张庆竹
环境化学、环境物理化学、化学反应动力学、环境友好材料
个性化签名
- 姓名:张庆竹
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学术头衔:
博士生导师, 教育部“新世纪优秀人才支持计划”入选者
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学科领域:
环境工程学
- 研究兴趣:环境化学、环境物理化学、化学反应动力学、环境友好材料
张庆竹教授,女,博士,首批新世纪优秀人才获得者。于1993年在山东大学化学院获学士学位;2000年及2003年分别获硕士及博士学位;2003年至2004年在香港城市大学作博士后。所撰写的博士学位论文荣获全国百篇优秀博士学位论文提名奖。已在J.Chem.Phys., J.Phys.Chem., J. Atmos. Chem., Chem. Phys. Lett.,中国科学等国内外著名刊物上发表40余篇学术论文,其中,刊物影响因子大于2的学术论文为36篇(第一作者的为30篇),且发表的论文全部被SCI收录,SCI收录率达100%。由于成果突出,在2004年7月被山东大学环境研究院按学术带头人人才引进。研究领域包括环境化学、环境物理化学、化学反应动力学、环境友好材料。2005年获教育部首批新世纪优秀人才支持计划资助。
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10
【期刊论文】Direct ab Initio Dynamics Studies of the Reactions of H with SiH4-nCln (n = 1-3)
张庆竹, Qingzhu Zhang, Shaokun Wang, and Yueshu Gu*
J. Phys. Chem. A 2002, 106, 3796-3803,-0001,():
-1年11月30日
The direct hydrogen abstraction reactions of H atoms with SiH3Cl, SiH2Cl2, and SiHCl3 have been studied systematically using ab initio molecular orbital theory. Geometries have been optimized at the UMP2 level with the 6-311G(2d, p) basis set. The G3MP2 theory has been used for the final single-point energy calculation. Theoretical analysis provides conclusive evidence that the main process occurring in each case is the hydrogen abstraction from the Si-H bond; the chlorine abstraction from the Si-Cl bond has a higher barrier and is difficult to react. Changes of geometries, generalized normal-mode vibrational frequencies, and potential energies along the reaction path of the reactions are discussed and compared. The kinetic calculations of the title reactions have been deduced using canonical variational transition state theory (CVT) with the smallcurvature tunneling (SCT) correction method over a wide temperature range of 200-3000K. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior. Three-parameter rate-temperature formulas have been fitted as follows: k1=1.54
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【期刊论文】Kinetic and mechanistic studies on the abstraction reactions of atomic O (3P) with
张庆竹, Qingzhu Zhang, Yueshu Gu, a) and Shaokun Wang
J. Chem. Phys., Vol. 118, No.2, 8 January 2003,-0001,():
-1年11月30日
The reactions of atomic O (3P) with (CH3)2SiH2 and (CH3)3SiH have been studied theoretically using ab initio molecular orbital theory for the first time. Geometries have been optimized at the MP2 level with the 6-311G(d,p) and 6-311G(2d,2p) basis sets. The single-point energy calculations have been carried at the QCISD(T)/6-3111G(3d f, 2p) level. Theoretical analysis provides conclusive evidence that the main process occurring in each reaction is the hydrogen abstraction from the Si-H bonds leading to the formation of the H2 and silyl radical; the hydrogen abstraction from the C-H bonds has higher barrier and is difficult to react. Two nearly degenerate transition states of 3A" and 3A' symmetries have been located for each hydrogen abstraction reaction from the Si-H bonds. Changes of geometries, generalized normal-mode vibrational frequencies, and potential energies along the reaction paths are discussed and compared. The rate constants have been deduced over a wide temperature range of 200-3000 K using canonical variational transition-state theory (CVT) with small curvature tunneling effect (SCT). The calculated CVT/SCT rate constants exhibit typical non-Arrhenius behavior, three-parameter rate-temperature formulas are fitted as follows (in units of cm3 molecule21 s21): k1(T)=(3.41×10216)T1.65 3exp(2411.72/T) and k2(T)=(1.85×10215)T1.42 exp(2372.57/T) for the reactions of O (3P) with (CH3)2SiH2 and (CH3)3SiH, respectively. The calculated rate constants are compared with the available experimental values.
