Electronic structure and optical properties of neutral and charged low band gap alternating copolyfluorenes （Green 1, which is based on alternating repeating units consisting of alkyl-substituted fluorene and a thiop...Electronic structure and optical properties of neutral and charged low band gap alternating copolyfluorenes （Green 1, which is based on alternating repeating units consisting of alkyl-substituted fluorene and a thiophene-[1,2,5]thiadiazolo-[3,4]quinoxaline-thiophene （T-TDQ-T） unit were investigated theoretically with time-dependent density functional theory （TD-DFT） method, and their excited state properties were further analyzed with 2D site and 3D cube representations. For neutral Green 1, the band gap, binding energy, exciton binding energy, and nuclear relaxation energy were obtained. The transition dipole moments of neutral and charged Green 1 are compared using 3D transition density, which reveals the orientation and strength of transition dipole moments. The charge redistribution of neutral and charged Green 1 upon excitation are displayed and compared with 3D charge difference density. The electron-hole coherences of neutral and charged Green 1 upon excitation are investigated with 2D site representation （transition density matrix）. The excited state properties of neutral Green 1 calculated with TD-DFT method are compared with that calculated with ZINDO method, which reveals the importance of electron-electron interaction （in TD-DFT） in the excited state properties.展开更多
Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer （MLCT） in ruthenium（II） ammine compl...Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer （MLCT） in ruthenium（II） ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os（bpy）2（p0p）Cl （＂Osp0p＂： bpy=2,2-bipyrldyl; p0p=4,4＇- bipyridyl） and the ligand-to-ligand charge transfer （LLCT） in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.展开更多
基金ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China （No.10505001, No.10875055, No.10874234, and No.10703064） and the Educational Department of Liaoning Province （No.2008228）.
文摘Electronic structure and optical properties of neutral and charged low band gap alternating copolyfluorenes （Green 1, which is based on alternating repeating units consisting of alkyl-substituted fluorene and a thiophene-[1,2,5]thiadiazolo-[3,4]quinoxaline-thiophene （T-TDQ-T） unit were investigated theoretically with time-dependent density functional theory （TD-DFT） method, and their excited state properties were further analyzed with 2D site and 3D cube representations. For neutral Green 1, the band gap, binding energy, exciton binding energy, and nuclear relaxation energy were obtained. The transition dipole moments of neutral and charged Green 1 are compared using 3D transition density, which reveals the orientation and strength of transition dipole moments. The charge redistribution of neutral and charged Green 1 upon excitation are displayed and compared with 3D charge difference density. The electron-hole coherences of neutral and charged Green 1 upon excitation are investigated with 2D site representation （transition density matrix）. The excited state properties of neutral Green 1 calculated with TD-DFT method are compared with that calculated with ZINDO method, which reveals the importance of electron-electron interaction （in TD-DFT） in the excited state properties.
基金This work was supported by National Natural Science Foundation of China （No.10505001, No.10875055, and No.10874234） and the Educational Department of Liaoning Province （No.2008228）.
文摘Three methods including the atomic resolved density of state, charge difference density, and the transition density matrix are used to visualize metal to ligand charge transfer （MLCT） in ruthenium（II） ammine complex. The atomic resolved density of state shows that there is density of Ru on the HOMOs. All the density is localized on the ammine, which reveals that the excited electrons in the Ru complex are delocalized over the ammine ligand. The charge difference density shows that all the holes are localized on the Ru and the electrons on the ammine. The localization explains the MLCT on excitation. The transition density matrix shows that there is electron-hole coherence between Ru and ammine. These methods are also used to examine the MLCT in Os（bpy）2（p0p）Cl （＂Osp0p＂： bpy=2,2-bipyrldyl; p0p=4,4＇- bipyridyl） and the ligand-to-ligand charge transfer （LLCT） in Alq3. The calculated results show that these methods are powerful to examine MLCT and LLCT in the metal-ligand system.
