DEVELOPMENT OF MOLECULAR THEORY FOR THE CALCULATION OF POTENTIAL ENEGY SURFACES
DEVELOPMENT OF MOLECULAR THEORY FOR THE CALCULATION OF POTENTIAL ENEGY SURFACES
批准号:
05453019
负责人:
HIRAO Kimihiko
金额:
$4.35万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for General Scientific Research (B)
财政年份:
1993
资助国家:
日本
项目状态:
已结题
起止时间:
1993 至 1994
中文摘要
单参考微扰理论和团簇展开理论,如对称性自适应团簇理论和耦合团簇理论,在描述动力学关联时非常有效,但在处理非动力学关联时效果很差。CI很容易以多参考形式应用,并可以处理非动力学关联,但CI展开随着系统中电子数量的增加而变得不那么紧凑和效率更低。因此,我们发展了基于多参考的瑞利-薛定谔微扰理论。该方法是可靠的,并保留了单参考MP方法的优点。由于独立的电子对模型,该理论具有概念上的简单性。它的尺寸几乎是一致的。这是非常有效率和成本效益的。多重参考技术可以正确地将一个分子解离成它的片段。该方法适用于开壳和激发态,并已成功地应用于化学反应势能面的计算。并将该理论应用于苯的价态和里德堡激发能的研究。计算结果与实验结果吻合较好。计算价pi-pi^*激发能(括号内实验值)分别为^1B_<;2U>;,4.77(4.90),^1B_<;1U>;,6.28(6.20),^1E_<;1U>;,6.98(6.94)和^1E_<;2g>;,7.88(7.80)eV。里德堡激发能的预测精度也达到了0.18 eV或更高。对环戊二烯、呋喃、吡咯、萘和臭氧的价激发能和里德堡激发能也得到了类似精度的结果。
英文摘要
Single reference perturbation theory and cluster expansion theory such as symmetry adapted cluster and coupled cluster theories are very effective in describing dynamical correlation but fail badly in dealing with nondynamical correlation. CI is easily applied in multireference form and can handle nondynamical correlation but the CI expansion becomes less compact and less efficient as the number of electrons in the system grows. Therefore we have developed multireference based Rayleigh-Schrodinger perturbation theory. The MRMP is reliable and retains the attractive features of the single reference MP method. The theory has conceptual simplicity due to the independent electron pair model. It is almost size consistent. It is very efficient and cost effective. Multireference technique can dissociate a molecule correctly into its fragments. It is applicable to open shells and excited states.The state-specific MRMP has been sucessfully applied to the calculations of the potential energy surfaces of chemical reactions. Also the theory was applied to the study of valence and Rydberg excitation energies of benzene. The results compare well with the experiment. The calculated valence pi-pi^* excitation energies (experimental values in parentheses) are ^1B_<2u>,4.77 (4.90), ^1B_<1u>,6.28 (6.20), ^1E_<1u>,6.98 (6.94) and ^1E_<2g>,7.88 (7.80) eV,respectively. The Rydberg excitation energies are also predicted with an accuracy of 0.18 eV or better. Results of similar accuracy are obtained for the valence and Rydberg excitation energies for cyclopentadiene, furan, pyrrole, naphthalene and ozone.
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K.Hirao: "State-specific multireference Moller-Plessetperturbation theatment for singlet and triplet excited states, ionized states and electron attached states of H20" Chem.Phys.Lett.201. 59-66 (1993)
K.Hirao:“H20 的单线态和三线态激发态、电离态和电子附着态的状态特定多参考 Moller-Plesset 微扰疗法”Chem.Phys.Lett.201。
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"Molecular application of the generalized symmetry adapted cluster theory" Chem.Phys.Lett.204. 315-319 (1993)
“广义对称性簇理论的分子应用”Chem.Phys.Lett.204。
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K.Hirao: "Calculation of potential energy surfaces for chemical reactions" New Functionality Materials. Vol.C. 63-68 (1993)
K.Hirao:“化学反应势能面的计算”新功能材料。
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K.Hirao: "Multireference Moller-Plesset Perturbation Theatment for Valence and Rydberg Excited States of Benzene" Chem.Phys.Lett.(in press).
K.Hirao:“苯的化合价和里德伯激发态的多参考 Moller-Plesset 微扰疗法”Chem.Phys.Lett.(印刷中)。
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S.Yamanaka,: "CASPT2 and MRMP2 calculations of potential curves and effective exchange integrals for the dimer of triplet methylene" Chem.Phys.Lett.225. 213-220 (1994)
S.Yamanaka,:“CASPT2 和 MRMP2 计算三重态亚甲基二聚体的电位曲线和有效交换积分”Chem.Phys.Lett.225。
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共 29 条
Simulation and Dynamics of Real Chemical Systems
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批准号:14002004
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项目类别:Grant-in-Aid for Specially Promoted Research
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资助金额:$321.98万
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财政年份:2002
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负责人:HIRAO Kimihiko
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依托单位:
Development of Molecular Theory for Molecular Design and Reaction Control
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批准号:11166215
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项目类别:Grant-in-Aid for Scientific Research on Priority Areas (A)
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资助金额:$10.18万
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财政年份:1999
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负责人:HIRAO Kimihiko
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依托单位:
Development of ab initio molecular orbital program for large-scale molecular systems
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批准号:10555298
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项目类别:Grant-in-Aid for Scientific Research (B).
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资助金额:$7.94万
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财政年份:1998
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负责人:HIRAO Kimihiko
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依托单位:
Molecular Physical Chemistry for Molecular Design and Reaction Control
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批准号:10185101
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项目类别:Grant-in-Aid for Scientific Research on Priority Areas (A)
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资助金额:$90.94万
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财政年份:1998
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负责人:HIRAO Kimihiko
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依托单位:
Theoretical Study on the Photoreactions of Biological Compounds
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批准号:09450314
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$8.51万
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财政年份:1997
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负责人:HIRAO Kimihiko
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依托单位:
Time-dependent Approach in Theoretical Chemistry
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批准号:08044063
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项目类别:Grant-in-Aid for international Scientific Research
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资助金额:$2.43万
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财政年份:1996
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负责人:HIRAO Kimihiko
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依托单位:
Development of parallel ab initio molecular orbital program package
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批准号:07554083
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项目类别:Grant-in-Aid for Scientific Research (A)
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资助金额:$3.58万
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财政年份:1995
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负责人:HIRAO Kimihiko
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依托单位:
Cluster Expansion of the Wavefunction Theory and its Applications
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批准号:01470008
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项目类别:Grant-in-Aid for General Scientific Research (B)
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资助金额:$4.03万
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财政年份:1989
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负责人:HIRAO Kimihiko
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依托单位:
海外基金