刘文剑
博士研究生 教授
北京大学 化学与分子工程学院
主要从事量子化学和相对论量子化学理论、计算方法和应用研究。
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- 姓名:刘文剑
- 目前身份:在职研究人员
- 担任导师情况:
- 学位:
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学术头衔:
博士生导师
- 职称:高级-教授
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学科领域:
物理化学
- 研究兴趣:主要从事量子化学和相对论量子化学理论、计算方法和应用研究。
刘文剑 1989年获山东大学理学学士,1992年获山东大学理学硕士,1995年获北京大学理学博士。1995-1997年,德国物理复杂体系马普研究所客座科学家。1998-2001年,德国鲁尔-波鸿大学工作。2002年起任山东大学、山东师范大学兼职教授。2006年获两次国际大奖:亚太理论与计算化学家协会“Pople Medal”(2006.1)和“国际量子分子科学院奖”(2006.5)。后者是国际上对40岁以下青年理论化学家的最高奖励,每年在世界范围内只授予一名在基础理论方面做出突出贡献的年轻学者,该奖项设立于1967年,刘文剑是中国第一位获奖者。主要从事量子化学和相对论量子化学理论、计算方法和应用研究:发展了独立完整、有特色、高精度、高效率的相对论密度泛函理论计算大型软件包BDF(Beijing Density Functional);发展了国际上第一个可以用于重元素体系激发态及电子多重态精细结构计算的完全相对论含时密度泛函理论方法,提出了含时密度泛函理论的统一形式和简化形式;发展了一个全新的精确准相对论方法(XQR),该方法不仅简单、计算量小,同时具有与完全相对论方法相同的计算精度;发展了可以处理准简并体系及激发态的相对论从头算多组态自洽场直接微扰理论。将该方法与有限微扰理论相结合,可以进行任意水平的电子相关计算;系统地研究了镧系、锕系、重过渡金属以及超重元素化合物的电子结构、分子结构及成键规律,推翻了前人“密度泛函理论用于f-元素不很成功”的论断,部分计算结果被后来的实验验证;发展了“分子中的原子轨道”的概念,大大降低了Mulliken电荷布局分析及Mayer键级对扩展基函数的敏感性。有关论文他引200余次。
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刘文剑, Wenjian Liu* and Daoling Peng
,-0001,():
-1年11月30日
The exact one-electron matrix quasirelativistic theory [W. Kutzelnigg and W. Liu, J. Chem. Phys. 123, 241102 (2005)] is extended to the effective one-particle Kohn-Sham scheme of density functional theory. Several variants of the resultant theory are discussed. Although they are in principle equivalent, consideration of computational effciency strongly favors the one (F+) in which the effective potential remains untransformed. Further combined with the atomic approximation for the matrix X relating the small and large components of the Dirac spinors as well as a simple ansatz for correcting the two-electron picture change errors, a very elegant, accurate, and effcient innite-order quasirelativistic approach is obtained, which is far simpler than all existing uasirelativistic theories and must hence be regarded as a breakthrough in relativistic quantum chemistry. In passing, it is also shown that the Dirac-Kohn-Sham scheme can be made as effcient as two-component approaches without compromising the accuracy. To demonstrate the performance of the new methods atomic calculations on Hg and E117 are rst carried out. The spectroscopic constants (bond length, vibrational frequency, and dissociation energy) of E1172 are then reported. All the results are in excellent agreement with those of the Dirac-Kohn-Sham calculations.
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刘文剑, Wenjian Liu, , Gongyi Hong, Dadi Dai, Lemin Li, Michael Dolg
Theor Chem Acc (1997) 96: 75-83,-0001,():
-1年11月30日
A four-component density functional program package (Beijing Density Functional), suitable for the calculation of total-energy-related chemical properties of systems containing heavy atoms, was developed. The code is based on modern sophisticated exchange-corre-lation functionals and was applied to calculate the spectroscopic constants of the lanthanide diatomic molecules of EuO, EuS, YbO and YbS. It is suggested that the experimental bond lengths for EuS and YbS, derived from empirical interpolations, need to be revised. Relativistic effects on the electronic structure are discussed and compared with results from previous work. The involvement of the lanthanide valence orbit-als in chemical bonding is investigated with a newly developed population and bonding analysis approach.
