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Giovanni F. Caramori - One of the best experts on this subject based on the ideXlab platform.
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Role of the cation Formal Charge in cation–π interaction. A survey involving the [2.2.2]paracyclophane host from relativistic DFT calculations
New Journal of Chemistry, 2020Co-Authors: Alexandre O. Ortolan, Giovanni F. Caramori, Gernot Frenking, Alvaro Muñoz-castroAbstract:The role of the metal Formal Charge in the cation–π interactions has been evaluated with relativistic DFT methods involving a versatile π-cryptating structure, namely [2.2.2]paracyclophane. Our study focuses on experimentally characterized [([2.2.2]pCp)M]n+ systems with M = Ag+ and Sn2+ and their Cd2+ and In+ counterparts, which exhibit 5s05p0 and 5s25p0 electron configurations. The acceptor capabilities increase when the metal Charges go from 1+ to 2+, resulting in a large stabilization of the interaction. For the studied 5s05p0 cations Ag+ and Cd2+, the most stable conformation namely [(η2:η2:η2-[2.2.2]pCp)M]n+, the electrostatic contribution is more favorable by −9.3 kcal mol−1, whereas the ΔEOrb contribution increases by −151.6 kcal mol−1 towards a more favourable situation in the 2+ counterpart. Similarly in the 5s25p0 cationic group, the isoelectronic Sn2+ and In+ systems depict variation of the electrostatic and orbital terms, with a considerable decrease of the stabilizing ΔEOrb contribution, and in a lesser amount the ΔEElstat term. Thus, the variation of the interaction energy between the M+ and M2+ isoelectronic counterparts can be ascribed mainly to the variation of the ΔEOrb term, leading to a more covalent character of the interaction retaining a similar bonding scheme.
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role of the cation Formal Charge in cation π interaction a survey involving the 2 2 2 paracyclophane host from relativistic dft calculations
New Journal of Chemistry, 2015Co-Authors: Alexandre O. Ortolan, Giovanni F. Caramori, Gernot Frenking, Alvaro MunozcastroAbstract:The role of the metal Formal Charge in the cation–π interactions has been evaluated with relativistic DFT methods involving a versatile π-cryptating structure, namely [2.2.2]paracyclophane. Our study focuses on experimentally characterized [([2.2.2]pCp)M]n+ systems with M = Ag+ and Sn2+ and their Cd2+ and In+ counterparts, which exhibit 5s05p0 and 5s25p0 electron configurations. The acceptor capabilities increase when the metal Charges go from 1+ to 2+, resulting in a large stabilization of the interaction. For the studied 5s05p0 cations Ag+ and Cd2+, the most stable conformation namely [(η2:η2:η2-[2.2.2]pCp)M]n+, the electrostatic contribution is more favorable by −9.3 kcal mol−1, whereas the ΔEOrb contribution increases by −151.6 kcal mol−1 towards a more favourable situation in the 2+ counterpart. Similarly in the 5s25p0 cationic group, the isoelectronic Sn2+ and In+ systems depict variation of the electrostatic and orbital terms, with a considerable decrease of the stabilizing ΔEOrb contribution, and in a lesser amount the ΔEElstat term. Thus, the variation of the interaction energy between the M+ and M2+ isoelectronic counterparts can be ascribed mainly to the variation of the ΔEOrb term, leading to a more covalent character of the interaction retaining a similar bonding scheme.
Alvaro Munozcastro - One of the best experts on this subject based on the ideXlab platform.
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role of the cation Formal Charge in cation π interaction a survey involving the 2 2 2 paracyclophane host from relativistic dft calculations
New Journal of Chemistry, 2015Co-Authors: Alexandre O. Ortolan, Giovanni F. Caramori, Gernot Frenking, Alvaro MunozcastroAbstract:The role of the metal Formal Charge in the cation–π interactions has been evaluated with relativistic DFT methods involving a versatile π-cryptating structure, namely [2.2.2]paracyclophane. Our study focuses on experimentally characterized [([2.2.2]pCp)M]n+ systems with M = Ag+ and Sn2+ and their Cd2+ and In+ counterparts, which exhibit 5s05p0 and 5s25p0 electron configurations. The acceptor capabilities increase when the metal Charges go from 1+ to 2+, resulting in a large stabilization of the interaction. For the studied 5s05p0 cations Ag+ and Cd2+, the most stable conformation namely [(η2:η2:η2-[2.2.2]pCp)M]n+, the electrostatic contribution is more favorable by −9.3 kcal mol−1, whereas the ΔEOrb contribution increases by −151.6 kcal mol−1 towards a more favourable situation in the 2+ counterpart. Similarly in the 5s25p0 cationic group, the isoelectronic Sn2+ and In+ systems depict variation of the electrostatic and orbital terms, with a considerable decrease of the stabilizing ΔEOrb contribution, and in a lesser amount the ΔEElstat term. Thus, the variation of the interaction energy between the M+ and M2+ isoelectronic counterparts can be ascribed mainly to the variation of the ΔEOrb term, leading to a more covalent character of the interaction retaining a similar bonding scheme.
