Metallophilic interaction is a unique type of weak intermolecular interaction,where the electronic configuration of two metal atoms is closed shell.Despite its significance in multidisciplinary fields,the nature of me...Metallophilic interaction is a unique type of weak intermolecular interaction,where the electronic configuration of two metal atoms is closed shell.Despite its significance in multidisciplinary fields,the nature of metallophilic interaction is still not well understood.In this work,we investigated the electronic structures and bonding characteristic of bimetallic Au2@Cu6 nanocluster through density functional theory method,which was reported in experiments recently[Angew.Chem.Int.Ed.55,3611(2016)].In general thinking,interaction between two moieties of(CuSH)6 ring and(Au2PH3)2 in the Au2@Cu6 nanocluster can be viewed as a d^10-σ closed-shell interaction.However,chemical bonding analysis shows that there is a ten center-two electron(10c-2e)multicenter bonding between two moieties.Further comparative studies on other bimetallic nanocluster M2@Cu6(M=Ag,Cu,Zn,Cd,Hg)also revealed that multicenter bonding is the origin of electronic stability of the complexes besides the d10-σclosed-shell interaction.This will provide valuable insights into the understanding of closed-shell interactions.展开更多
Dissociation of molecular hydrogen （H2） is extensively studied to understand the mechanism of hydrogenation reactions. In this study, H2 dissociation by Aul-doped closed-shell titanium oxide cluster anions AuTi3O7 a...Dissociation of molecular hydrogen （H2） is extensively studied to understand the mechanism of hydrogenation reactions. In this study, H2 dissociation by Aul-doped closed-shell titanium oxide cluster anions AuTi3O7 and AuTi3O8 has been identified by mass spectrometry and quantum chemistry calculations. The clusters were generated by laser ablation and mass- selected to react with H2 in art ion trap reactor. In the reaction of AuTi3O8 with H2, the ion pair Au＋-O22 rather than Au＋-O2 is the active site to promote H2 dissociation. This finding is in contrast with the previous result that the lattice oxygen is usually the reactive oxygen species in H2 dissociation. The higher reactivity of the peroxide species is further supported by frontier molecular orbital analysis. This study provides new insights into gold catalysis involving H2 activation and dissociation.展开更多
Ab initio calculations of the orbital and the ground state energies of some open- and closed-shell atoms over Slater type orbitals with quantum numbers integer and Slater type orbitals with quantum numbers noninteger ...Ab initio calculations of the orbital and the ground state energies of some open- and closed-shell atoms over Slater type orbitals with quantum numbers integer and Slater type orbitals with quantum numbers noninteger have been performed. In order to increase the efficiency of these calculations the atomic two-electron integrals were expressed in terms of incomplete beta function. Results were observed to be in good agreement with the literature.展开更多
基金supported by the National Natural Science Foundation of China(No.21873001 and No.21873002)the Foundation of Distinguished Young Scientists of Anhui Province。
文摘Metallophilic interaction is a unique type of weak intermolecular interaction,where the electronic configuration of two metal atoms is closed shell.Despite its significance in multidisciplinary fields,the nature of metallophilic interaction is still not well understood.In this work,we investigated the electronic structures and bonding characteristic of bimetallic Au2@Cu6 nanocluster through density functional theory method,which was reported in experiments recently[Angew.Chem.Int.Ed.55,3611(2016)].In general thinking,interaction between two moieties of(CuSH)6 ring and(Au2PH3)2 in the Au2@Cu6 nanocluster can be viewed as a d^10-σ closed-shell interaction.However,chemical bonding analysis shows that there is a ten center-two electron(10c-2e)multicenter bonding between two moieties.Further comparative studies on other bimetallic nanocluster M2@Cu6(M=Ag,Cu,Zn,Cd,Hg)also revealed that multicenter bonding is the origin of electronic stability of the complexes besides the d10-σclosed-shell interaction.This will provide valuable insights into the understanding of closed-shell interactions.
基金supported by the National Natural Science Foundation of China(No.21573246,No.21773253,and No.21773254)the Beijing Natural Science Foundation(2172059)the Youth Innovation Promotion Association,Chinese Academy of Sciences(2016030)
文摘Dissociation of molecular hydrogen （H2） is extensively studied to understand the mechanism of hydrogenation reactions. In this study, H2 dissociation by Aul-doped closed-shell titanium oxide cluster anions AuTi3O7 and AuTi3O8 has been identified by mass spectrometry and quantum chemistry calculations. The clusters were generated by laser ablation and mass- selected to react with H2 in art ion trap reactor. In the reaction of AuTi3O8 with H2, the ion pair Au＋-O22 rather than Au＋-O2 is the active site to promote H2 dissociation. This finding is in contrast with the previous result that the lattice oxygen is usually the reactive oxygen species in H2 dissociation. The higher reactivity of the peroxide species is further supported by frontier molecular orbital analysis. This study provides new insights into gold catalysis involving H2 activation and dissociation.
文摘Ab initio calculations of the orbital and the ground state energies of some open- and closed-shell atoms over Slater type orbitals with quantum numbers integer and Slater type orbitals with quantum numbers noninteger have been performed. In order to increase the efficiency of these calculations the atomic two-electron integrals were expressed in terms of incomplete beta function. Results were observed to be in good agreement with the literature.