Relativistic effects-Density functional theory-Beijing Density Functional-Lanthanide diatomics- Atomic orbitals in molecules
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刘文剑, Wenjian Liu, Michael Dolg, Lemin Li
J. Chem. Phys., Vol. 108, No.7, 15 February 1998,-0001,():
-1年11月30日
Fully relativistic density functional calculations using the recently developed Beijing 4-component density functional program package (BDF) were performed for a large number of excited states of the ytterbium atom and the spectroscopic constants of the ground and some excited states of the diatomic molecules YbH, YbF and YbO. It is shown that in a relativistic framework based on the Dirac-Coulomb Hamiltonian modern (nonrelativistic) density functionals work fairly well even for the rather compact 4 f shell, i.e., they quantitatively reproduce the excitation energies due to the occupation changes in the 4 f shell, in contrast to previous statements made by other authors. The nondegeneracy induced by the approximate density functionals to the degenerate open 4 f shell is found to be almost independent of the occupancy of outer shells as well as Hund's coupling and of the same order as that for the first transition metals. After subtracting the unphysical nondegeneracy we obtain reasonable patterns of excited states due to different occupations of the 4 f spinors for the molecules studied here. Although the spectroscopic constants for YbH and YbF obtained by this and other theoretical work are all in good agreement with available experimental data, the theoretical results for YbO show remarkable disagreement with each other and experiment. The present calculations favor a V501 ground state with a leading f 14s0 configuration, which is in agreement with the interpretation of experimental data.
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【期刊论文】Relativistic MCSCF by means of quasidegenerate direct perturbation theory. Ⅰ. Theory
刘文剑, Werner Kutzelnigg a) and Wenjian Liu
J. Chem. Phys., Vol. 112, No.8, 22 February 2000,-0001,():
-1年11月30日
Relativistic MC-SCF (multiconfiguration self-consistent field) in terms of quasidegenerate direct perturbation theory (DPT) of relativistic effects is formulated based on a recently presented theory of effective Hamiltonians for electrons in a model space. The appropriately defined diagonal and nondiagonal parts of operators play a key role in this context. Their definition is based on stationary conditions for the MC-SCF wave function. The formalism starts from nonrelativistic MC-SCF theory. The leading relativistic correction appears as an expectation value in terms of the nonrelativistic MC-SCF function, while the higher-order relativistic corrections require a coupled-MC-SCF type approach.
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刘文剑, Daoling Peng, Wenli Zou, and Wenjian Liu a)
J. Chem. Phys. 123, 144101 (2005),-0001,():
-1年11月30日
A time-dependent quasirelativistic density-functional theory for excitation energies of systems containing heavy elements is developed, which is based on the zeroth-order regular approximation (ZORA) for the relativistic Hamiltonian and a noncollinear form for the adiabatic exchange-correlation kernel. To avoid the gauge dependence of the ZORA Hamiltonian a model atomic potential, instead of the full molecular potential, is used to construct the ZORA kinetic operator in ground-state calculations. As such, the ZORA kinetic operator no longer responds to changes in the density in response calculations. In addition, it is shown that, for closed-shell ground states, time-reversal symmetry can be employed to simplify the eigenvalue equation into an approximate form that is similar to that of time-dependent nonrelativistic density-functional theory. This is achieved by invoking an independent-particle approximation for the induced density matrix. The resulting theory is applied to investigate the global potential-energy curves of low-lying Sand-coupled electronic states of the AuH molecule. The derived spectroscopic parameters, including the adiabatic and vertical excitation energies, equilibrium bond lengths, harmonic and anharmonic vibrational constants, fundamental frequencies, and dissociation energies, are in good agreement with those of time-dependent four-component relativistic density-functional theory and ab initio multireference second-order perturbation theory. Nonetheless, this two-component relativistic version of time-dependent density-functional theory is only moderately advantageous over the four-component one as far as computational efforts are concerned.