Alexandre O. Ortolan - One of the best experts on this subject based on the ideXlab platform.
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Role of the cation Formal Charge in cation–π interaction. A survey involving the [2.2.2]paracyclophane host from relativistic DFT calculations
New Journal of Chemistry, 2020Co-Authors: Alexandre O. Ortolan, Giovanni F. Caramori, Gernot Frenking, Alvaro Muñoz-castroAbstract:The role of the metal Formal Charge in the cation–π interactions has been evaluated with relativistic DFT methods involving a versatile π-cryptating structure, namely [2.2.2]paracyclophane. Our study focuses on experimentally characterized [([2.2.2]pCp)M]n+ systems with M = Ag+ and Sn2+ and their Cd2+ and In+ counterparts, which exhibit 5s05p0 and 5s25p0 electron configurations. The acceptor capabilities increase when the metal Charges go from 1+ to 2+, resulting in a large stabilization of the interaction. For the studied 5s05p0 cations Ag+ and Cd2+, the most stable conformation namely [(η2:η2:η2-[2.2.2]pCp)M]n+, the electrostatic contribution is more favorable by −9.3 kcal mol−1, whereas the ΔEOrb contribution increases by −151.6 kcal mol−1 towards a more favourable situation in the 2+ counterpart. Similarly in the 5s25p0 cationic group, the isoelectronic Sn2+ and In+ systems depict variation of the electrostatic and orbital terms, with a considerable decrease of the stabilizing ΔEOrb contribution, and in a lesser amount the ΔEElstat term. Thus, the variation of the interaction energy between the M+ and M2+ isoelectronic counterparts can be ascribed mainly to the variation of the ΔEOrb term, leading to a more covalent character of the interaction retaining a similar bonding scheme.
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role of the cation Formal Charge in cation π interaction a survey involving the 2 2 2 paracyclophane host from relativistic dft calculations
New Journal of Chemistry, 2015Co-Authors: Alexandre O. Ortolan, Giovanni F. Caramori, Gernot Frenking, Alvaro MunozcastroAbstract:The role of the metal Formal Charge in the cation–π interactions has been evaluated with relativistic DFT methods involving a versatile π-cryptating structure, namely [2.2.2]paracyclophane. Our study focuses on experimentally characterized [([2.2.2]pCp)M]n+ systems with M = Ag+ and Sn2+ and their Cd2+ and In+ counterparts, which exhibit 5s05p0 and 5s25p0 electron configurations. The acceptor capabilities increase when the metal Charges go from 1+ to 2+, resulting in a large stabilization of the interaction. For the studied 5s05p0 cations Ag+ and Cd2+, the most stable conformation namely [(η2:η2:η2-[2.2.2]pCp)M]n+, the electrostatic contribution is more favorable by −9.3 kcal mol−1, whereas the ΔEOrb contribution increases by −151.6 kcal mol−1 towards a more favourable situation in the 2+ counterpart. Similarly in the 5s25p0 cationic group, the isoelectronic Sn2+ and In+ systems depict variation of the electrostatic and orbital terms, with a considerable decrease of the stabilizing ΔEOrb contribution, and in a lesser amount the ΔEElstat term. Thus, the variation of the interaction energy between the M+ and M2+ isoelectronic counterparts can be ascribed mainly to the variation of the ΔEOrb term, leading to a more covalent character of the interaction retaining a similar bonding scheme.
Gernot Frenking - One of the best experts on this subject based on the ideXlab platform.
