王曙光
“重原子体系”结构与性能的理论研究
个性化签名
- 姓名:王曙光
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学术头衔:
博士生导师
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学科领域:
物理化学
- 研究兴趣:“重原子体系”结构与性能的理论研究
王曙光,教授,博士生导师。 研究方向为理论化学。1968-1978在建筑公司当工人;1978-1989在华东师范大学化学系学习与工作,获得化学专业理学学士与量子化学专业自然科学硕士学位,先后担任助教与讲师;1989-2000赴联邦德国 Siegen大学攻读博士学位和博士后研究,获得Dr. rer. nat (自然科学博士)学位,任理论化学专业科学工作者。2000.9- 在上海交通大学化学化工学院任教。现任化学化工学院副院长。学术领域主要集中在“重原子体系”结构与性能的理论研究方面:1)在“化学键中的相对论效应”研究中,通过对相对论“mass-velocity效应”、“Darwin效应”、“spin-orbit效应”和“非直接效应”在原子及分子周围的立体空间分布的研究,发现 s, p, d, f 轨道的四种相对论效应的不同分布。相对论效应依原子核电荷数增加而增强,特别是发现即使是价电子,其相对论效应对分子化学键键能的影响也主要分布在近核周围的K壳层。化学键的相对论校正能与分子形成过程中近核周围K壳层电子密度的变化成线性关系。2)我们在国际上首先成功运用相对论密度泛函理论方法于镧系化合物分子结构研究中,在国际权威专著 “Handbook on the Physics and Chemistry of Rare Earths” Vol. 22 (Elsevier, Amsterdam)中,本工作被引述及讨论多达9个段落,并在6个表格中引述了我们的结果。3)我们对第一过渡周期金属卤化物分子电子结构的研究纠正了自1950年以来的实验理论基础的错误,提出新的能级次序(近年来最新实验已采用我们的新理论)。我们的这一结论已被当前化学界所接受(见 Chem. Rev. 100 (2000) 2233-2301)。4)密度泛涵理论(DFT)能很好地解决一般化学问题(甚至包括库伦相关效应),但不能解决非动态(Nondynamical)电子相关效应。我们深入分析和应用分数轨道占据数(FON)优化方法,来模拟电子的非动态电子相关效应,成功地解决了相同组态不相交问题,解决了一般 DFT 所不能解决的问题。本文被国际著名量子化学程序ADF指定为DFT分数轨道占据数(FON)方法的唯一参考文献。 在此领域的工作,已在国际顶级化学刊物Angew. Chem. Int. Ed. 和J. Am. Chem. Soc. 上发表了3篇论文;在J.Chem.Phys., J.Phy.Chem, Chem.Phys.Lett. 等国际化学核心期刊发表论文二十余篇,第一作者文章的SCI他引210余次。
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成果数
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【期刊论文】On Relativity, Bonding, and Valence Electron Distribution
王曙光, Shu-guang Wang, †, ‡ Wenjian Liu, §, ¶ and W. H. Eugen Schwarz*, ‡
J. Phys. Chem. A 2002, 106, 795-803,-0001,():
-1年11月30日
The scalar relativistic contributions to bond or atomization energies of homo- or hetero-polar s-p-bonded atoms, △relE(bond), correlate well with the changes on bond formation of the electron density, integrated throughout the spatial K-shell region of the heavy nucleus, △bondFK-region, times Z4, where Z is the nuclear charge. The "bond density changes" in the innermost atomic core regions, however, have no direct simple relationship to the electron density reorganizations in the outer atomic valence shell regions, which determine the nonrelativistic main contribution to the bond energy, △nonrelE(bond). Also, scalar relativistic bond energy changes and bond length changes, △relRe, are not directly correlated. Namely, △relE(bond) correlates with the difference △bondFK-region, whereas △relRe correlates with the derivative (dFK-region/dR). Reducing the internuclear distance from the separated to the united atom limit through the equilibrium distance value, Re, the density around the nucleus at first decreases in many cases, goes through a minimum, and finally increases again. Therefore (dFK-region/dR) may be positive or negative at Re.
