On the entanglement of chromophore and solvent orbitals.

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Tác giả: Kim Ngan Huynh, Xinwei Ji, Yuezhi Mao, Xiaoliang Pan, Zheng Pei, Yihan Shao, Binju Wang, Junjie Yang

Ngôn ngữ: eng

Ký hiệu phân loại: 594.38 *Pulmonata

Thông tin xuất bản: United States : The Journal of chemical physics , 2025

Mô tả vật lý:

Bộ sưu tập: NCBI

ID: 961

Among various types of chromophore-solvent interactions, the entanglement of chromophore and solvent orbitals, when significant, can cause the chromophore frontier orbitals to spread over to nearby solvent molecules, introducing partial charge-transfer character to the lowest excitations of the chromophore and lowering the excitation energies. While highly intuitive, the physical details of such orbital entanglement effects on the excitation energies of chromophores have yet to be fully explored. Here, using two well-known biochromophores (oxyluciferin and p-hydroxybenzyledene imidazolinone) as examples, we show that the chromophore-solvent orbital entanglements can be elucidated using two quantum mechanical embedding schemes: density matrix embedding theory and absolutely localized molecular orbitals. However, there remains a great challenge to incorporate the orbital entanglement effect in combined quantum mechanical molecular mechanical (QM/MM) calculations, and we hope that our findings will stimulate the development of new methods in that direction.
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