DFT and TD-DFT studies of halogens adsorption on cobalt-doped porphyrin: Effect of the external electric field

Badran, H.M.; Eid, Kh.M.; Ammar, H.Y.

doi:10.1016/j.rinp.2021.103964

Cited by 28 publications

(21 citation statements)

References 69 publications

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“…The calculation results for the energy levels of LUMO, HOMO, singlet and triplet excited states, and dipole moment are provided in Table S2, Figure S22, and Figure . As shown in Figure S22, in the absence of an electric field, the LUMO–HOMO energy gap is 2.488 eV, which decreases linearly to 2.452 eV at the electric field of +0.257 V/Å and increases linearly to 2.518 eV at the electric field of −0.257 V/Å, both in agreement with previous results. , As shown in Figure b and Table S2, the singlet excitation of methylene blue is S 0 → S 1 transition (π–π∗ valence transitions), in which the major electronic component is HOMO → LUMO. The triplet excitations are composed of S 0 → T 1 , S 0 → T 2 , and S 0 → T 3 transitions, in which the major electronic components are HOMO → LUMO, HOMO-1 → LUMO, and HOMO-3 → LUMO, respectively.…”

Section: Resultssupporting

confidence: 90%

“…All density functional theory (DFT) calculations are performed using Gaussian 09 software with visualizations performed using GaussView 6.0.16. We used the GaussSum 3.0 program to visualize the densities of states (DOS) for methylene blue . Becke 3-parameter, Lee, Yang, and Parr (B3LYP) hybrid DFT calculations with the 3-21g basis set were used for ground-state optimization of methylene blue .…”

Section: Methodsmentioning

confidence: 99%

“…We also applied the B3LYP-D3 method to include van der Waals (London dispersion) interactions . In order to investigate the influence of an external electric field on the energy levels of singlet and triplet excitons, we applied five different values of the electric field between −0.257 and 0.257 V/Å along the y axis, which is parallel to the dipole (μ) orientation of methylene blue.…”

Section: Methodsmentioning

confidence: 99%

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Machine Learning-Aided Design of Gold Core–Shell Nanocatalysts toward Enhanced and Selective Photooxygenation

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Guo

Tyagi

et al. 2022

ACS Appl. Mater. Interfaces

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We demonstrate the use of the machine learning (ML) tools to rapidly and accurately predict the electric field as a guide for designing core–shell Au–silica nanoparticles to enhance 1O2 sensitization and selectivity of organic synthesis. Based on the feature importance analysis, obtained from a deep neural network algorithm, we found a general and linear dependent descriptor (θ ∝ aD 0.25 t –1, where a, D, and t are the shape constant, size of metal nanoparticles, and distance from the metal surface) for the electric field around the core–shell plasmonic nanoparticle. Directed by the new descriptor, we synthesized gold-silica nanoparticles and validated their plasmonic intensity using scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) mapping. The nanoparticles with θ = 0.40 demonstrate an ∼3-fold increase in the reaction rate of photooxygenation of anthracene and 4% increase in the selectivity of photooxygenation of dihydroartemisinic acid (DHAA), a long-standing goal in organic synthesis. In addition, the combination of ML and experimental investigations shows the synergetic effect of plasmonic enhancement and fluorescence quenching, leading to enhancement for 1O2 generation. Our results from time-dependent density functional theory (TD-DFT) calculations suggest that the presence of an electric field can favor intersystem crossing (ISC) of methylene blue to enhance 1O2 generation. The strategy reported here provides a data-driven catalyst preparation method that can significantly reduce experimental cost while paving the way for designing photocatalysts for organic drug synthesis.

