Intersystem crossing rates of S1 state keto-amino cytosine at low excess energy

Lobsiger, Simon; Etinski, Mihajlo; Blaser, Susan; Frey, Hans-Martin; Marian, Christel; Leutwyler, Samuel (2015). Intersystem crossing rates of S1 state keto-amino cytosine at low excess energy. The Journal of Chemical Physics, 143(23), p. 234301. American Institute of Physics 10.1063/1.4937375

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The amino-keto tautomer of supersonic jet-cooled cytosine undergoes intersystem crossing (ISC) from the v = 0 and low-lying vibronic levels of its S1(¹ππ*) state. We investigate these ISC rates experimentally and theoretically as a function of S1 state vibrational excess energy Eexc. The S1 vibronic levels are pumped with a ~5 ns UV laser, the S1 and triplet state ion signals are separated by prompt or delayed ionization with a second UV laser pulse. After correcting the raw ISC yields for the relative S1 and T1ionization cross sections, we obtain energy dependent ISC quantum yields Q corr ISC =1% –5%. These are combined with previously measured vibronic state-specific decay rates, giving ISC rates kISC = 0.4–1.5 ⋅ 10⁹ s⁻¹, the corresponding S1⇝S0internal conversion (IC) rates are 30–100 times larger. Theoretical ISC rates are computed using SCS-CC2 methods, which predict rapid ISC from the S1; v = 0 state with kISC = 3 ⋅ 10⁹ s⁻¹ to the T1(³ππ*) triplet state. The surprisingly high rate of this El Sayed-forbidden transition is caused by a substantial admixture of ¹nOπ* character into the S1(¹ππ*) wave function at its non-planar minimum geometry. The combination of experiment and theory implies that (1) below Eexc = 550 cm⁻¹ in the S1 state, S1⇝S0internal conversion dominates the nonradiative decay with kIC ≥ 2 ⋅ 10¹⁰ s⁻¹, (2) the calculated S1⇝T1 (¹ππ*⇝³ππ*) ISC rate is in good agreement with experiment, (3) being El-Sayed forbidden, the S1⇝T1 ISC is moderately fast (kISC = 3 ⋅ 10⁹ s⁻¹), and not ultrafast, as claimed by other calculations, and (4) at Eexc ~ 550 cm⁻¹ the IC rate increases by ~50 times, probably by accessing the lowest conical intersection (the C5-twist CI) and thereby effectively switching off the ISC decay channels.

Item Type:

Journal Article (Original Article)

Division/Institute:

08 Faculty of Science > Institute of Applied Physics
08 Faculty of Science > Departement of Chemistry and Biochemistry

UniBE Contributor:

Lobsiger, Simon; Blaser, Susan; Frey, Hans-Martin and Leutwyler, Samuel

Subjects:

500 Science > 570 Life sciences; biology
500 Science > 540 Chemistry
600 Technology > 620 Engineering
500 Science

ISSN:

0021-9606

Publisher:

American Institute of Physics

Language:

English

Submitter:

Beatrice Niederhauser

Date Deposited:

03 Feb 2016 16:31

Last Modified:

06 Jul 2016 20:56

Publisher DOI:

10.1063/1.4937375

BORIS DOI:

10.7892/boris.75040

URI:

https://boris.unibe.ch/id/eprint/75040

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