The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/P...The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/PM3 method based on the RHF/6-31G （TPC and TPP） or semiempirical PM3 （1, 2, 3, 4） optimized geometries. Calculation results showed TPC and TPP have C1 and D2h symmetry, respectively when N-H protons are localized on the nitrogen atoms. TPC is the second-order NLO active chromophore due to the cancellation of centrosymmetrical structure and its first hyperpolarizability β increases to 11.524×10^-30 esu. Under electrical dipole approximation, βvalues of bis-corroles 1, 2, 3 and 4 vary from 9.831×10^-30 to 14.221×10^-30 esu, and no much improvement in the first hyperpolarizability was observed as compared to TPC monomer.However, β values of bis-corroles 1, 2, 3 and 4 are improved by about 4 times as compared to their bis-porphyrin counterparts. The analysis of β components indicates that β of this kind of bis-corroles is mainly contributed from its radial component βr. With the variation of amino acid side chains, βHRS, β,βxyz, βr and βa of bis-corroles change remarkably. Chiral L-amino acid bridged bis-corroles 2, 3 and 4 have a right-handed helix structure, and their chiral component βxyz matches βxyz ∝ r^2 ζ/L^4 （helix parameters）, showing the second-order chiral NLO response of these bis-corroles could be described by one-electron helical model theory. It was found that the radial component βr of chiral helix bis-corroles also matches βr ∝ r^2 ζ/L^4.展开更多
Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemi...Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipola- rizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic χ (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.展开更多
电子的运动与演化是贯穿许多物理化学过程的主线,而对这一过程的精确模拟和分析是发展有效的电子调控方法和应用的关键.传统方法,如TDHF(time-dependent Hartree-Fock)、TDDFT(time-dependent density functional theory)等,在模拟小尺...电子的运动与演化是贯穿许多物理化学过程的主线,而对这一过程的精确模拟和分析是发展有效的电子调控方法和应用的关键.传统方法,如TDHF(time-dependent Hartree-Fock)、TDDFT(time-dependent density functional theory)等,在模拟小尺度体系内的电子演化时表现优异,然而,在模拟大尺度体系时计算复杂度偏高,成本较大.在一些大尺度体系内,原子核位置相对固定,并且微扰对整体相互作用的哈密顿量影响较小.为此提出了一种简单有效的基于哈密顿矩阵的电子波函数演化方法,这一方法能处理远远大于TDDFT计算尺度的大体系.通过将该方法应用于四个不同的体系进行测试分析,验证了这一方法在处理大体系时的可行性,并为相关的电子调控应用提供了新的思路.展开更多
The quasifission dynamics in the reaction ^(48)Ca+^(244)Pu is investigated in the framework of time-dependent Hartree-Fock(TDHF)theory. The calculations are performed in three-dimensional Cartesian coordinate without ...The quasifission dynamics in the reaction ^(48)Ca+^(244)Pu is investigated in the framework of time-dependent Hartree-Fock(TDHF)theory. The calculations are performed in three-dimensional Cartesian coordinate without any symmetry restrictions. The full Skyrme energy functional is incorporated in our TDHF implementation. The quasifission dynamics is quite sensitive to the angular momentum of colliding system. The contact time of quasifission decreases as a function of angular momentum and then forms a plateau with small oscillations. The quasifission process is accompanied by an important multi-nucleon transfer. The quantum shell effect plays a crucial role in the mass and charge of quasifission fragments. The mass-angle distribution of the fragments is calculated, which can be compared directly with future experiments.展开更多
The entrance-channel dynamics including capture, fusion, and quasifission processes for the reaction ^40Ca+^208Pb is investigated in the fully microscopic time-dependent Hartree-Fock(TDHF) theory. The calculations are...The entrance-channel dynamics including capture, fusion, and quasifission processes for the reaction ^40Ca+^208Pb is investigated in the fully microscopic time-dependent Hartree-Fock(TDHF) theory. The calculations are performed in three-dimensional Cartesian coordinate without any symmetry restrictions, in which the full Skyrme energy functional SLy4d and SLy5 are adopted.We study the energy dependence of capture cross sections, and find that the experimental data are well reproduced by the TDHF calculations. Both fusion and quasifission events are observed in the reaction ^40Ca+^208Pb. The contact time, mass and charge of quasifission fragments show a wide distribution in SLy4d compared with SLy5, implying that more nucleons are transferred in the SLy4d calculations. We find that the total kinetic energy of quasifission fragments in the TDHF calculations is distributed around Viola systematics, indicating that most of the relative kinetic energy is dissipated in quasifission dynamics.展开更多
基金Supported by the NNSFC (20476034), Research Grants Council of Hongkong and SRF for ROCS, State Education Ministry
文摘The second-order nonlinear optical （NLO） properties of 5,10,15-triphenylcorrole （TPC）, 5,10,15,20-tetraphenylporphyrin （TPP） and L-amino acid bridged bis-corroles 1,2,3 and 4 have been calculated by using TDHF/PM3 method based on the RHF/6-31G （TPC and TPP） or semiempirical PM3 （1, 2, 3, 4） optimized geometries. Calculation results showed TPC and TPP have C1 and D2h symmetry, respectively when N-H protons are localized on the nitrogen atoms. TPC is the second-order NLO active chromophore due to the cancellation of centrosymmetrical structure and its first hyperpolarizability β increases to 11.524×10^-30 esu. Under electrical dipole approximation, βvalues of bis-corroles 1, 2, 3 and 4 vary from 9.831×10^-30 to 14.221×10^-30 esu, and no much improvement in the first hyperpolarizability was observed as compared to TPC monomer.However, β values of bis-corroles 1, 2, 3 and 4 are improved by about 4 times as compared to their bis-porphyrin counterparts. The analysis of β components indicates that β of this kind of bis-corroles is mainly contributed from its radial component βr. With the variation of amino acid side chains, βHRS, β,βxyz, βr and βa of bis-corroles change remarkably. Chiral L-amino acid bridged bis-corroles 2, 3 and 4 have a right-handed helix structure, and their chiral component βxyz matches βxyz ∝ r^2 ζ/L^4 （helix parameters）, showing the second-order chiral NLO response of these bis-corroles could be described by one-electron helical model theory. It was found that the radial component βr of chiral helix bis-corroles also matches βr ∝ r^2 ζ/L^4.
