DFT, NBO, HOMO-LUMO, NCI, stability, Fukui function and hole – Electron analyses of tolcapone

Isravel, Antony Danish; Jeyaraj, Jebasingh Kores; Thangasamy, Sasitha; John, Winfred Jebaraj

doi:10.1016/j.comptc.2021.113296

Cited by 62 publications

(16 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Natural bond order (NBO) analysis is known for describing phenomena involving electron density transfer, such as intermolecular forces , and interactions between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), , which are related to stabilization energy ( E (2)), estimated by the second-order perturbative approach E ( 2 ) = q i false[ F ( i , j ) false] 2 ε j − ε i in which q i is the occupancy of the bond orbital, ε j and ε i are the energies of the natural orbitals (acceptor and donor, respectively), and F ( i , j ) is the Fock operator. − An NBO analysis was done for the frontier orbital interactions in the transition states (TSs), using NBO 3.1 software (included in Gaussian 09 software). Atomic partial charges were calculated using different models: Mulliken (MPA), charges from electrostatic potentials using a grid-based method (CHELPG), Hirshfeld (HPA), − its improvement, proposed by Marenich et al (called CM5), and natural charges (NPA) at the ωB97X-D/6-31G(d,p)-LANL2DZ-PCM level (water and acetonitrile solvents).…”

Section: Methodsmentioning

confidence: 99%

“…Natural bond order (NBO) analysis is known for describing phenomena involving electron density transfer, such as intermolecular forces 20 , 21 and interactions between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), 22 , 23 which are related to stabilization energy ( E (2)), estimated by the second-order perturbative approach in which q i is the occupancy of the bond orbital, ε j and ε i are the energies of the natural orbitals (acceptor and donor, respectively), and F ( i , j ) is the Fock operator. 24 − 28 An NBO analysis was done for the frontier orbital interactions in the transition states (TSs), using NBO 3.1 software 29 (included in Gaussian 09 software 30 ).…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical Investigation of Regiodivergent Addition of Anilines and Phenolates to p-Benzoquinone Ring

et al. 2022

View full text Add to dashboard Cite

Two different products were obtained by the regiodivergent reaction of benzoquinone derivatives with phenolates and anilines: 3-aryloxybenzoquinone and 2-phenylamino-3-bromobenzoquinone. Calculated density functional theory free energies of reaction values corroborate the experimental observation of the formation of the substitution product in the reaction with phenolates in acetonitrile and the product of addition/oxidation for the reaction with aniline in water. Calculated charges and Fukui functions are similar for C2 and C3 atoms, indicating an equal possibility to suffer a nucleophilic attack. The calculated energy barriers for nucleophilic attack steps indicated that the first steps of the substitution with phenolates and addition/oxidation with anilines are faster, which justifies the formation of the respective products. The natural bond order analysis for the transition states revealed that there is a strong interaction between lone pairs of N and O atoms and the πC2C3 * for the O → C2 and N → C3 attacks and a weak interaction for the O → C3 and N → C2 attacks, which also agrees with experimental observations.

show abstract

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Theoretical Investigation of Regiodivergent Addition of Anilines and Phenolates to p-Benzoquinone Ring

et al. 2022

View full text Add to dashboard Cite

show abstract

“…The NBO calculations were conducted using NBO 3.1 module embedded in Gaussian09W (Bassey et al, 2022). Highest occupied and lowest unoccupied molecular orbital (HOMO and LUMO) isosurface maps were plotted using Multiwfn 3.7 dev software (Isravel et al, 2021). Origin 8.0 Pro was used for charge analysis.…”

