New insights into the photophysics of the DNA base thymine

DNA stores our genetic code. Solar UV radiation is sufficiently high energy to break bonds in the DNA and thus cause DNA damage. However, even though DNA (eg in our skin cells) is exposed to intense UV rays from the sun daily, the DNA turns out to be astonishingly light-stable. It has long been known that this can be explained by mechanisms that highly efficiently transform electronic energy into other forms of energy, especially heat. Interfaces of the multidimensional potential energy surfaces, so-called conical intersections, play an important role between the electronically excited states and the electronic ground state. These conical penetrations are associated with structural changes in the molecules. The exact ways back to the electronic ground state are the subject of intensive research.

Although the DNA is a macromolecule with several billion atoms (in the case of human DNA), it can be divided into only a few different structural (and functional) elements: four DNA bases, a sugar residue and a phosphate group. The absorption of UV light takes place exclusively in the DNA bases. Therefore, it is a common research approach to first study only the reaction of the DNA bases to UV absorption.

Fig. 1 After UV excitation, the photoreaction in thymine occurs along two different paths: 1. the twist of the aromatic ring and 2. a movement of the carbonyl group from the ring plane. In contradiction to the existing literature, the nπ state seems to play no role.

A team of scientists from MBI and the universities of Hokkaido and Hirosaki in Japan has now for the first time investigated the DNA base thymine in aqueous solution with the help of time-resolved photoelectron spectroscopy and questioned existing ideas for the relaxation process in this base. So far it has been suggested that a significant portion of the excited state initially remains in a dark nπ* state and does not immediately return to the ground state via conical interpenetration. This dark state can not be directly observed by optical spectroscopy (such as time-resolved fluorescence or time-resolved absorption). However, there are no corresponding restrictions for photoelectron spectroscopy.

In the interplay between experiment and simulation, two different reaction pathways could be identified for the first time. Both paths are in the first excited (ππ*) state. The faster reaction pathway is associated with a drive of the aromatic ring and returns to the ground state in about 100 fs. The second path is about 400 fs back to the ground state via the movement of the carbonyl group from the ring plane. Evidence that the next higher excited nπ* state plays an important role in the relaxation dynamics of thymine, the scientists did not find, from which they concluded that this state is not involved in the relaxation process.

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Publications since 2025

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A1-P-2025.01
Melting, bubblelike expansion, and explosion of superheated plasmonic nanoparticles

S. Dold, T. Reichenbach, A. Colombo, J. Jordan, I. Barke, P. Behrens, N. Bernhardt, J. Correa, S. Düsterer, B. Erk, T. Fennel, L. Hecht, A. Heilrath, R. Irsig, N. Iwe, P. Kolb, B. Kruse, B. Langbehn, B. Manschwetus, P. Marienhagen, F. Martinez, K.-H. Meiwes-Broer, K. Oldenburg, C. Passow, C. Peltz, M. Sauppe, F. Seel, R. M. P. Tanyag, R. Treusch, A. Ulmer, S. Walz, M. Moseler, T. Möller, D. Rupp, B. v. Issendorff

Physical review letters 134 (2025) 136101/1-7

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A3-P-2025.01
Second-harmonic generation in OP-GaAs0.75P0.25 heteroepitaxially grown from the vapor phase

L. Wang, S. R. Vangala, S. Popien, M. Beutler, J. M. Mann, V. L. Tassev, E. Büttner, V. Petrov

CrystEngComm 27 (2025) 1373-1376

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A3-P-2025.02
Diode-pumped Kerr-lens mode-locked Yb:MgWO4 laser

H.-Y. Nie, Z.-L. Lin, P. Loiko, H.-J. Zeng, L. Zhang, Z. Lin, G. Z. Elabedine, X. Mateos, V. Petrov, G. Zhang, W. Chen

Optics Letters 50 (2025) 1049-1052

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A3-P-2025.03
Growth, anisotropy, and spectroscopy of Tm3+ and Yb3+ doped MgWO4 crystals

G. Z. Elabedine, R. M. Solé, S. Slimi, M. Aguiló, F. Díaz, W. Chen, V. Petrov, X. Mateos

CrystEngComm 27 (2025) 1619-1631

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A3-P-2025.04
Growth, structure, spectroscopic, and laser properties of Ho-doped yttrium gallium garnet crystal

S. Slimi, H. Yu, H. Zhang, C. Kränkel, P. Loiko, R. M. Solé, M. Aguiló, F. Díaz, W. Chen, U. Griebner, V. Petrov, X. Mateos

Optics Express 33 (2025) 2529-2541

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A3-P-2025.05
Growth, spectroscopy and laser operation of disordered Tm,Ho:NaGd (MoO4)2 crystal

G. Z. Elabedine, Z. Pan, P. Loiko, H. Chu, D. Li, K. Eremeev, K. Subbotin, S. Pavlov, P. Camy, A. Braud, S. Slimi, R. M. Solé, M. Aguiló, F. Díaz, W. Chen, U. Griebner, V. Petrov, X. Mateos