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Section: Resultssupporting

confidence: 90%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Machine Learning-Aided Design of Gold Core–Shell Nanocatalysts toward Enhanced and Selective Photooxygenation

Tamtaji

Guo

Tyagi

et al. 2022

ACS Appl. Mater. Interfaces

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“…It is obvious the potential energy trivially varies and no considerable distortion is observed for the nano-cages; this emphasizes the stability of Be 12 O 12 and Mg 12 O 12 . In addition, the optimized geometries of discussed nano-cages were verified as true minima on the potential energy surfaces by the absence of imaginary frequencies [ 68 , 69 , 70 , 71 ].…”

Section: Resultsmentioning

confidence: 99%

“…Bond order and overlap population are estimated for the free adsorbed gasses as well gas/nano-cage complexes. As the overlap value decreases, the interaction between the two atoms decreases and vice versa whereas the values close to zero mean no interaction while overlapping positive and negative values indicate the bonding and anti-bonding states, respectively [ 71 , 75 , 80 ]. Table 5 concerns the free H 2 S molecule, H 2 S/Be 12 O 12 , and H 2 S/Mg 12 O 12 complexes.…”

Section: Resultsmentioning

confidence: 99%

Mg12O12 and Be12O12 Nanocages as Sorbents and Sensors for H2S and SO2 Gases: A Theoretical Approach

et al. 2022

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Theoretical calculations based on the Density Functional Theory (DFT) have been performed to investigate the interaction of H2S as well SO2 gaseous molecules at the surfaces of Be12O12 and Mg12O12 nano-cages. The results show that a Mg12O12 nano-cage is a better sorbent than a Be12O12 nano-cage for the considered gases. Moreover, the ability of SO2 gas to be adsorbed is higher than that of H2S gas. The HOMO–LUMO gap (Eg) of Be12O12 nano-cage is more sensitive to SO2 than H2S adsorption, while the Eg value of Mg12O12 nano-cage reveals higher sensitivity to H2S than SO2 adsorption. The molecular dynamic calculations show that the H2S molecule cannot be retained at the surface of a Be12O12 nano-cage within 300–700 K and cannot be retained on a Mg12O12 nano-cage at 700 K, while the SO2 molecule can be retained at the surfaces of Be12O12 and Mg12O12 nano-cages up to 700 K. Moreover, the thermodynamic calculations indicate that the reactions between H2S as well SO2 with Be12O12 and Mg12O12 nano-cages are exothermic. Our results suggest that we can use Be12O12 and Mg12O12 nano-cages as sorbents as well as sensors for H2S and SO2 gases.

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Recent Advances in Main Group Coordination Driven Porphyrins: A Comprehensive Review

Dar,

Shahnawaz,

Taneja

et al. 2024

ChemistrySelect

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The novel and exciting class of porphyrin‐based compounds are the main group coordination‐driven porphyrins (MGCPs) with a central main group element into the porphyrin macrocycle. MGCPs have unique properties, reactivity, and potential applications in catalysis, sensing, biomedicine etc. This comprehensive review article discusses recent advances in the field of main group coordination driven porphyrins and explores some of its potential uses in solar cells, catalysis, antimicrobial, optoelectronic devices, sensing, and catalysis. The addition of main group elements to porphyrin systems has resulted in the production of entirely novel compounds that have intriguing qualities including increased stability and catalytic activity. Significant modifications in these unique compounds features are apparent through the analysis of their structural properties. It encompasses FTIR, proton NMR, electrical and optical characterisation in addition to an electrochemical analysis of those parameters. They serve as significant building blocks for the creation of cutting‐edge materials and technologies in a variety of scientific and technical disciplines because to their special qualities and adaptability. Researchers working in the domains of coordination chemistry, catalysis, and materials science will find this study to be of interest since it offers a thorough examination of current developments in main group coordination driven porphyrins and their prospective applications. Overall, main group porphyrins are used in many different fields, such as sensing, catalysis, and optoelectronic devices.

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DFT and TD-DFT studies of halogens adsorption on cobalt-doped porphyrin: Effect of the external electric field

Cited by 28 publications

References 69 publications

Machine Learning-Aided Design of Gold Core–Shell Nanocatalysts toward Enhanced and Selective Photooxygenation

Machine Learning-Aided Design of Gold Core–Shell Nanocatalysts toward Enhanced and Selective Photooxygenation

Mg12O12 and Be12O12 Nanocages as Sorbents and Sensors for H2S and SO2 Gases: A Theoretical Approach

Recent Advances in Main Group Coordination Driven Porphyrins: A Comprehensive Review

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