Issues

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2022

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vol. 20 /

Issue 2

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О. D. Kachkovsky, A. P. Naumenko, V. I. Borisyuk, N. V. Obernikhina, and Yu. L. Slominskiy
Nature of Lowest Electron Transitions in Anionic Polymethine Dyes with Keto-Containing Terminal Groups
0473–0486 (2022)

PACS numbers: 31.15.ee, 78.40.Me, 78.55.-m, 81.07.Nb, 82.50.Hp, 82.80.Dx, 87.85.Qr

The complex quantum-chemical and spectral studies of the anionic polymethine dyes with the simplest symmetrical terminal groups and with different-length polymethine chain are performed. As shown, these dyes produce the specific molecular orbitals (МО) positioned nearly the energy gap and located only within the terminal groups. By investigation of the absorption spectra, it is established that the typical highly intensive long-wave-length spectral band is observed and bathochromically shifted upon lengthening of the open conjugated chain; this polymethine band is concerned with the electron transition between the frontier levels of the opposite symmetry. In the contrast, the local MO takes part in so-called quasi-local electron transitions involving also the frontier orbital. The local transitions have small dipole moments, and hence, they do not practically appear in the absorption spectra; however, the local transitions cause the appearance of the non-deep minima in the spectra of the fluorescence-excitation anisotropy.

Key words: anionic polymethine dyes, excitation fluorescence anisotropy spectra, quantum-chemical calculations, excited state, higher electron transitions.

https://doi.org/10.15407/nnn.20.02.473

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