“…We found that, the bond length C–O for the CO is 1.17 Å and 1.14 Å for LanL2dz and 6-31G(d) basis sets, respectively, this is in good agreement with greenwood [27] and Shalabi et al. [3]. Secondly, the geometrical optimization without any constrains were done for the CO/P.…”
Section: Resultssupporting
confidence: 82%
“…The properties of the adsorbed CO remain close to those of the gas phase, where there is no significant change in C–O bond length, the net charge on CO in CO/P approximately equals to zero, and the CO/P HOMO-LUMO energy gap closes to that of bare porphyrin. Assuming a boundary value of 0.21 eV between physical adsorption and chemical adsorption [3], one can say that, the CO adsorption on P is physisorption and the CO molecule prefers to interact with porphyrin molecule via its carbon head where the adsorption energy value for mode 1 is more negative than that for mode 2.Fig. 2The optimized structures for CO/P complex, calculated at B3LYP/LanL2DZ.…”
Section: Resultsmentioning
confidence: 99%
“…It is one of the most air pollutants. Thus, in order to reduce environmental pollution, it is necessary to use catalysts/sorbents to detect, remove or trap the carbon monoxide [2, 3].…”
The structural, electronic and optical properties of transition metal doped porphyrin (TM@P; TM = Mn, Co, Fe, Cu, Ni, Zn) as well as the effect of CO adsorption on TM@P properties have been investigated using the density functional theory (DFT). The presented results include adsorption energies, bond lengths, electronic configurations, magnetic moments, density of states, frontier molecular orbitals, and UV-Vis. spectra. Our calculation results show that, the CO molecule favors to be adsorbed on TM-doped Porphyrin with its carbon head. The most energetically stable adsorption of CO is reported for Fe doped Porphyrin. The interaction between CO molecules with TM@P is attributed to donation-back donation as well as charge transfer mechanisms. Mn, Co and Fe-doped porphyrins have visible active nature which may be affected by CO adsorption, whereas, Ni, Cu and Zn-doped porphyrins have UV active nature which not affected by CO adsorption. These results may be meaningful for CO removal and detection.
“…We found that, the bond length C–O for the CO is 1.17 Å and 1.14 Å for LanL2dz and 6-31G(d) basis sets, respectively, this is in good agreement with greenwood [27] and Shalabi et al. [3]. Secondly, the geometrical optimization without any constrains were done for the CO/P.…”
Section: Resultssupporting
confidence: 82%
“…The properties of the adsorbed CO remain close to those of the gas phase, where there is no significant change in C–O bond length, the net charge on CO in CO/P approximately equals to zero, and the CO/P HOMO-LUMO energy gap closes to that of bare porphyrin. Assuming a boundary value of 0.21 eV between physical adsorption and chemical adsorption [3], one can say that, the CO adsorption on P is physisorption and the CO molecule prefers to interact with porphyrin molecule via its carbon head where the adsorption energy value for mode 1 is more negative than that for mode 2.Fig. 2The optimized structures for CO/P complex, calculated at B3LYP/LanL2DZ.…”
Section: Resultsmentioning
confidence: 99%
“…It is one of the most air pollutants. Thus, in order to reduce environmental pollution, it is necessary to use catalysts/sorbents to detect, remove or trap the carbon monoxide [2, 3].…”
The structural, electronic and optical properties of transition metal doped porphyrin (TM@P; TM = Mn, Co, Fe, Cu, Ni, Zn) as well as the effect of CO adsorption on TM@P properties have been investigated using the density functional theory (DFT). The presented results include adsorption energies, bond lengths, electronic configurations, magnetic moments, density of states, frontier molecular orbitals, and UV-Vis. spectra. Our calculation results show that, the CO molecule favors to be adsorbed on TM-doped Porphyrin with its carbon head. The most energetically stable adsorption of CO is reported for Fe doped Porphyrin. The interaction between CO molecules with TM@P is attributed to donation-back donation as well as charge transfer mechanisms. Mn, Co and Fe-doped porphyrins have visible active nature which may be affected by CO adsorption, whereas, Ni, Cu and Zn-doped porphyrins have UV active nature which not affected by CO adsorption. These results may be meaningful for CO removal and detection.
“…For the first adsorption mode (a), the CHCl 3 molecule was weakly chemically adsorbed, and for the other modes (b, c, and d), the CHCl 3 molecule was physically adsorbed. The boundary value between the physical and chemical adsorption was considered to be 0.21 eV [50,51]. In mode (a), owing to the chemical interaction, the Fermi level (E FL ) for the cluster was reduced by 0.17 eV, and the dipole moment (D) was increased to 3.05 Debye.…”
Section: Chcl 3 Interaction With the Zn 12 O 12 Nanocagementioning
We investigated the detection of chloroform (CHCl3) using ZnO nanoclusters via density functional theory calculations. The effects of various concentrations of CHCl3, as well as the deposition of O atoms, on the adsorption over ZnO nanoclusters were analyzed via geometric optimizations. The calculated difference between the highest occupied molecular orbital and the lowest unoccupied molecular orbital for ZnO was 4.02 eV. The most stable adsorption characteristics were investigated with respect to the adsorption energy, frontier orbitals, elemental positions, and charge transfer. The results revealed that ZnO nanoclusters with a specific geometry and composition are promising candidates for chloroform-sensing applications.
“…As far as the cluster model is concerned, we follow a procedure previously reported for alkali halide and alkaline earth oxide supports12–18. A finite ionic crystal of 292 point charges was first constructed.…”
ABSTRACT:We have analyzed spin quenching of first row transition metals deposited on (001) defect-free and defect-containing surfaces of MgO insulator and CdO semiconductor by means of density functional calculations and embedded cluster model. Clusters of moderate sizes were embedded in the simulated Coulomb fields that closely approximate the Madelung fields of the host surfaces, and relaxation of ions that surround the defect sites was taken into account. Spin states of metals deposited on the defect free surfaces were maintained as in the isolated metals except for Ti, V, and Co on MgO, and Ti, V, and Cr on CdO. On the defect containing surfaces, spin states were maintained too except for Fe on MgO, and V and Cr on CdO. The metal-support interactions stabilize the low spin state of the adsorbed metal with respect to the isolated metal, but the effect was not in general enough to quench the spin. Spin polarization effects tend to preserve the spin states of the adsorbed metals relative to those of the isolated metals. Although charge transfer took place from the adsorbed metal to the insulator surface, it took place the other way round from the semiconductor surface to the adsorbed metal. The encountered variations in magnetic properties were attributed to the smaller band gap of the semiconductor, and the behavior of a single metal atom adsorbed on a particular surface was a result of a competition between Hund's rule for the adsorbed metal and the formation of a chemical bond at the interface. V
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