A DFT study of the reactions of the Cu+ ion with methylamine and dimethylamine

Cheng, Wei; Zhang, Dongju; Zhang, Changqiao

doi:10.1016/j.theochem.2008.10.027

Cited by 5 publications

(3 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The obtained lattice constants were a = b = 4.572 Å, c = 7.018 Å for PbI 2 and 6.337 Å for MAPbI 3 , which agree well with their experimental values of a = b = 4.558 Å, c = 6.986 Å and a = 6.329 Å, respectively (Figure ). We also performed atomic relaxations of the isolated CH 3 NH 2 molecule, for which the bond lengths are 1.101, 1.020, and 1.475 Å for C–H, N–H, and C–N bonds, in good agreement with the previous theoretical and experimental values of 1.093, 1.011, and 1.474 Å (Figure S1). These indicate that the calculations undertaken here could provide a reasonable description for the systems under study.…”

Section: Resultssupporting

confidence: 86%

Ab Initio Thermodynamic Study of PbI₂ and CH₃NH₃PbI₃ Surfaces in Reaction with CH₃NH₂ Gas for Perovskite Solar Cells

Kim¹,

Ri²,

Kye³

et al. 2022

J. Phys. Chem. C

View full text Add to dashboard Cite

Hybrid organic–inorganic halide perovskites for photovoltaics have attracted research interest due to their unique material properties, but suffer from poor material stability. In this work, we investigated the surface phase diagrams of PbI2 and cubic CH3NH3PbI3 (MAPbI3) for a better understanding of the precursor effect on perovskite synthesis via solid–gas reaction, by density functional theory calculations combined with thermodynamics. Using the devised slab models of PbI2(001) and MAPbI3(100), (110), and (111) surfaces with perfect and various vacant defect terminations, we calculated their formation energies and the adsorption energies of the CH3NH2 molecule on the PbI2(001) surfaces under different synthesis conditions of temperature, pressure, and pH via chemical potentials of species. Our calculations revealed that the adsorption can be facilitated by including the HI or NH4I molecule by dissociation of this additive and formation of the CH3NH3 + cation or NH3–CH3NH3 + complex, which is beneficial for conversion of PbI2 to MAPbI3 via solid–gas reaction. Furthermore, we found that among different perovskite MAPbI3 surfaces, the MA-terminated (110) and MAI-terminated (100) surfaces are placed in the thermodynamically stable region of the chemical potentials at pH values of 1 and 6, agreeing well with the experimental findings. We believe this work gives a fundamental understanding of the solid–gas reaction for high-crystallinity perovskite synthesis towards perovskite solar cells with improved stability.

show abstract

Section: Resultssupporting

confidence: 86%

Ab Initio Thermodynamic Study of PbI₂ and CH₃NH₃PbI₃ Surfaces in Reaction with CH₃NH₂ Gas for Perovskite Solar Cells

Kim¹,

Ri²,

Kye³

et al. 2022

J. Phys. Chem. C

View full text Add to dashboard Cite

show abstract

“…The obtained lattice constants were a = b = 4.572 Å, c = 7.018 Å for PbI 2 and 6.337 Å for MAPbI 3 , which agree well with their experimental values of a = b = 4.558 Å, c = 6.986 Å [39] and a = 6.329 Å [40], respectively (Figure 1). We also performed atomic relaxations of the isolated CH 3 NH 2 molecule, for which the bond lengths are 1.101, 1.020 and 1.475 Å for C−H, N−H and C−N bonds in good agreement with the previous theoretical and experimental values of 1.093, 1.011 and 1.474 Å [41] (Figure S1). These indicate that the calculations undertaken here could provide reasonable description for the systems under study.…”

Section: Surface Phase Diagram Of Pbi 2 Surfacesupporting

confidence: 85%

Ab Initio Thermodynamic Study of PbI$_2$ and CH$_3$NH$_3$PbI$_3$ Surfaces in Reaction with CH$_3$NH$_2$ Gas for Perovskite Solar Cells

Kim¹,

Ri²,

Kye³

et al. 2021

Preprint

View full text Add to dashboard Cite

Hybrid organic-inorganic halide perovskites for photovoltaics have attracted research interest due to their unique material properties, but suffered from poor material stability. In this work, we investigated the surface phase diagrams of PbI 2 and cubic CH 3 NH 3 PbI 3 (MAPbI 3 ) for a better understanding of precursor effect on perovskite synthesis via solid-gas reaction, by density functional theory calculations combined with thermodynamics. Using the devised slab models of PbI 2 (001) and MAPbI 3 (100), ( 110) and ( 111) surfaces with perfect and various vacant defect terminations, we calculated their formation energies and adsorption energies of CH 3 NH 2 molecule on the PbI 2 (001) surfaces under different synthesis conditions of temperature, pressure and pH via chemical potentials of species. Our calculations revealed that the adsorption can be facilitated by including HI or NH 4 I molecule by dissociation of this additive and formation of CH 3 NH + 3 cation or NH 3 -CH 3 NH + 3 complex, which is beneficial for conversion of PbI 2 to MAPbI 3 via solid-gas reaction. Furthermore, we found that among different perovskite MAPbI 3 surfaces, the MA-terminated (110) and MAI-terminated (100) surfaces are placed on the thermodynamically stable region of chemical potentials at pH values of 1 and 6, being agreed well with the experimental findings. We believe this work gives a fundamental understanding of solid-gas reaction for high-crystallinity perovskite synthesis towards perovskite solar cells with improved stability.

