Energetic and topological analyses of the oxidation reaction between Mo_n (n = 1, 2) and N₂O

Abstract

The interaction between molybdenum, atom, and dimer, with nitrous oxide has been investigated using density functional theory. The analysis of the potential energy surfaces for both reactions has revealed that a single molybdenum atom can activate the N--O bond of N2O requiring a small activation energy. However, the presence of several intersystem crossings between three different spin states, namely, septet, quintet and triplet states, seems to be the major constraint to the Mo + N2O reaction. Contrarily, the low-lying excited states (triplet and quintet) do not participate in the reaction between the molybdenum dimer and N2O. The latter reaction fully evolves on the singlet spin surface. Three different regions have been distinguished along the pathway: formation of an adduct complex, formation of an inserted compound, and the N2 detachment. The connection between the two first regions has been characterized by the formation of a special complex in which the N--O bond is so weakened that it could be considered as a first step in the insertion process. It has been shown that the topological changes along the pathways provide a clear explanation for the geometrical changes that occur along the reaction pathway. In summary, the detachment of the N2 molecule is found to be kinetically an effective process for both reactions, owing to the high exothermicity and consequently to the high internal energy of the insertion intermediates. However, in the case of Mo atom, the reaction should be a slow process due to the presence of spin-forbidden transitions. These results fully agree with previous experimental works.

The interaction of NOx on Ni(111) surface investigated with quantum-chemical calculations

“…The investigators demonstrated that the NO 2 molecule adsorbs dissociatively on Pt(111), Ru(001), Ag(110), Ag(111) and Pd(111) surfaces at temperatures of about 150 K, but adsorbs molecularly on Au(111) and polycrystalline Au. The N 2 O molecule was studied theoretically with metal atoms [27][28][29] and in the reactions on fcc (111) surfaces of Rh, 30 Pt, 31 Ir 32 and Ni. 33 Nickel is an important electroactive material that displays a great adsorption ability for a molecule such as ethyne 34 relative to Rh, Pd, and Pt, and also a great catalytic ability for steam reforming.…”

3D Dense Convolutional Neural Networks Utilizing Molecular Topological Features for Accurate Atomization Energy Predictions

“…52,53 Additionally, localization functions have been widely used to characterize the bonding nature in transition metal complexes and thus could be an indispensable tool for their tensorial representation. [53][54][55][56][57][58][59][60] The encouraging results in the present article show incredible promise for future endeavors to tackle even more challenging problems. The existing frameworks could be further refined by leveraging recent developments in the field of computer vision.…”

Describing the Molecular Mechanism of Organic Reactions by Using Topological Analysis of Electronic Localization Function

“…BET [37] has been applied to different elementary reactions as proton transfers [36,58], isomerisations [59], electron transfers [60] and studies on two-state reactivity [61][62][63]. A systematic investigation of the mechanism of important organic reactions such as the Diels-Alder reactions [45,46] the 1,3-dipolar reaction between fulminic acid and acetylene [44], the molecular mechanism of the Bergman cyclization [64], the trimerization of acetylene [65] the "chameleonic vs centauric" mechanisms of the Cope rearrangement of 1,5 hexadiene and its cyano derivatives [66] the Nazarov cyclization [67] and the S N 2 reaction [68].…”