fluorophores. The calculations were based on the optimized geometries of ground states and excited states at the B3LYP functional and LanL2DZ basis set. The results clarified the nature of the optical properties of the compounds and agreed well with the experimental data. The approximate values of excitation energies and emission energies of compounds were also identified. The calculated excitation energies were about 0.01 to 0.56 eV higher than experimental values. Meanwhile, the emission energies were from 0.34 to 0.89 eV higher than experimental values. These large errors occurred when there were great variations between the optimized geometries of ground state and excited states. They could be due to the presence of components of solvent in real solution that stabilized the excited states, leading to reduce the excitation and emission energies in the experiments.

Temperature-dependent electronic structure of γ-phase CuI: first-principles insights

Journal of Physics Condensed Matter ◽

10.1088/1361-648x/ac45b8 ◽

2021 ◽

Author(s):

Ze-Li Xu ◽

Chang Yang ◽

Yu-Ning Wu

Keyword(s):

Electronic Structure ◽

Temperature Effect ◽

Density Functional ◽

Phonon Scattering ◽

Temperature Phase ◽

Temperature Dependent ◽

Functional Theory ◽

Fundamental Understanding ◽

Transparent Display ◽

Abstract To deepen the understanding of CuI that emerges as a promising nextgeneration transparent display material, we investigate the temperature effect on the electronic structures of its room-temperature phase γ-CuI. Using density-functional-theory-based approaches, we investigate the bandgap renormalization, which is contributed by the electron-phonon (elph) interaction and lattice thermal expansion. Different from most semiconductors, the bandgap widens as temperature increases, although it only widens by 88.3 meV from 0 to 600 K. In addition, based on the temperature-dependent band structure and conventional Drude model, we investigate the influences of the effective masses and evaluate the hole mobilities limited by phonon scattering along different directions. The calculated mobilities agree well with existing experimental values. Our study not only provides a fundamental understanding of the temperature effect on the electronic structure of CuI, but also gives insights for further improvement of the electronic and thermoelectric devices based on CuI.