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张庆竹, Qingzhu Zhang, Yueshu Gu, a) and Shaokun Wang
J. Chem. Phys., Vol. 119, No.8, 22 August 2003,-0001,():
-1年11月30日
The hydrogen abstraction reactions of atomic O (3P) with CH3Cl and CH2Cl2 have been studied theoretically using ab initio molecular orbital theory for the first time. In the Cs symmetry, both reactions proceed over two potential-energy surfaces, 3A" and 3A' generated by the pseudo-Jahn- Teller effect. Two nearly degenerate transition states of 3A" and 3A' symmetries have been located for each hydrogen abstraction reaction from the C-H bonds. Geometries of the reactants, transition states, and products have been optimized at the second-order M
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张庆竹, Qingzhu Zhang, Shaokun Wang, and Yueshu Gu a)
J. Chem. Phys., Vol. 119, No.21, 1 December 2003,-0001,():
-1年11月30日
The reaction of atomic O (3P) with CH3CHCl2 has been studied theoretically using ab initio direct dynamics methods for the first time. This reaction involves two channels: H abstraction from the methyl group (CH3), and H abstraction from the methyne group (CH). Two nearly degenerate saddle points of 3A" and 3A' symmetries have been located for each hydrogen abstraction channel At the QCISD(T)/6-3111G(3d f, 2p)//MP2/6-311G(d,p) level, the potential barrier of H abstraction from the CH3 group is higher about 6 kcal/mol than that of H abstraction from the CH group. Changes of geometries, generalized normal-mode vibrational frequencies, and potential energies along the reaction paths for all the channels are discussed and compared. On the basis of the ab initio data, the rate constants of each channel have been deduced by canonical variational transition state theory with small-curvature tunneling correction method over a wide temperatures range of 200-3000K. The theoretical results have been compared with available experimental data. The kinetics calculations show that the variational effect is small and in the low temperature range (200-800K), the small curvature tunneling contribution is important for all the channels. The detailed branching ratios have been discussed.
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【期刊论文】Ab Initio and Kinetic Calculations for the Reactions of H with (CH3)(4-n)GeHn n = 1, 2, 3, 4)
张庆竹, Qingzhu Zhang, Dongju Zhang, Shaokun Wang, and Yueshu Gu*
J. Phys. Chem. A 2002, 106, 122-129,-0001,():
-1年11月30日
The direct hydrogen abstraction reactions of H atom with GeH4, CH3GeH3, (CH3)2GeH2, and (CH3)3GeH have been studied systematically using ab initio molecular orbital theory. Geometries have been optimized at the UMP2 level with 6-31G (d) and 6-311G (2df,p) basis sets. G2MP2 theory has been used in the final singlepoint energy calculation. Theoretical analysis provided conclusive evidence that the main process occurring in each case is the hydrogen abstraction from the Ge-H bond leading to the formation of the H2 and germyl radicals; the hydrogen abstraction from the C-H bond has higher barriers and is difficult to react. The kinetic calculations of the title reactions have been deduced using the canonical variational transition-state theory (CVT) with the small-curvature tunneling correction method (SCT) over the temperature range of 200-3000K. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior. Three-parameter rate-temperature formulas have been fitted as follows: k1=(2.17×10-17)T2.16 exp(-294.2/T), k2=(2.21×10-17)T2.22 exp(-161.6/T), k3=(1.96×10-17)T2.18 exp(-108.0/T), and k4=(6.66×10-18)T2.33 exp(-60.3/T) for the reactions of H with GeH4, CH3GeH3, (CH3)2GeH2, and (CH3)3GeH, respectively (in units of cm3 molecule-1 s-1). Studies show that the methyl substitution has an effect on the strength and reactivity of the Ge-H bond in (CH3) (4-n)GeHn (n) 1-3). The calculated CVT/SCT rate constants are in excellent agreement with the available experimental values.
