We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic ligh...We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.展开更多
Polarons are widely considered to play a crucial role in the charge transport and photocatalytic performance of materials,but the mechanisms of their formation and the underlying driving factors remain a matter of con...Polarons are widely considered to play a crucial role in the charge transport and photocatalytic performance of materials,but the mechanisms of their formation and the underlying driving factors remain a matter of controversy.This study delves into the formation of polarons in different crystalline forms of TiO_(2) and their connection with the materials'structure.By employing density functional theory calculations with on-site Coulomb interaction correction(DFT+U),we provide a detailed analysis of the electronic polarization behavior in the anatase and rutile forms of TiO_(2).We focus on the polarization properties of defect-induced and photoexcited excess electrons on various TiO_(2) surfaces.The results reveal that the defect electrons can form small polarons on the anatase TiO_(2)(101)surface,while on the rutile TiO_(2)(110)surface,both small and large polarons(hybrid-state polarons)are formed.Photoexcited electrons are capable of forming both small and large polarons on the surfaces of both crystal types.The analysis indicates that the differences in polaron distribution are primarily determined by the intrinsic properties of the crystals;the structural and symmetry differences between anatase and rutile TiO_(2) lead to the distinct polaron behaviors.Further investigation suggests that the polarization behavior of defect electrons is also related to the arrangement of electron orbitals around the Ti atoms,while the polarization of photoexcited electrons is mainly facilitated by the lattice distortions.These findings elucidate the formation mechanisms of different types of polarons and may contribute to understanding the performance of TiO_(2)in different fields.展开更多
Chemical concepts such as structure,bonding,reactivity,etc.have been widely used in the literature and text books to appreciate molecular properties and chemical transformations.Even though modern theoretical and comp...Chemical concepts such as structure,bonding,reactivity,etc.have been widely used in the literature and text books to appreciate molecular properties and chemical transformations.Even though modern theoretical and computational chemistry is well established from the perspective of accuracy and complexity,how to quantify these concepts is a still unresolved task.Conceptual density functional theory and its related recent developments provide unique opportunities to tackle this problem.In this Special Issue,27 contributions from top investigators over the world are collected to highlight the state-of-art research on this topic,which not only showcases the status of where we are now but also unveils a number to possible future directions to be pursued.展开更多
Various incorporation of Au in pyrite and its effects on the geometrical structure,electronic structure and flotability of pyrite were theoretically investigated and fully discussed by performing density functional th...Various incorporation of Au in pyrite and its effects on the geometrical structure,electronic structure and flotability of pyrite were theoretically investigated and fully discussed by performing density functional theory(DFT).The calculated incorporation energy shows that gold would most likely exist in pyrite via incorporating into interstitial lattice sites in the absence of As impurity.As a result of incorporated Au,the covalence levels of the S—Fe and S—S bonds are changed,and the tonicity of Au—S bonds and antibonding of Au—Fe bonds are found to form in the pyrite,which would change the natural flotability of pyrite.The Au impurity energy levels are introduced into the energy band and result in the transformation of pyrite semiconductivity type.The calculated band-gap value suggests that the incorporated Au significantly decreases pyrite semiconductivity level,which enhances the formation and the adsorption stability of dixanthogen during pyrite flotation.The DOS results reveal that the stability and depression difficulty level of pyrites increases in the following order:Fe_(32)S_(63)As<Fe_(32)S_(64)<Fe_(32)S_(63)As Au<Fe_(32)S_(64)Au.展开更多
Based on the pseudo potential plane-wave method of density functional theory （DFT）, Ti1-xNbxAk （x=0, 0.062 5, 0.083 3, 0.125, 0.250） crystals＇ geometry structure, elastic constants, electronic structure and Mulli...Based on the pseudo potential plane-wave method of density functional theory （DFT）, Ti1-xNbxAk （x=0, 0.062 5, 0.083 3, 0.125, 0.250） crystals＇ geometry structure, elastic constants, electronic structure and Mulliken populations were calculated, and the effects of doping on the geometric structure, electronic structure and bond strength were systematically analyzed. The results show that the influence of Nb on the geometric structure is little in terms of the plasticity, and with the increase of Nb content, the covalent bond strength remarkably reduces, and Ti-Al, Nb-M （M=Ti, Al） and other hybrid bonds enhance; meanwhile, the peak district increases and the pseudo-energy gap first decreases and then increases, the overall band structure narrows, the covalent bond and direction of bonds reduce. The population analysis also shows that the results are consistent with the electronic structure analysis. The density of states of TiAINb shows that Nb doping can enhance the activity of Al and benefit the form of Al2O3 film. All the calculations reveal that the room temperature plasticity and the antioxidation properties of the compounds can be improved with the Nb content of 8.33%-12.5% （mole fraction）.展开更多
Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, the...Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference. The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.展开更多
文摘We have examined the theoretical implications of combining two main and three auxiliary ligands to form several Ir(Ⅲ)complexes featuring a transition metal as their core atom to identify some appropriate organic lightemitting diode(OLED)materials.By utilizing electronic structure,frontier molecular orbitals,minimum single-line absorption,triplet excited states,and emission spectral data derived from the density functional theory,the usefulness of these Ir(Ⅲ)complexes,including(piq)_(2)Ir(acac),(piq)_(2)Ir(tmd),(piq)_(2)Ir(tpip),(fpiq)_(2)Ir(acac),(fpiq)_(2)Ir(tmd),and(fpiq)_(2)Ir(tpip),in OLEDs was examined,where piq=1-phenylisoquinoline,fpiq=1-(4-fluorophenyl)isoquinoline,acac=(3Z)-4-hydroxypent-3-en-2-one,tmd=(4Z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one,and tpip=tetraphenylimido-diphosphonate.These complexes all have low-efficiency roll-off properties,especially(fpiq)_(2)Ir(tpip).Some researchers have successfully synthesized complexes extremely similar to(piq)_(2)Ir(acac)through the Suzuki-Miyaura coupling reaction.
