2005 Fiscal Year Final Research Report Summary
Four-Component Dirac-type Electron-Correlation Theory : Excited State Chemistry and Magnetic Chemistry
| Project/Area Number |
14340179
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Physical chemistry
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| Research Institution | Tokyo Metropolitan University |
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Principal Investigator |
HADA Masahiko Tokyo Metropolitan University, Chemistry, Professor, 理工学研究科, 教授 (20228480)
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| Project Period (FY) |
2002 – 2005
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| Keywords | Dirac Method / Nuclear Magnetic Shielding Tensor / Molecular Magnetizability / Relativistic Effect / Magnetic Circular Dichroism / Infinite-Order FW Method / GUHF Method / Heme |
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| Research Abstract |
Guarantee on the accuracy of quantum-chemical calculations over all types of molecules containing all atoms is one of the most important subjects in the quantum chemistry. Electron-correlation methods must be re-constructed with relativistic hamiltonians. The new theories and methods concerning relativistic electronic-correlation are required to be checked carefully by applying to calculations of energies and molecular properties, in special, molecular magnetic properties. This project was planed on the viewpoint described above.
At the Final stage of this project, we summarize the results briefly as follows. First, we developed the basis functions for 4-component Dirac wave-functions. The nuclear magnetic shielding tensor was calculated using the 4-component electron-correlation (CCSD) method. As one of the concrete and economic methods, we developed an accurate 2-component relativistic method in which the finite-order FW transformation is used. A series of applications were carried out for molecules and molecular properties which are required the relativistic corrections. We show the listing below.
1. Basis Sets for the Four-Component Dirac-Hartree-Fock-Roothaan Method
2. Infinite-Order FW transformation Method
3. Applications
(1) Circular Dichroism and Magnetic Circular Dichroims
(2) Nuclear Magnetic Shielding Tensdrs
(i) HX (X = F, Cl, Br, I) by the 4-component CCSD method
(ii) X(-) and XO4(-) (X = F, Cl, Br, I) : Synergistic effects of electron-correlations and relativistic corrections.
(iii) Paramagnetic 13-C NMR chemical shifts of iron-bounded CN of Fe(III)-porphyrins :
(3) Molecular Magnetizability
The Time-Dependent Generalized UHF (TD-GUHF) method was developed incorporating with the second-order spin-dependent Douglas-Kroll method. We showed the relativistic effects on the molecular magnetizabilities in TeH2.
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