Computational analyses of singlet-singlet and singlet-triplet transitions in mononuclear gold-capped carbon-rich conjugated complexes |
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Authors: | Cao Zexing Zhang Qianer |
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Affiliation: | State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China. zxcao@xwu.edu.cn |
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Abstract: | Density functional theory and CASSCF calculations have been used to determine equilibrium geometries and vibrational frequencies of metal-capped one-dimensional pi-conjugated complexes (H3P)Au(C[triple chemical bond]C)(n)(Ph) (n = 1-6), (H3P)Au(C[triple chemical bond]CC6H4)(C[triple chemical bond]CPh), and H3P--Au(C[triple chemical bond]CC6H4)C[triple chemical bond]CAu--PH3 in their ground states and selected low-lying pi(pi)* excited states. Vertical excitation energies for spin-allowed singlet-singlet and spin-forbidden singlet-triplet transitions determined by the time-dependent density functional theory show good agreement with available experimental observations. Calculations indicate that the lowest energy 3(pi(pi)*) excited state is unlikely populated by the direct electronic excitation, while the low-lying singlet and triplet states, slightly higher in energy than the lowest triplet state, are easily accessible by the excitation light used in experiments. A series of radiationless transitions among related excited states yield the lowest 3(pi(pi)*) state, which has enough long lifetimes to exhibit its photochemical reactivities. |
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Keywords: | Au‐containing carbon chains excited states spin‐orbit coupling theoretical calculations |
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