Planarizing cytosine: The S1 state structure, vibrations, and nonradiative dynamics of jet-cooled 5,6-trimethylenecytosine

Maria A Trachsel; Simon Lobsiger; Tobias Schär; Lluís Blancafort; Samuel Leutwyler

doi:10.1063/1.4989465

Planarizing cytosine: The S₁ state structure, vibrations, and nonradiative dynamics of jet-cooled 5,6-trimethylenecytosine

J Chem Phys. 2017 Jun 28;146(24):244308. doi: 10.1063/1.4989465.

Authors

Maria A Trachsel¹, Simon Lobsiger¹, Tobias Schär¹, Lluís Blancafort², Samuel Leutwyler¹

Affiliations

¹ Department of Chemistry and Biochemistry, University of Bern, Freiestrasse 3, CH-3012 Bern, Switzerland.
² Institut de Química Computacional i Catàlisi and Departament de Química, Facultat de Ciències, Universitat de Girona, C/M. A. Campmany 69, 17003 Girona, Spain.

PMID: 28668059
DOI: 10.1063/1.4989465

Abstract

We measure the S₀ → S₁ spectrum and time-resolved S₁ state nonradiative dynamics of the "clamped" cytosine derivative 5,6-trimethylenecytosine (TMCyt) in a supersonic jet, using two-color resonant two-photon ionization (R2PI), UV/UV holeburning, and ns time-resolved pump/delayed ionization. The experiments are complemented with spin-component scaled second-order approximate coupled cluster (SCS-CC2), time-dependent density functional theory, and multi-state second-order perturbation-theory (MS-CASPT2) ab initio calculations. While the R2PI spectrum of cytosine breaks off ∼500 cm^-1 above its 0₀⁰ band, that of TMCyt extends up to +4400 cm^-1 higher, with over a hundred resolved vibronic bands. Thus, clamping the cytosine C⁵-C⁶ bond allows us to explore the S₁ state vibrations and S₀ → S₁ geometry changes in detail. The TMCyt S₁ state out-of-plane vibrations ν₁^', ν₃^', and ν₅^' lie below 420 cm^-1, and the in-plane ν₁₁^', ν₁₂^', and ν₂₃^' vibrational fundamentals appear at 450, 470, and 944 cm^-1. S₀ → S₁ vibronic simulations based on SCS-CC2 calculations agree well with experiment if the calculated ν₁^', ν₃^', and ν₅^' frequencies are reduced by a factor of 2-3. MS-CASPT2 calculations predict that the ethylene-type S₁ ⇝ S₀ conical intersection (CI) increases from +366 cm^-1 in cytosine to >6000 cm^-1 in TMCyt, explaining the long lifetime and extended S₀ → S₁ spectrum. The lowest-energy S₁ ⇝ S₀ CI of TMCyt is the "amino out-of-plane" (OP_X) intersection, calculated at +4190 cm^-1. The experimental S₁ ⇝ S₀ internal conversion rate constant at the S₁(v^'=0) level is k_IC=0.98-2.2⋅10⁸ s^-1, which is ∼10 times smaller than in 1-methylcytosine and cytosine. The S₁(v^'=0) level relaxes into the T₁(³ππ*) state by intersystem crossing with k_ISC=0.41-1.6⋅10⁸ s^-1. The T₁ state energy is measured to lie 24 580±560 cm^-1 above the S₀ state. The S₁(v^'=0) lifetime is τ=2.9 ns, resulting in an estimated fluorescence quantum yield of Φ_fl=24%. Intense two-color R2PI spectra of the TMCyt amino-enol tautomers appear above 36 000 cm^-1. A sharp S₁ ionization threshold is observed for amino-keto TMCyt, yielding an adiabatic ionization energy of 8.114±0.002 eV.