On the Validity of the Maximum Hardness Principle and the Minimum Electrophilicity Principle during Chemical Reactions

Pan, Sudip; Solà, Miquel; Chattaraj, Pratim Kumar

doi:10.1021/jp312750n

Cited by 163 publications

(89 citation statements)

References 93 publications

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“…67 The hardness value of the product is generally greater than that of the reactants for an exothermic process. 68 The HOMO−LUMO gap values of the bare BeCN 2 and BeNBO clusters are 6.78 and 7.96 eV, respectively. These values are improved significantly upon binding with Ng (Table 1).…”

Section: ■ Computational Detailsmentioning

confidence: 96%

In Quest of Strong Be–Ng Bonds among the Neutral Ng–Be Complexes

et al. 2013

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The global minimum geometries of BeCN2 and BeNBO are linear BeN-CN and BeN-BO, respectively. The Be center of BeCN2 binds He with the highest Be-He dissociation energy among the studied neutral He-Be complexes. In addition, BeCN2 can be further tuned as a better noble gas trapper by attaching it with any electron-withdrawing group. Taking BeO, BeS, BeNH, BeNBO, and BeCN2 systems, the study at the CCSD(T)/def2-TZVP level of theory also shows that both BeCN2 and BeNBO systems have higher noble gas binding ability than those related reported systems. ΔG values for the formation of NgBeCN2/NgBeNBO (Ng = Ar-Rn) are negative at room temperature (298 K), whereas the same becomes negative at low temperature for Ng = He and Ne. The polarization plus the charge transfer is the dominating term in the interaction energy.

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Section: ■ Computational Detailsmentioning

confidence: 96%

In Quest of Strong Be–Ng Bonds among the Neutral Ng–Be Complexes

et al. 2013

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“…14 Several pericyclic reactions were studied 15 to assess the applicability of electronic structure principles towards the prediction of Woodward-Hoffmann rules and it was concluded that these principles are consistent with the predictions of Woodward-Hoffmann rules on transition states (TSs) associated with the symmetry-forbidden disrotation and symmetry-allowed conrotation. In fact, most of the non-totally symmetric vibrations obey the MHP well due to the near constant value of chemical potential and external potential during nuclear displacements.…”

Section: Introductionmentioning

confidence: 94%

Analyzing torquoselectivity in electrocyclic ring opening reactions of trans-3,4-dimethylcyclobutene and 3-formylcyclobutene through electronic structure principles

Morales-Bayuelo

Pan

Caballero

et al. 2015

Phys. Chem. Chem. Phys.

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The validity of maximum hardness, minimum electrophilicity and minimum polarizability principles is assessed to explain the phenomenon of torquoselectivity (inward and outward preference) in the conrotatory ring opening reactions of trans-3,4-dimethylcyclobutene into Z,Z- and E,E-butadienes and 3-formylcyclobutene into E- and Z-2,4-pentadienals. The hardness, average polarizability and electrophilicity profiles are computed along the intrinsic reaction coordinate and divided into three relevant stages. The transition states involved in the unfavorable inward conrotation of trans-3,4-dimethylcyclobutene and in the unfavorable outward conrotation of 3-formylcyclobutene are found to be higher in energy, softer, more electrophilic and more polarizable than the transition states corresponding to the torquoselective outward and inward conrotations, respectively. These observations are in conformity with the maximum hardness, minimum electrophilicity and minimum polarizability principles. The sharp changes in the local reactivity descriptors are also observed around the transition states in their respective profiles.

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“…Hence, it reflects the electronic stability of a system. It may be noted that as HOMO-LUMO energy gap of a system is a measure of hardness, the stability is connected with the maximum hardness principle (MHP) [100][101][102]. The HOMO-LUMO energy gap in CB[6] is quite high (10.81 eV) reflecting its high stability.…”

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confidence: 99%

Cucurbit[6]uril: A Possible Host for Noble Gas Atoms

2015

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Density functional and ab initio molecular dynamics studies are carried out to investigate the stability of noble gas encapsulated cucurbit[6]uril (CB[6]) systems. Interaction energy, dissociation energy and dissociation enthalpy are calculated to understand the efficacy of CB[6] in encapsulating noble gas atoms. CB[6] could encapsulate up to three Ne atoms having dissociation energy (zero-point energy corrected) in the range of 3.4-4.1 kcal/mol, whereas due to larger size, only one Ar or Kr atom encapsulated analogues would be viable. The dissociation energy value for the second Ar atom is only 1.0 kcal/mol. On the other hand, the same for the second Kr is -0.5 kcal/mol, implying the instability of the system. The noble gas dissociation processes are endothermic in nature, which increases gradually along Ne to Kr. Kr encapsulated analogue is found to be viable at room temperature. However, low temperature is needed for Ne and Ar encapsulated analogues. The temperature-pressure phase diagram highlights the region in which association and dissociation processes of Kr@CB[6] would be favorable. At ambient temperature and pressure, CB[6] may be used as an effective noble gas carrier. Wiberg bond indices, noncovalent interaction indices, electron density, and energy decomposition analyses are used to explore the nature of interaction between noble gas atoms and CB[6]. Dispersion interaction is found to be the most important term in the attraction energy. Ne and Ar atoms in one Ng entrapped analogue are found to stay inside the cavity of CB[6] throughout the simulation at 298 K. However, during simulation Ng2 units in Ng2@CB[6] flip toward the open faces of CB[6]. After 1 ps, one Ne atom of Ne3@CB[6] almost reaches the open face keeping other two Ne atoms inside. At lower temperature (77 K), all the Ng atoms in Ngn@CB[6] remain well inside the cavity of CB[6] throughout the simulation time (1 ps).

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On the Validity of the Maximum Hardness Principle and the Minimum Electrophilicity Principle during Chemical Reactions

Cited by 163 publications

References 93 publications

In Quest of Strong Be–Ng Bonds among the Neutral Ng–Be Complexes

In Quest of Strong Be–Ng Bonds among the Neutral Ng–Be Complexes

Analyzing torquoselectivity in electrocyclic ring opening reactions of trans-3,4-dimethylcyclobutene and 3-formylcyclobutene through electronic structure principles

Cucurbit[6]uril: A Possible Host for Noble Gas Atoms

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