| Budget Amount *help |
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2003: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2002: ¥2,900,000 (Direct Cost: ¥2,900,000)
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| Research Abstract |
Photophysical properties of singlet and triplet metal-to-ligand charge transfer states (MLCT) of d^<10> metal compounds with tetrahedral structure, e.g., [Cu(I)(diimine)_2]^+ or [Pt(0)(binap)_2] have been studied. The lifetimes of 'MLCT were determined to be 13-16 ps for the Cu(I) compounds and 3.2 ps for the Pt(O) compound, much longer than expected from strong spin-orbit coupling constant of Cu-3d (880 cm^<-1>) or Pt-5d (4000 cm^<-1>) orbitals. Theoretical analysis based on density functional theory revealed that structural distortion in the MLCT states causes large energy splitting between HOMO and HOMO -1, which prevents a very fast ISC due to the strong spin-orbit interactions between these orbitals. Although the phosphorescence observed at lower temperatures is due to intensity borrowing from ^1MLCT→GS transition the large energy difference between HOMO and HOMO -2 reduces the extent of mixing between the lowest ^3MLCT and ^1MLCT due to spin-orbit interaction, thereby decreasing
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the radiative rate of the phosphorescence.
A PC-clustering computer system with the peak' performance of 90Gflops was developed. To understand ultrafast photochemical processes following the light excitation of Ru(II)-Co(III) binuclear compounds, potential energy curves along with both intramolecular coordinates and solvent coordinates were calculated and the magnitudes of intramolecular electronic interaction energy between these potential curves were evaluated. It was revealed that ultrafact energy and electron transfer from MLCT state of the Ru(II) moiety to the Co(III) moiety occurred with vibronic coupling due to asymmetric vibrations which mixed d_<x2-y2> orbital on cobalt and π-orbitals on nitrogen coordinating to the cobalt.
A new method to assess the geometries obtained from quantum chemical calculations using experimental emission spectra was developed. The fluorescence spectra simulated from geometries obtained using several quantum chemical models such as UHF, UDFT, TDDFT, CIS, and CASSCF were compared with the experimental ones, confirming the accuracy of UDFT and TDDFT calculation on geometries. Less
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