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刘文剑, Jun Gao, Wenli Zou, Wenjian Liu, a), Yunlong Xiao, Daoling Peng, and Bo Song, Chengbu Liu
J. Chem. Phys. 123, 054102 (2005),-0001,():
-1年11月30日
We extend our previous formulation of time-dependent four-component relativistic density-functional theory J. Gao, W. Liu, B. Song, and C. Liu, J. Chem. Phys. 121, 6658 (2004) by using a noncollinear form for the exchange-correlation kernel. The new formalism can deal with excited states involving moment spin-flipped configurations which are otherwise not accessible with ordinary exchange-correlation functionals. As a first application, the global potential-energy curves of 16 low-lying-coupled electronic states of the AuH molecule have been investigated. The derived spectroscopic parameters, including the adiabatic and vertical excitation energies, equilibrium bond lengths, harmonic and anharmonic vibrational constants, fundamental frequencies, and dissociation energies, are grossly in good agreement with those of ab initio multireference second-order perturbation theory and the available experimental data
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【期刊论文】Time-dependent four-component relativistic density functional theory for excitation energies
刘文剑, Jun Gao, Wenjian Liu a) and Bo Song, Chengbu Liu
J. Chem. Phys., Vol. 121, No.14, 8 October 2004,-0001,():
-1年11月30日
Time-dependent four-component relativistic density functional theory within the linear response regime is developed for calculating excitation energies of heavy element containing systems. Since spin is no longer a good quantum number in this context, we resort to time-reversal adapted Kramers basis when deriving the coupled Dirac-Kohn-Sham equation. The particular implementation of the formalism into the Beijing density functional program package utilizes the multipolar expansion of the induced density to facilitate the construction of the induced Coulomb potential. As the first application, pilot calculations on the valence excitation energies and fine structures of the rare gas (Ne to Rn) and Group 12 (Zn to Hg) atoms are reported. To the best of our knowledge, it is the first time to be able to account for spin-orbit coupling within time-dependent density functional theory for excitation energies.
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【期刊论文】Spectroscopic constants of MH and M2 (M=Tl, E113, Bi, E115
刘文剑, Wenjian Liu a), Christoph van W
J. Chem. Phys., Vol. 116, No.9, 1 March 2002,-0001,():
-1年11月30日
The two-component DFT-ZORA (density functional theory, zeroth order regular approximation) method is implemented into the BDF (Beijing four-component density functional) program package so that systematic and direct comparisons between two-and four-component approaches are made possible for the first time. Different implementations of the ZORA method are also compared in this work. The calculated spectroscopic constants (bond lengths, binding energies, and force constants) for MH and M2 (M5Tl, E113, Bi, E115) by the two-and four-component approaches are very similar. The ionization and excitation energies for the metals obtained by these methods also agree very well with each other. Still, minor higher order relativistic effects beyond ZORA can be identified occasionally, but can be "safely" neglected. Therefore, the applicability of transformed (two-component) Hamiltonians to valence properties is well justified. However, the computational efficiency of four-component DFT compares favorably with that of two-component DFT. The problems of symmetry breaking and different treatments of open-shell systems are discussed by taking the Bi atom as an example.
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刘文剑, Wenjian Liu and Christoph van W
J. Chem. Phys., Vol. 110, No.8, 22 February 1999,-0001,():
-1年11月30日
Scalar-relativistic density functional calculations in the zeroth-order regular approximation as well as fully relativistic Dirac-Kohn-Sham calculations have been performed to investigate spectroscopic constants of the eka-gold (element 111) compounds (111) X (X5H, F, Cl, Br, O, Au) and the dimer of element 111. For calibration, we also report results for homologous gold compounds. The bond lengths for the compounds of element 111 are similar but slightly larger than those of the gold compounds. Spin-orbit coupling increases the bond length by a few pm. For the hydride and the halides, the force constants of the eka-gold compounds are generally larger than those of the gold compounds although the dissociation energy is smaller. The oxide of eka-gold is more strongly bound than the gold oxide. The dimer of element 111 has an open shell instead of a closed-shell electronic structure and is less stable than the gold dimer. The effect of spin-orbit coupling on the dissociation energy depends on the extent to which spin-orbit coupling is quenched in the molecule. This effect has been estimated based on a spinor occupation population analysis.
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