文摘Polarons are widely considered to play a crucial role in the charge transport and photocatalytic performance of materials,but the mechanisms of their formation and the underlying driving factors remain a matter of controversy.This study delves into the formation of polarons in different crystalline forms of TiO_(2) and their connection with the materials'structure.By employing density functional theory calculations with on-site Coulomb interaction correction(DFT+U),we provide a detailed analysis of the electronic polarization behavior in the anatase and rutile forms of TiO_(2).We focus on the polarization properties of defect-induced and photoexcited excess electrons on various TiO_(2) surfaces.The results reveal that the defect electrons can form small polarons on the anatase TiO_(2)(101)surface,while on the rutile TiO_(2)(110)surface,both small and large polarons(hybrid-state polarons)are formed.Photoexcited electrons are capable of forming both small and large polarons on the surfaces of both crystal types.The analysis indicates that the differences in polaron distribution are primarily determined by the intrinsic properties of the crystals;the structural and symmetry differences between anatase and rutile TiO_(2) lead to the distinct polaron behaviors.Further investigation suggests that the polarization behavior of defect electrons is also related to the arrangement of electron orbitals around the Ti atoms,while the polarization of photoexcited electrons is mainly facilitated by the lattice distortions.These findings elucidate the formation mechanisms of different types of polarons and may contribute to understanding the performance of TiO_(2)in different fields.
基金We are immensely indebted to the Editor-in-Chief as well as the entire crew of the Editorial Office of Acta Physico-Chimica Sinica for making the Special Issue possible. I am in particular grateful to Dr. Xiaojuan Zhang, the Managing Editor, and Dr. Ying
文摘Chemical concepts such as structure,bonding,reactivity,etc.have been widely used in the literature and text books to appreciate molecular properties and chemical transformations.Even though modern theoretical and computational chemistry is well established from the perspective of accuracy and complexity,how to quantify these concepts is a still unresolved task.Conceptual density functional theory and its related recent developments provide unique opportunities to tackle this problem.In this Special Issue,27 contributions from top investigators over the world are collected to highlight the state-of-art research on this topic,which not only showcases the status of where we are now but also unveils a number to possible future directions to be pursued.
基金Projects(51504109,51504107)supported by the National Natural Science Foundation of China
文摘Various incorporation of Au in pyrite and its effects on the geometrical structure,electronic structure and flotability of pyrite were theoretically investigated and fully discussed by performing density functional theory(DFT).The calculated incorporation energy shows that gold would most likely exist in pyrite via incorporating into interstitial lattice sites in the absence of As impurity.As a result of incorporated Au,the covalence levels of the S—Fe and S—S bonds are changed,and the tonicity of Au—S bonds and antibonding of Au—Fe bonds are found to form in the pyrite,which would change the natural flotability of pyrite.The Au impurity energy levels are introduced into the energy band and result in the transformation of pyrite semiconductivity type.The calculated band-gap value suggests that the incorporated Au significantly decreases pyrite semiconductivity level,which enhances the formation and the adsorption stability of dixanthogen during pyrite flotation.The DOS results reveal that the stability and depression difficulty level of pyrites increases in the following order:Fe_(32)S_(63)As<Fe_(32)S_(64)<Fe_(32)S_(63)As Au<Fe_(32)S_(64)Au.
基金Project(07JJ3102) supported by Hunan Provincial Natural Science Foundation,ChinaProject(k0902132-11) supported by Changsha Municipal Science and Technology,China
文摘Based on the pseudo potential plane-wave method of density functional theory （DFT）, Ti1-xNbxAk （x=0, 0.062 5, 0.083 3, 0.125, 0.250） crystals＇ geometry structure, elastic constants, electronic structure and Mulliken populations were calculated, and the effects of doping on the geometric structure, electronic structure and bond strength were systematically analyzed. The results show that the influence of Nb on the geometric structure is little in terms of the plasticity, and with the increase of Nb content, the covalent bond strength remarkably reduces, and Ti-Al, Nb-M （M=Ti, Al） and other hybrid bonds enhance; meanwhile, the peak district increases and the pseudo-energy gap first decreases and then increases, the overall band structure narrows, the covalent bond and direction of bonds reduce. The population analysis also shows that the results are consistent with the electronic structure analysis. The density of states of TiAINb shows that Nb doping can enhance the activity of Al and benefit the form of Al2O3 film. All the calculations reveal that the room temperature plasticity and the antioxidation properties of the compounds can be improved with the Nb content of 8.33%-12.5% （mole fraction）.
文摘Pyrite （FeS2） bulk and （100） surface properties and the oxygen adsorption on the surface were studied by using density functional theory methods. The results show that in the formation of FeS2 （100） surface, there exists a process of electron transfer from Fe dangling bond to S dangling bond. In this situation, surface Fe and S atoms have more ionic properties. Both Fe2+ and S2- have high electrochemistry reduction activity, which is the base for oxygen adsorption. From the viewpoint of adsorption energy, the parallel form oxygen adsorption is in preference. The result also shows that the state of oxygen absorbed on FeS2 surface acts as peroxides rather than O2.