Journal of Alloys and Compounds 1020 (2025) 179211/1-12

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A3-P-2025.06
Kerr-lens mode-locked, diode-pumped Yb,Gd:YAP laser generating 23 fs pulses

H.-Y. Nie, P. Zhang, P. Loiko, Z.-L. Lin, H.-J. Zeng, G. Zhang, Z. Li, X. Mateos, H.-C. Liang, V. Petrov, Z. Chen, W. Chen

Optics Express 33 (2025) 11793-11799

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A3-P-2025.07
Nanoindentation and laser-induced optical damage tests of CdSe nonlinear crystals

G. Exner, A. Carpenter, K. Cissner, A. Hildenbrand-Dhollande, S. Schmitt, A. Grigorov, M. Piotrowski, S. Guha, V. Petrov

Journal of the Optical Society of America B 42 (2025) A10-A14

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A3-P-2025.08
Phase-matching properties of AgGa(Se1-xTex)2 for SHG of a CO2 laser

K. Kato, V. Petrov, K. Miyata

Proceedings of SPIE 13347 (2025) 133470S/1-4

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A3-P-2025.09
Phase-matching properties of ZnSiAs2 in the mid-IR

T. Okamoto, N. Umemura, K. Kato, V. Petrov

Proceedings of SPIE 13347 (2025) 133470C/1-5

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A3-P-2025.10
Direct generation of 3.5 optical-cycle pulses from a rare-earth laser

N. Zhang, Y. Wang, H. Ding, F. Liang, Y. Zhao, J. Xu, H. Yu, H. Zhang, V. Petrov

Optics Letters 50 (2025) 3150-3153

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A3-P-2025.11
Power scaling of a non-resonant optical parametric oscillator based on periodically poled LiNbO3 with spectral narrowing

S. Das, T. Temel, G. Spindler, A. Schirrmacher, I. B. Divliansky, R. T. Murray, M. Piotrowski, L. Wang, W. Chen, O. Mhibik, V. Petrov

Optics Express 33 (2025) 5662-5669

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A3-P-2025.12
Sub-40-fs diode-pumped ytterbium-doped mixed rare-earth calcium oxoborate laser

H.-J. Zeng, Z.-L. Lin, H. Lin, P. Loiko, L. Zhang, Z. Lin, H.-C. Liang, X. Mateos, V. Petrov, G. Zhang, W. Chen

Optics Express 33 (2025) 17965-17975

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A3-P-2025.13
Spectroscopy and SESAM mode-locking of a disordered Yb:Gd2SrAl2O7 crystal

H.-J. Zeng, Z.-L. Lin, P. Loiko, F. Yuan, G. Zhang, Z. Lin, X. Mateos, V. Petrov, W. Chen

Optics Express 33 (2025) 15057-15066

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A3-P-2025.14
Watt-level, 1.6 ps χ(2)-lens mode-locking of an in-band pumped Nd:LuVO4 laser

H. Iliev, V. Aleksandrov, V. Petrov, L. S. Petrov, H. Zhang, H. Yu, I. Buchvarov

Optics Express 33 (2025) 17773-17781

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A3-P-2025.15
Refined phase-matching predictions for AgGa1-xInxS2 mixed chalcopyrite crystals

K. Kato, K. Miyata, V. Petrov

Journal of the Optical Society of America B 42 (2025) A6-A9

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A3-P-2025.16
35-fs diode-pumped mode-locked ytterbium-doped multi-component alkaline-earth fluoride laser

Z. Zhang, Z.-Q. Li, P. Loiko, H.-J. Zeng, G. Zhang, Z.-L. Lin, S. Normani, A. Braud, F. Ma, X. Mateos, H.-C. Liang, V. Petrov, D. Jiang, L. Su, W. Chen

Optics Letters 50 (2025) 1835-1838

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A3-P-2025.17
Diode-pumped few-optical-cycle laser based on an ytterbium-doped disordered strontium yttrium borate crystal

H. Zeng, Z. Lin, S. Sun, P. Loiko, H. Lin, G. Zhang, Z. Lin, C. Mou, X. Mateos, V. Petrov, W. Chen

Optics Letters 50 (2025) 2203-2206

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A3-P-2025.18
Refined Sellmeier and thermo-optic dispersion formulas for CdGeAs2

K. Kato, K. Miyata, V. Petrov

Journal of the Optical Society of America B 42 (2025) A24-A28

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A3-P-2025.19
Diode-pumped mode-locked Yb:Ca3La2(BO3)4 laser generating 35 fs pulses

H.-J. Zeng, Z.-L. Lin, G. Zhang, Z. Pan, P. Loiko, X. Mateos, V. Petrov, H. Lin, W. Chen

Optics Express 33 (2025) 22988-22996

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