An application of the Tamm-Dancoff and random phase approximations to the thermal decomposition of 1,2-dioxetane

Aoyama, T.; Yamakawa, Hiroshi; Akiba, Kazuto; Inamoto, Naoki

doi:10.1016/0009-2614(76)80380-6

Cited by 9 publications

(1 citation statement)

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“…The DFT and TDDFT calculations were performed with the Gaussian16 program . The B3LYP functional was used to obtain the ground-state minimum, , while the Tamm–Dancoff approximation (TDA) to TDDFT in combination with the TPSS functional was adopted by us to estimate the vertical excitation properties of lutein. The 6-31G*, 6-31G ** , and 6-31+G* basis sets were used in these calculations. , …”

Section: Computational Detailsmentioning

confidence: 99%

Understanding the Excited-State Relaxation Mechanisms of Xanthophyll Lutein by Multi-configurational Electronic Structure Calculations

Yin

Wang

Xue

et al. 2023

J. Chem. Inf. Model.

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The contradictory behaviors in light harvesting and non-photochemical quenching make xanthophyll lutein the most attractive functional molecule in photosynthesis. Despite several theoretical simulations on the spectral properties and excited-state dynamics, the atomic-level photophysical mechanisms need to be further studied and established, especially for an accurate description of geometric and electronic structures of conical intersections for the lowest several electronic states of lutein. In the present work, semiempirical OM2/MRCI and multi-configurational restricted active space self-consistent field methods were performed to optimize the minima and conical intersections in and between the 1Ag − , 2Ag − , 1Bu + , and 1Bu − states. Meanwhile, the relative energies were refined by MS-CASPT2(10,8)/6-31G*, which can reproduce correct electronic state properties as those in the spectroscopic experiments. Based on the above calculation results, we proposed a possible excitedstate relaxation mechanism for lutein from its initially populated 1Bu + state. Once excited to the optically bright 1Bu + state, the system will propagate along the key reaction coordinate, i.e., the stretching vibration of the conjugated carbon chain. During this period of time, the 1Bu − state will participate in and forms a resonance state between the 1Bu − and 1Bu + states. Later, the system will rapidly hop to the 2Ag − state via the 1Bu + /2Ag − conical intersection. Finally, the lutein molecule will survive in the 2Ag − state for a relatively long time before it internally converts to the ground state directly or via a twisted S 1 /S 0 conical intersection. Notably, though the photophysical picture may be very different in solvents and proteins, the current theoretical study proposed a promising calculation protocol and also provided many valuable mechanistic insights for lutein and similar carotenoids.

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