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【期刊论文】Relativistic effects of p-block molecules
王曙光, S.G. Wang a, W.H.E. Schwarz a, b, *
Journal of Molecular Structurc (Thcochcm) 338(1995)347-362,-0001,():
-1年11月30日
Density functional calculations including relativistic as well as nonlocal exchange and correlation corrections have been performed on group 14 molecules MO. MH4, MCI4 (M=C, Si, Ge, Sn, Pb). Good bond lengths, and reasonable bond energies and force constants have been obtained. The dipole moments of the MO series are quite good, and dμ/dR of CO is close to the experimental results. Relativistic corrections are important for the heavier molecules (M=Ge, Sn, Pb). Fractional relativistic changes of bond energies, bond lengths and force constants are nearly exactly proportional to Z2 (Z: heavy nuclear charge). The origin of the relativistic changes has been analyzed: the change upon bond formation of the valence orbitals near the heavy nucleus is decisive.
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【期刊论文】Density functional study of first row transition metal dihalides
王曙光, S. G. Wang and W. H. E. Schwarz a)
J. Chem. Phys., Vol. 109, No.17, 1 November 1998,-0001,():
-1年11月30日
In contrast to former ligand field predictions, the standard energetic order of the metal 3d orbitals, δ<π<σ, is not reproduced here. Throughout, the 3ds molecular orbital (MO) level is found rather low lying because of s-donating ligand induced 3d-4s hybridization in these linear dicoordinated compounds, while the 3dp is rather high due to the pronounced p-donor character of the halogen ligands at the short distances of the digonal halides. This results in an unexpected electron distribution for the ground state and in an unusual order of electronic states. The calculations are in general consistent with recent experimental findings. The approach yields semiquantitatively correct geometric parameters and vibrational frequencies, and qualitatively correct trends for the dissociation energies. Those properties show a secondary periodicity, similar to the one known for octahedral high-spin complexes, though for different electronic reasons. Unknown structures, vibrational frequencies, and dissociation energies are predicted.
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【期刊论文】On oxides of monovalent transition metals
王曙光, S.G. Wang, W.H.E. Schwarz
Journal of Alloys and Compounds 246(1997)131-138,-0001,():
-1年11月30日
l surrounding was simulated by a Madelung field. The influence of the surrounding alkali metal ions was examined. The electronic structure differs from that of the isoelectronic dihalides M'X2 (M'=M+1). Orbital mixing is more pronounced in [MO2]3-. The M3d-πg atomic orbital (a.o.) correlates in [MO2]3- with an antibonding M3d-O2p-π* molecular orbital (m.o.), the M3d-σg a.o. correlates with a strongly mixed nonbonding M3d-4s-σg hybrid-m.o. There is significant covalency in the dioxometallate(Ⅰ) anions in contrast to the more ionic dihalides. As a result the orders of calculated levels are different in some cases. The charge distribution may be symbolized by [M2δ-O2(1.5-δ)-]. The M-O bond length varies significantly with the π* occupation. The assignment of the electronic ground states and electronic spectra is still an unsolved problem. Its solution would throw light on the reliability of present-day DFT approaches.
Monovalent transition metal oxides, Density functional theory
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【期刊论文】Lanthanide Diatomics and Lanthanide Contractions
王曙光, S. G. Wang and W. H. E. Schwarz*
J. Phys. Chem. 1995, 99, 11687-11695,-0001,():
-1年11月30日
Density functional (DF) calculations including gradient-exchange and correlation corrections have been performed on the LnH, LnO, and LnF series (Ln = La, Gd, Yb, and Lu). Relativistic first-order perturbations including S-0 couplings are accounted for. The calculated molecular constants are in reasonable agreement with the experimental ones. The calculated lanthanide contractions of the three series, i.e. R(La-X) - R(Lu-X), are quite different, 0.198, (0.19 A) for LnH, 0.108, (0.11 A) for LnF, and only 0.05 A (0.04A) for LnO. There is good agreement between the calculated values and the experimental ones (values in parentheses). This astonishing variation has two origins, a monoatomic and a diatomic one, which are related to each other. The first point is the noninteger 4f-shell population. Participation of unoccupied 4f-AOs in outervalence shell bonding is important for strongly bound lighter lanthanides. The second point is the "rigidity" of the bond: the larger the bond energy or the force constant, the smaller the lanthanide contraction.