基金This work was supported by the NNSFC (20476034 NSFC/HKUST43)+1 种基金 NSF of Guangdong Province (000489) and SRF for ROCS State Education Ministry.
文摘Static second-order nonlinear optical effects of amino acid zinc(II) porphyrins 1, 2, 3 and 4 were calculated by the TDHF/PM3 method based on the molecular structures optimized at the semiempirical PM3 quantum chemistry level, showing due to the cancellation of symmetric center, these amino acid zinc(II) porphyrins exhibit second order nonlinear optical response. The analysis of β components indicated that these amino acid zinc(II) porphyrins are of multipola- rizabilities, and they may be ascribed as the “mixture” of octupolar and dipoar molecules with ||βJ=3||/||βJ=1|| ≈ 5. It is found that there are no significant differences between the static β values of non-chiral and chiral amino acid zinc(II) porphyrins. However, the βxyz component, which is quite important to quadratic macroscopic χ (2) susceptibility of chiral material, is increased significantly with the increase of side chain group of amino acids.
文摘电子的运动与演化是贯穿许多物理化学过程的主线,而对这一过程的精确模拟和分析是发展有效的电子调控方法和应用的关键.传统方法,如TDHF(time-dependent Hartree-Fock)、TDDFT(time-dependent density functional theory)等,在模拟小尺度体系内的电子演化时表现优异,然而,在模拟大尺度体系时计算复杂度偏高,成本较大.在一些大尺度体系内,原子核位置相对固定,并且微扰对整体相互作用的哈密顿量影响较小.为此提出了一种简单有效的基于哈密顿矩阵的电子波函数演化方法,这一方法能处理远远大于TDDFT计算尺度的大体系.通过将该方法应用于四个不同的体系进行测试分析,验证了这一方法在处理大体系时的可行性,并为相关的电子调控应用提供了新的思路.
基金supported by the National Natural Science Foundation of China(Grants Nos.11175252,and 11575189)Presidential Fund of University of Chinese Academy of Sciencesthe Natural Science Foundation of China-Japan Society for the Promotion of Science International Cooperation and Exchange Program(Grant No.11711540016)
文摘The quasifission dynamics in the reaction ^(48)Ca+^(244)Pu is investigated in the framework of time-dependent Hartree-Fock(TDHF)theory. The calculations are performed in three-dimensional Cartesian coordinate without any symmetry restrictions. The full Skyrme energy functional is incorporated in our TDHF implementation. The quasifission dynamics is quite sensitive to the angular momentum of colliding system. The contact time of quasifission decreases as a function of angular momentum and then forms a plateau with small oscillations. The quasifission process is accompanied by an important multi-nucleon transfer. The quantum shell effect plays a crucial role in the mass and charge of quasifission fragments. The mass-angle distribution of the fragments is calculated, which can be compared directly with future experiments.
基金supported by the National Natural Science Foundation of China(Grant Nos.11575189,and 11175252)NSFC-JSPS International Cooperation Program(Grant No.11711540016)the Presidential Fund of Universities and Colleges Admissions Service(UCAS)
文摘The entrance-channel dynamics including capture, fusion, and quasifission processes for the reaction ^40Ca+^208Pb is investigated in the fully microscopic time-dependent Hartree-Fock(TDHF) theory. The calculations are performed in three-dimensional Cartesian coordinate without any symmetry restrictions, in which the full Skyrme energy functional SLy4d and SLy5 are adopted.We study the energy dependence of capture cross sections, and find that the experimental data are well reproduced by the TDHF calculations. Both fusion and quasifission events are observed in the reaction ^40Ca+^208Pb. The contact time, mass and charge of quasifission fragments show a wide distribution in SLy4d compared with SLy5, implying that more nucleons are transferred in the SLy4d calculations. We find that the total kinetic energy of quasifission fragments in the TDHF calculations is distributed around Viola systematics, indicating that most of the relative kinetic energy is dissipated in quasifission dynamics.
