A comprehensive decomposition analysis of stabilization energy (CDASE) and its application in locating the rate-determining step of multi-step reactions

Abstract

Stabilization energy, as proposed by Parr and Pearson (J. Am. Chem. Soc., 1983, 105, 7512) is decomposed into fragments. When the donor is not a perfect one and both the donor and the acceptor are ordinary organic molecules this decomposition is shown to provide energy fragments which, individually, can be correlated to the reaction rate of that particular step. It is shown how these different energy fragments can be used, together with the global electrophilicity value of the acceptor (w(A)), to locate the rate-determining step in multi-step reactions.

The analysis of electronic structures, adsorption properties, NBO, QTAIM and NMR parameters of the adsorbed hydrogen sulfide on various sites of the outer surface of aluminum phosphide nanotube: a DFT study

“…In the present study, kinetic aspects of the interaction between the AlPNT and the H 2 S gas molecule are investigated by using Dw (i.e., the difference of global electrophilicity values between the acceptors and the donors) and DE B(A) , whereas DE A(B) and DE SE (AB) are exploited to understand the thermodynamic stability of the resultant adducts. It is worth mentioning that the electron transfer values (i.e., DN) are used to explain both the rate of interaction and the stability of adducts as it is formally linked to all the kinetic and thermodynamic descriptors [37][38][39][40]. According to our theoretical results, we concluded that the H 2 S gas is B (i.e., donor) and the AlPNT is A (i.e., acceptor).…”

“…Also, E def AlPNT and E def H 2 S are the deformation energy of the nanotube and H 2 S gas molecule in complex, respectively. Roy et al [37,38] proposed modified expression of stabilization energy (SE) as well as its different components when interaction happens between donors and acceptors with a comparable size. The interaction of the H 2 S gas and the AlPNT on the basis of five reactivity descriptors (i.e., Dw, DN, DE B (A) , DE A (B) and DE SE (AB) ) has been explained.…”

“…DE B(A) can be used to study the kinetics, whereas DE A(B) is for thermodynamics of chemical reactions [37,38]. In the present study, kinetic aspects of the interaction between the AlPNT and the H 2 S gas molecule are investigated by using Dw (i.e., the difference of global electrophilicity values between the acceptors and the donors) and DE B(A) , whereas DE A(B) and DE SE (AB) are exploited to understand the thermodynamic stability of the resultant adducts.…”

Study of noncovalent interactions of end-caped sulfur-doped carbon nanotubes using DFT, QTAIM, NBO and NCI calculations

“…6) or net electron transfers (DN, Eq. 7) in donor-acceptor systems [43,44]. These equations have been employed in recent reports for simple organic molecules [45,46] and nanostructures [43,47].…”

“…Table 4 has provided the values of HOMO and LUMO energy, the energy gap between them and reactivity parameters such as chemical potential, hardness, softness and electrophilicity indexes for CNTs, SCNTs and S2CNTs. Moreover, based on the works of Roy and coworkers [43][44][45][46][47], stabilization energies and net electron transfers (obtained from chemical potentials and chemical hardnesses) in all donor-acceptor systems were calculated and the results are listed in Table 5. In addition, DOS plot for each CNT and SCNT (alone, without adsorbate) are shown in Fig.…”