DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phe...DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,the βvec value of complex 1b-5b is larger than one of complex a,while the βvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,the βvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.展开更多
Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) cha...Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) charge transfer characteristics of calculated molecules were studied and compared with corresponding experimental results. All the theoretical results agree well with the measurement. For 2 D molecule with two fold symmetry, the dominant charge transfer is off diagonal, while for three fold symmetry 2 D molecule, the dominant charge transfer is not only between branches and central group but also among branches.展开更多
In this work, density functional theory (DFT) combined with the finite field (FF) method has been adopted to analyze the second-order nonlinear optical (NLO) properties of the triarylborane (TAB) derivatives obtained ...In this work, density functional theory (DFT) combined with the finite field (FF) method has been adopted to analyze the second-order nonlinear optical (NLO) properties of the triarylborane (TAB) derivatives obtained by introducing different inductive electron groups into the phenylene ring of the TAB (RTAB, where R=2-C6H5-C2B10H10(1),R=F(2), R=Me(3),R=NO2(4),R=NH2(5)). The static first hyperpolarizabilities (βtot) of the RTAB molecules can be switched by binding one F- to the boron center (RTAB′) or one-electron reduction (RTAB"). The DFT-FF calculations show that the βtot values of 2′, 3′ and 5′ decrease while those of 1′ and 4′ increase compared with the values of their neutral molecules, which was attributed to the fact that the charge transfers of 2, 3 and 5 become smaller and those of 1 and 4 become larger by binding one F- ion to the boron center, according to time-domain DFT (TD-DFT) analysis. However, the incorporation of one electron enhances the second-order NLO properties of the RTAB molecules remarkably, especially for system 1. It is notable that the βtot value of reduced form 1″ is 508.69×10-30 esu, i.e. about 578 times larger than that of system 1. Frontier molecular orbital (FMO) and natural bond orbital (NBO) analyses suggest that the reversal of the charge distribution between the neutral molecules and their reduced forms leads to low HOMO-LUMO energy gaps (E0) and thus large βtot values for the reduced forms.展开更多
Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalis...Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalism to calculate the second-order NLO properties. The results indicate that the structures of n-vertex bis-substituted carborane (n=5, 6, 7) are changed due to bridged donor and acceptor moieties. The distances between two C atoms are becoming longer. And the stability and dipole moment are in- fluenced by changing substituted positions of C atoms. The isomers with the substituents connecting with C atoms of lower coordination number have better stability and larger values of polarizability. One-dimensional structure of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) is in favor of intramolecular charge-transfer. Meanwhile, the isomer with a larger change of dipole moment has larger value of second-order NLO properties during the charge-transfer process.展开更多
基金Supported by Program for Changjiang Scholars and Innovative Research Team in University, the Foundation of Jilin Provincial Excellent Youth (Grant No. 20050107)Youth Science Foundation of Northeast Normal University (Grant No. 111494117)
文摘DFT B3LYP/LANL2DZ method was employed to calculate electron properties and the second-order nonlinear optical(NLO) respond of platinum(Ⅱ) complexes which have been synthesized by Weinstein group.4,7-diphenyl-1,10-phenanthroline shows the ability to push electron in these complexes.Metal Pt plays a balancing charge role.Comparing complex 1b-6b with complex a,the βvec value of complex 1b-5b is larger than one of complex a,while the βvec value of complex 6b is smaller than one of com-plex a.In these seven complexes,the βvec values of complexes increase with decreasing of the energy difference between HOMO and LUMO.Moreover,the electron transfers from deeper layer occupied orbitals to empty orbitals have a distinct contribution to second-order NLO coefficient.
文摘Time dependent density functional theory (TDDFT) has been applied to calculate the electronic structure and second order nonlinear optical (NLO) properties of some organic molecules. The two dimensional (2 D) charge transfer characteristics of calculated molecules were studied and compared with corresponding experimental results. All the theoretical results agree well with the measurement. For 2 D molecule with two fold symmetry, the dominant charge transfer is off diagonal, while for three fold symmetry 2 D molecule, the dominant charge transfer is not only between branches and central group but also among branches.
基金supported by the National Natural Science Foundation of China (20873017)the Natural Science Foundation of Jilin Province(20101154)
文摘In this work, density functional theory (DFT) combined with the finite field (FF) method has been adopted to analyze the second-order nonlinear optical (NLO) properties of the triarylborane (TAB) derivatives obtained by introducing different inductive electron groups into the phenylene ring of the TAB (RTAB, where R=2-C6H5-C2B10H10(1),R=F(2), R=Me(3),R=NO2(4),R=NH2(5)). The static first hyperpolarizabilities (βtot) of the RTAB molecules can be switched by binding one F- to the boron center (RTAB′) or one-electron reduction (RTAB"). The DFT-FF calculations show that the βtot values of 2′, 3′ and 5′ decrease while those of 1′ and 4′ increase compared with the values of their neutral molecules, which was attributed to the fact that the charge transfers of 2, 3 and 5 become smaller and those of 1 and 4 become larger by binding one F- ion to the boron center, according to time-domain DFT (TD-DFT) analysis. However, the incorporation of one electron enhances the second-order NLO properties of the RTAB molecules remarkably, especially for system 1. It is notable that the βtot value of reduced form 1″ is 508.69×10-30 esu, i.e. about 578 times larger than that of system 1. Frontier molecular orbital (FMO) and natural bond orbital (NBO) analyses suggest that the reversal of the charge distribution between the neutral molecules and their reduced forms leads to low HOMO-LUMO energy gaps (E0) and thus large βtot values for the reduced forms.
基金Supported by the Foundation of Jilin Provincial Excellent Youth (Grant No. 20050107)Youth Science Foundation of Northeast Normal University (Grant No. 111494117)
文摘Density functional theory (DFT) B3LYP at 6-31G* level is employed to optimize the structures of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) and combined with finite field (FF) formalism to calculate the second-order NLO properties. The results indicate that the structures of n-vertex bis-substituted carborane (n=5, 6, 7) are changed due to bridged donor and acceptor moieties. The distances between two C atoms are becoming longer. And the stability and dipole moment are in- fluenced by changing substituted positions of C atoms. The isomers with the substituents connecting with C atoms of lower coordination number have better stability and larger values of polarizability. One-dimensional structure of the molecules bridged through n-vertex bis-substituted carborane (n=5, 6, 7) is in favor of intramolecular charge-transfer. Meanwhile, the isomer with a larger change of dipole moment has larger value of second-order NLO properties during the charge-transfer process.
