Nonadiabatic Derivative Couplings through Multiple Franck-Condon Modes Dictate the Energy Gap Law for Near and Short-Wave Infrared Dye Molecules.

Autor:	Ramos P; Department of Chemistry and Biochemistry, Queens College, City University of New York, 65-30 Kissena Boulevard, New York, New York 11367, United States., Friedman H; Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States., Li BY; Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States., Garcia C; Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States., Sletten E; Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States., Caram JR; Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095, United States., Jang SJ; Department of Chemistry and Biochemistry, Queens College, City University of New York, 65-30 Kissena Boulevard, New York, New York 11367, United States.; Chemistry and Physics PhD programs, Graduate Center, City University of New York, New York, New York 10016, United States.
Jazyk:	angličtina
Zdroj:	The journal of physical chemistry letters [J Phys Chem Lett] 2024 Feb 22; Vol. 15 (7), pp. 1802-1810. Date of Electronic Publication: 2024 Feb 08.
DOI:	10.1021/acs.jpclett.3c02629
Abstrakt:	Near infrared (NIR, 700-1000 nm) and short-wave infrared (SWIR, 1000-2000 nm) dye molecules exhibit significant nonradiative decay rates from the first singlet excited state to the ground state. While these trends can be empirically explained by a simple energy gap law, detailed mechanisms of nearly universal behavior have remained unsettled for many cases. Theoretical and experimental results for two representative NIR/SWIR dye molecules reported here clarify the key mechanism for the observed energy gap law behavior. It is shown that the first derivative nonadiabatic coupling terms serve as major coupling pathways for nonadiabatic decay processes from the first excited singlet state to the ground state for these NIR and SWIR dye molecules and that vibrational modes other than the highest frequency modes also make significant contributions to the rate. This assessment is corroborated by further theoretical comparison with possible alternative mechanisms of intersystem crossing to triplet states and also by comparison with experimental data for deuterated molecules.
Databáze:	MEDLINE
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