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张庆竹, Qingzhu Zhang, Yueshu Gu, * and Shaokun Wang
J. Phys. Chem. A 2003, 107, 3069-3075,-0001,():
-1年11月30日
The hydrogen abstraction reaction of atomic O (3P) with CHF2Cl has been studied theoretically for the first time using ab initio molecular orbital theory. Two nearly degenerate saddle points of 3A" and 3A' symmetries have been located for this hydrogen abstraction reaction from the C-H bond. The potential energy surface information has been obtained at the MP2 level with the 6-311G (2d,p) basis set. Energies along the minimum energy path have been improved by a series of single-point ab initio QCISD (T)//MP2 calculation. Changes of geometries, generalized normal-mode vibrational frequencies, and potential energies along the reaction path are discussed. The kinetics nature is obtained using canonical variational transition state theory (CVT) with the small-curvature tunneling (SCT) correction method over a wide temperature range of 200 3000K. The result shows that the variational effect is small, and in the lower-temperature range, the SCT effect is important for the title reaction. The calculated CVT/SCT rate constants exhibit typical non-Arrhenius behavior, and a three-parameter rate-temperature formula is fitted as follows (in units of cm3 molecule-1 s-1): k (T) = 4.75
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张庆竹, Qingzhu Zhang, Yueshu Gu, * and Shaokun Wang
J. Phys. Chem. A 2003, 107, 3884-3890,-0001,():
-1年11月30日
The reactions of H atoms with GeH4, GeH3Cl, GeH2Cl2, and GeHCl3 have been studied systematically using ab initio molecular orbital theory. Theoretical analysis provides conclusive evidence that the main process occurring in each case is hydrogen abstraction from the Ge-H bonds. The reaction thermal rate constants for the temperature range 200-3000K are deduced by canonical variational transition state theory (CVT) with small curvature tunneling (SCT) correction method. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior. Three-parameter rate-temperature formulas have been fitted as follows: k1) 3.09×10-17T2.16 exp (-286.74/T), k2=1.94×10-17T2.18 exp(-276.82/T), k3=4.19 10-18T2.37 exp (-227.64/T), and k4=2.02×10-17 T1.98 exp (-218.51/T) for the reactions of H with GeH4, GeH3Cl, GeH2Cl2, and GeHCl3, respectively (in units of cm3 molecule-1 s-1). Studies show that chlorine substitution has a very slight effect on the strength and reactivity of the Ge-H bonds in GeH (4-n)Cln (n=1-3).
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张庆竹, Qingzhu Zhang, Yueshu Gu, * and Shaokun Wang
J. Phys. Chem. A 2003, 107, 8295-8301,-0001,():
-1年11月30日
The reaction of atomic H and EtSiH3 (CH3CH2SiH3) has been studied theoretically by ab initio direct dynamics methods for the first time. This reaction involves three channels: H abstraction from the silicyl group (SiH3), H abstraction from the methylene group (CH2), and H abstraction from the methyl group (CH3). At the QCISD (T)/6-311+G(3df,2p)//MP2/6-311G(2d,p) level, H abstraction from the silicyl group has the smallest potential barrier (4.58kcal/mol). The potential barriers of H abstraction from the methylene and methyl groups are higher by 4-6kcal/mol than that of H abstraction from the silicyl group. Changes of geometries, generalized normal-mode vibrational frequencies, and potential energies along the reaction paths for all the channels are discussed and compared. On the basis of the ab initio data, the rate constants of each channel have been deduced by canonical variational transition state theory (CVT) with a small-curvature tunneling (SCT) correction method over a wide temperatures range of 200-3000K. The theoretical result has been compared with available xperimental data. The kinetics calculations show that the variational effect is small, and in the low-temperature range (200-500K), the small curvature tunneling effect is important for all the channels. The detailed branching ratios have been discussed.
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【期刊论文】Ab Initio and Kinetic Calculation for the Abstraction Reaction of Atomic O (3P) with SiH4
张庆竹, Qingzhu Zhang, Shaokun Wang, Jianhua Zhou, and Yueshu Gu*
J. Phys. Chem. A 2002, 106, 115-121,-0001,():
-1年11月30日
The reaction of O (3P) with silane was studied theoretically. The detailed mechanism was revealed for the first time. Two nearly degenerate transition states of 3A"and 3A" symmetries were located for the title reaction. Geometries were optimized at the UMP2 level with the 6-311G(2d,2p) basis set. The QCISD (T) level with the 6-311++G (3df, 3pd) basis set was used in the final single-point energy calculations. On the basis of the ab initio data, the kinetic nature was studied using canonical variational transition-state theory (CVT) with small-curvature tunneling effect (SCT) correction. The rate constants were calculated over a wide temperature range of 200-3000K. The CVT/SCT rate constants exhibit typical non-Arrhenius behavior, a three-parameterrate-temperature formula was fitted as follows: k (T)=(1.53
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张庆竹, Qingzhu Zhang, Shaokun Wang, Yueshu Gu *
Chemical Physics Letters 352(2002)521-528,-0001,():
-1年11月30日
The hydrogen abstraction reaction of O ð3PÞ with CH3Br has been studied theoretically for the first time. Two nearly degenerate transition states of 3A00 and 3A0 symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 level with the 6-311G(2d, p) basis set. The G2MP2 method has been used for the final single-point energy calculation. On the basis of the ab initio data, the rate constants have been deduced over a wide temperature range 200-3000K using canonical variational transition-state theory (CVT) with a small curvature tunneling effect (SCT). The calculated CVT/SCT rate constants exhibit typical non-Arrhenius behavior, a three-parameter rate-temperature formula is fitted in units of cm3 molecule-1 s -1 as follows: k(T)=(2:83×10-19)T 2:33 exp (-2115.97/T).
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