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【期刊论文】Density functional calculations of lanthanide oxides
王曙光, S. G. Wang, D. K. Pan, a) and W. H. E. Schwarz b)
J. Chem. Phys. 102 (23), 15 June 1995,-0001,():
-1年11月30日
Density functional (DF) calculations have been performed on LaO, EuO, GdO, YbO and YbF. Gradient-exchange and correlation functionals work satisfactorily in the outer valence shells of these molecules, but less well for the localized lanthanide f -shells. Relativistic corrections to bond lengths, bond energies and vibrational frequencies are of quite different magnitudes and origins. The inner Ln 4f -shell has a fractional electron population in several molecular states. We corroborate the assignment of the 01 ground state of YbO as configuration mixed Yb21(f 14/ f 13s)O22. The effective charge distribution of the lanthanide oxides is at best approximated by Ln1O2.
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王曙光, S. G. Wang and W. H. E. Schwarz
J. Chem. Phys. 105 (11), 15 September 1996,-0001,():
-1年11月30日
If the energies of occupied and empty orbitals as functions of N geometric parameters vary in different manners, single determinantal approaches such as the density functional ones may violate the Aufbau principle and the noncrossing rule, i.e., states of the same symmetry may cross in an (N21)-dimensional parameter subspace. If dominant configuration mixing is simulated by a mixed ensemble density with fractional occupation numbers of the orbitals at the Fermi level, the density functional approaches recover the avoided crossing, as first pointed out by Dunlap and Mei [J. Chem. Phys. 78, 4997 (1983)]. However, present density functional approaches do not recover the nonavoided crossing in (N22)-dimensional subspaces. The density functional-fractional occupation number approach yields reasonable pathways for the transition from the cyclic to the open ground state of O3 and SO2 molecules.
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王曙光, Shu-Guang Wang and W. H. Eugen Schwarz*
Angew Chem Int Ed. 2000, 39, No.10,-0001,():
-1年11月30日
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【期刊论文】Quasi-Relativistic Density Functional Study of Aurophilic Interactions
王曙光, Shu-Guang Wang and W. H. Eugen Schwarz*
J. AM. CHEM. SOC. 2004, 126, 1266-1276,-0001,():
-1年11月30日
Abstract: Fifteen molecules containing the Au(I) species have been calculated by ab initio HF and MP2 methods and by five different density functional approaches. The aurophilic Au(d10)-Au(d10) bonding mechanism has been investigated. Both, one-electron interactions (i.e., electrostatic, polarization, charge transfer, and orbital interference) and two-electron effects (i.e., correlation, dispersion) contribute significantly to the so-called 'secondary' or metallophilic bonds representing the Au-Au interaction. Second, the applicability of density functional approaches to this type of bonding has been tested. It is well-known that present day density functionals are not yet designed to simulate the long-range London dispersion forces between nonoverlapping systems, whereas they approximately reproduce the short range dynamical electron correlations of strongly overlapping chemically bonded nondegenerate species. It is found here empirically for the investigated groups of gold(I) cluster compounds that simple local density functionals (LDF) of the Slater (or Slater plus Vosko) type yield rather reasonable estimates for the equilibrium distances, and (on the average) also for the aurophilic interaction energies, though with rather large standard deviations. Still LDF are useful for survey investigations of Au cluster compounds. Common gradient corrected DF are not recommended here, nor are the large core pseudopotentials for Au.
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