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Signature of the neighbor's quantum nuclear dynamics in the electron transfer mediated decay spectra.

ABSTRACT: We computed fully quantum nuclear dynamics, which accompanies electron transfer mediated decay (ETMD) in weakly bound polyatomic clusters. We considered two HeLi₂ clusters - with Li₂ being either in the singlet electronic ground state or in the triplet first excited state - in which ETMD takes place after ionization of He. The electron transfer from Li₂ to He⁺ leads to the emission of another electron from Li₂ into the continuum. Due to the weak binding of He to Li₂ in the initial states of both clusters, the involved nuclear wavepackets are very extended. This makes both the calculation of their evolution and the interpretation of the results difficult. We showed that despite the highly delocalized nature of the wavepackets the nuclear dynamics in the decaying state is imprinted on the ETMD electron spectra. The analysis of the latter helps understanding the effect which electronic structure and binding strength in the cluster produce on the quantum motion of the nuclei in the decaying state. The results produce a detailed picture of this important charge transfer process in polyatomic systems.

SUBMITTER: Ghosh A

PROVIDER: S-EPMC8278904 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature

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Signature of the neighbor's quantum nuclear dynamics in the electron transfer mediated decay spectra.

Ghosh Aryya A Cederbaum Lorenz S LS Gokhberg Kirill K

Chemical science 20210609 27

We computed fully quantum nuclear dynamics, which accompanies electron transfer mediated decay (ETMD) in weakly bound polyatomic clusters. We considered two HeLi2 clusters - with Li2 being either in the singlet electronic ground state or in the triplet first excited state - in which ETMD takes place after ionization of He. The electron transfer from Li2 to He+ leads to the emission of another electron from Li2 into the continuum. Due to the ...[more]

PMID: 34349910

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Project description:Theoretical prediction of electronic absorption spectra without input from experiments is no easy feat, as it requires addressing all of the factors that affect line shapes. In practice, however, the methodologies are limited to treat these ingredients only to a certain extent. Here, we present a multiscale protocol that addresses the temperature, solvent, and nuclear quantum effects as well as anharmonicity and the reconstruction of the final spectra from individual transitions. First, quantum mechanics/molecular mechanics (QM/MM) molecular dynamics is conducted to obtain trajectories of solute-solvent configurations, from which the corresponding quantum-corrected ensembles are generated through the generalized smoothed trajectory analysis (GSTA). The optical spectra of the ensembles are then produced by calculating vertical transitions using time-dependent density-functional theory (TDDFT) with implicit solvation. To obtain the final spectral shapes, the stick spectra from TDDFT are convoluted with Gaussian kernels where the half-widths are determined by a statistically motivated strategy. We have tested our method by calculating the UV-vis spectra of a recently discovered acridine photocatalyst in two redox states. Vibronic progressions and broadenings due to the finite lifetime of the excited states are not included in the methodology yet. Nuclear quantization affects the relative peak intensities and widths, which is necessary to reproduce the experimental spectrum. We have also found that using only the optimized geometry of each molecule works surprisingly well if a proper empirical broadening factor is applied. This is explained by the rigidity of the conjugated chromophore moieties of the selected molecules, which are mainly responsible for the excitations in the spectra. In contrast, we have also shown that other parts of the molecules are flexible enough to feature anharmonicities that impair the use of other techniques such as Wigner sampling.

Dataset Information

Signature of the neighbor's quantum nuclear dynamics in the electron transfer mediated decay spectra.

Publications

Signature of the neighbor's quantum nuclear dynamics in the electron transfer mediated decay spectra.

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