Section: Methodsmentioning

confidence: 99%

Experimental, DFT, molecular docking and in silico ADMET studies of cadmium-benzenetricarboxylates

et al. 2022

View full text Add to dashboard Cite

The structure of the polymer [Cd(BTC)(H2O)2]n was identified by X-ray single-crystal crystallography. The complex’s stability and overall reactivity were examined at the B3LYP/6-311++G (d,p) level of theory whereas the lighter elements (H, C, and O) were studied using the LanL2DZ basis set. The electron distribution in the complex’s highest occupied molecular orbital is solely concentrated in a small area, with no electrons distributed over the cadmium. Consequently, the electrons in the complex’s lowest unoccupied molecular orbital (LUMO) were dispersed equally. The Cd atom is partially obscured by charge delocalization in the LUMO. The natural bond orbital analysis supports the result for reactivity studies. The rate of absorption, distribution, metabolism, excretion, and toxicity (ADMET) of the complex evaluated by molecular docking in a bid allowed comprehend the biological applicability. The [Cd(BTC)(H2O)2]n exhibited excellent binding affinity with proteins 1D7U and 2XCS, while by ADMET it is suggested that cytotoxicity and carcinogenicity were inactive. It is clearly shown that the complex has strong biological uses, notably for the treatment of microbial diseases.

show abstract

“…e figure shows a high degree of overlap between holes and electrons in the ligand as they widely spread over the entire molecule specifically on O and N (of the isoxazole ring), S (thiophene ring), and N (azomethine bond), respectively. By combining hole-electron maps and the indices, it can be deduced that the ligand excitation S 0 ⟶ S 1 may be regarded as a CT excitation characterized by large values of S r (0.759 Å) and D index (0.360 Å) [76] as reported in Table 8.…”

Section: Electron Excitation Analysismentioning

confidence: 99%

Theoretical Study of the Structural, Optoelectronic, and Reactivity Properties of N-[5′-Methyl-3′-Isoxasolyl]-N-[(E)-1-(-2-)]Methylidene] Amine and Some of Its Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ Complexes for OLED and OFET Applications

Tendongmo

Tasheh

Fouégué³

et al. 2022

Journal of Chemistry

View full text Add to dashboard Cite

Herein, we report the structural, electronic, and charge transfer properties of N-[5′-methyl-3′-isoxasolyl]-N-[(E)-1-(-2-thiophene)] methylidene] amine (L) and its Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ complexes (dubbed A, B, C, D, and E, respectively) using the density functional theory (DFT). All molecules investigated were optimized at the BP86/def2-TZVP/RI level of theory. Single point energy calculations were carried out at the M06-D3ZERO/def2-TZVP/RIJCOSX level of theory. Reorganization energies of the hole and electron (λh and λe) and the charge transfer mobilities of the electron and hole (μe and μh) have been computed and reported. The λe and λh values vary in the order D > E > A > B > C > L and E > A > D > L > C > B, respectively, while μe and μh vary in the order B > C > L > A > E > D and C > B > A > L > E > D, respectively. μh of B (39.5401 cm2·V−1S−1) and C (366.4740 cm2·V−1s−1) is remarkably large, suggesting their application in organic light-emitting diode (OLED) and organic field-effect transistor (OFET) technologies. Electron excitation analysis based on time-dependent (TD)-DFT calculations revealed that charge transfer excitations may significantly affect charge transfer mobilities. Based on charge transfer mobility results, B and C are outstanding and are promising molecules for the manufacture of electron and hole-transport precursor materials for the construction of OLED and OFET devices as compared to L. The results also show that L and all its complexes interestingly have higher third-order NLO activity than those of para-nitroaniline, a prototypical NLO molecule.

show abstract

DFT, NBO, HOMO-LUMO, NCI, stability, Fukui function and hole – Electron analyses of tolcapone

Cited by 62 publications

References 28 publications

Theoretical Investigation of Regiodivergent Addition of Anilines and Phenolates to p-Benzoquinone Ring

Theoretical Investigation of Regiodivergent Addition of Anilines and Phenolates to p-Benzoquinone Ring

Experimental, DFT, molecular docking and in silico ADMET studies of cadmium-benzenetricarboxylates

Theoretical Study of the Structural, Optoelectronic, and Reactivity Properties of N-[5′-Methyl-3′-Isoxasolyl]-N-[(E)-1-(-2-)]Methylidene] Amine and Some of Its Fe2+, Co2+, Ni2+, Cu2+, and Zn2+ Complexes for OLED and OFET Applications

Contact Info

Product

Resources

About