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Role of the cation Formal Charge in cation–π interaction. A survey involving the [2.2.2]paracyclophane host from relativistic DFT calculations
New Journal of Chemistry, 2020Co-Authors: Alexandre O. Ortolan, Giovanni F. Caramori, Gernot Frenking, Alvaro Muñoz-castroAbstract:The role of the metal Formal Charge in the cation–π interactions has been evaluated with relativistic DFT methods involving a versatile π-cryptating structure, namely [2.2.2]paracyclophane. Our study focuses on experimentally characterized [([2.2.2]pCp)M]n+ systems with M = Ag+ and Sn2+ and their Cd2+ and In+ counterparts, which exhibit 5s05p0 and 5s25p0 electron configurations. The acceptor capabilities increase when the metal Charges go from 1+ to 2+, resulting in a large stabilization of the interaction. For the studied 5s05p0 cations Ag+ and Cd2+, the most stable conformation namely [(η2:η2:η2-[2.2.2]pCp)M]n+, the electrostatic contribution is more favorable by −9.3 kcal mol−1, whereas the ΔEOrb contribution increases by −151.6 kcal mol−1 towards a more favourable situation in the 2+ counterpart. Similarly in the 5s25p0 cationic group, the isoelectronic Sn2+ and In+ systems depict variation of the electrostatic and orbital terms, with a considerable decrease of the stabilizing ΔEOrb contribution, and in a lesser amount the ΔEElstat term. Thus, the variation of the interaction energy between the M+ and M2+ isoelectronic counterparts can be ascribed mainly to the variation of the ΔEOrb term, leading to a more covalent character of the interaction retaining a similar bonding scheme.
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role of the cation Formal Charge in cation π interaction a survey involving the 2 2 2 paracyclophane host from relativistic dft calculations
New Journal of Chemistry, 2015Co-Authors: Alexandre O. Ortolan, Giovanni F. Caramori, Gernot Frenking, Alvaro MunozcastroAbstract:The role of the metal Formal Charge in the cation–π interactions has been evaluated with relativistic DFT methods involving a versatile π-cryptating structure, namely [2.2.2]paracyclophane. Our study focuses on experimentally characterized [([2.2.2]pCp)M]n+ systems with M = Ag+ and Sn2+ and their Cd2+ and In+ counterparts, which exhibit 5s05p0 and 5s25p0 electron configurations. The acceptor capabilities increase when the metal Charges go from 1+ to 2+, resulting in a large stabilization of the interaction. For the studied 5s05p0 cations Ag+ and Cd2+, the most stable conformation namely [(η2:η2:η2-[2.2.2]pCp)M]n+, the electrostatic contribution is more favorable by −9.3 kcal mol−1, whereas the ΔEOrb contribution increases by −151.6 kcal mol−1 towards a more favourable situation in the 2+ counterpart. Similarly in the 5s25p0 cationic group, the isoelectronic Sn2+ and In+ systems depict variation of the electrostatic and orbital terms, with a considerable decrease of the stabilizing ΔEOrb contribution, and in a lesser amount the ΔEElstat term. Thus, the variation of the interaction energy between the M+ and M2+ isoelectronic counterparts can be ascribed mainly to the variation of the ΔEOrb term, leading to a more covalent character of the interaction retaining a similar bonding scheme.
Gianfranco Pacchioni - One of the best experts on this subject based on the ideXlab platform.
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Metal Deposition on Oxide Surfaces: A Quantum-Chemical Study of the Interaction of Rb, Pd, and Ag Atoms with the Surface Vacancies of MgO
The Journal of Physical Chemistry, 1996Co-Authors: Anna Maria Ferrari, Gianfranco PacchioniAbstract:The interaction of Rb, Pd, and Ag atoms with the surface vacancies of MgO, the Fs and the Vs centers, has been studied by ab initio cluster model wave functions. We have considered the interaction of each atom with Fs, Fs+, Fs2+, Vs, Vs-, and Vs2- sites. These sites correspond to the removal of O, O-, O2-, Mg, Mg+, and Mg2+ atoms or ions, respectively, from the surface. The bond with the metal atoms, which is found to be very weak on the regular surface sites, can be very different depending of the Formal Charge of the vacancy. Neutral Fs centers are in general rather unreactive as their electronic structure resembles that of the regular surface; Fs+ paramagnetic centers have a relatively large electron affinity and tend to ionize metal atoms with low ionization potentials, such as alkali-metal atoms or to form covalent polar bonds with the adsorbed metal atoms; Fs2+ centers have a very high electron affinity so that all metal atoms are ionized when interacting with these sites. Neutral Vs sites are also ...