show abstract

“…(3) and (4). We have scanned the details of the PES relevant for these two reactions along three possible entrances in our recent work 35: Cu + abstracting the H atom at the methyl, Cu + inserting the CH bond, and the Cu + inserting the NH bond. The calculated results show that the transition‐state structure along the NH bond insertion pathway did not located, despite careful searches, whereas the CH insertion pathway is found to be energetically less favorable than the H‐abstraction pathway: the transition‐state structures for Cu + inserting the CH bonds of MA and DMA are calculated to be less stable by 37.3 and 31.8 kJ mol −1 than the H‐abstracting transition state.…”

Section: Resultsmentioning

confidence: 99%

A comparative theoretical study of the reactivities of the Al⁺ and Cu⁺ ions toward methylamine and dimethylamine

Liu

Zhang

et al. 2009

Int J of Quantum Chemistry

Self Cite

View full text Add to dashboard Cite

A very recent laser ablation-molecular beam experiment shows that an Al ϩ ion can react with a single methylamine (MA, CH 3 NH 2 ) or dimethylamine (DMA, (CH 3 ) 2 NH) molecule to form a 1:1 ion-molecule complex Al ϩ [CH 3 NH 2 ] or Al ϩ [(CH 3 ) 2 NH)], whereas a dehydrogenated complex ion Cu ϩ [CH 3 N] or Cu ϩ [C 2 H 5 N] is detected, respectively, in the similar reaction for a Cu ϩ ion. Here, we show a comparative density functional theory study for the reactivities of the Al ϩ and Cu ϩ ions toward MA and DMA to reveal the intrinsic mechanism. It is found that the interactions of the Al ϩ ion with MA and DMA are mostly electrostatic, leading to the direct ion-molecule complexes, Al ϩ ONH 2 CH 3 and Al ϩ ONH(CH 3 ) 2 , in contrast to the non-negligible covalent character in the corresponding Cu ϩ -containing complexes, Cu ϩ ONH 2 CH 3 and Cu ϩ ONH(CH 3 ) 2 . The general dehydrogenation mechanism for MA and DMA promoted by the Cu ϩ ion has been shown, and the preponderant structures contributing to the mass spectra of the product ions Cu ϩ [CH 3 N] and Cu ϩ [C 2 H 5 N] are rationalized as Cu ϩ ONHCH 2 and Cu ϩ ON(CH 2 )(CH 3 ). The presumed dehydrogenation reactions are also discussed for the Al ϩ -containing systems. However, the involved barriers are found to be too high to be overcome at low energy conditions. These results have rationalized all the experimental observations well. FIGURE 5. Calculated minimum energy paths for forming the dehydrogenation products ions Al ϩ (C 2 H 5 N) andCu ϩ (C 2 H 5 N). Numbers refer to the relative stability (in kJ/mol) with respect to the separated reactants calculated at the B3LYP/6-311ϩG(d,p) level.

show abstract

A DFT study of the reactions of the Cu+ ion with methylamine and dimethylamine

Cited by 5 publications

References 25 publications

Ab Initio Thermodynamic Study of PbI₂ and CH₃NH₃PbI₃ Surfaces in Reaction with CH₃NH₂ Gas for Perovskite Solar Cells

Ab Initio Thermodynamic Study of PbI₂ and CH₃NH₃PbI₃ Surfaces in Reaction with CH₃NH₂ Gas for Perovskite Solar Cells

Ab Initio Thermodynamic Study of PbI$_2$ and CH$_3$NH$_3$PbI$_3$ Surfaces in Reaction with CH$_3$NH$_2$ Gas for Perovskite Solar Cells

A comparative theoretical study of the reactivities of the Al⁺ and Cu⁺ ions toward methylamine and dimethylamine

Contact Info

Product

Resources

About

A DFT study of the reactions of the Cu+ ion with methylamine and dimethylamine

Cited by 5 publications

References 25 publications

Ab Initio Thermodynamic Study of PbI2 and CH3NH3PbI3 Surfaces in Reaction with CH3NH2 Gas for Perovskite Solar Cells

Ab Initio Thermodynamic Study of PbI2 and CH3NH3PbI3 Surfaces in Reaction with CH3NH2 Gas for Perovskite Solar Cells

Ab Initio Thermodynamic Study of PbI$_2$ and CH$_3$NH$_3$PbI$_3$ Surfaces in Reaction with CH$_3$NH$_2$ Gas for Perovskite Solar Cells

A comparative theoretical study of the reactivities of the Al+ and Cu+ ions toward methylamine and dimethylamine

Contact Info

Product

Resources

About

Ab Initio Thermodynamic Study of PbI₂ and CH₃NH₃PbI₃ Surfaces in Reaction with CH₃NH₂ Gas for Perovskite Solar Cells

Ab Initio Thermodynamic Study of PbI₂ and CH₃NH₃PbI₃ Surfaces in Reaction with CH₃NH₂ Gas for Perovskite Solar Cells

A comparative theoretical study of the reactivities of the Al⁺ and Cu⁺ ions toward methylamine and dimethylamine