Publisher’s Note: “Mechanism for ultrafast internal conversion of adenine” [J. Chem. Phys. <b>118</b>, 6717 (2003)]

Kang, Hyuk; Jung, Boyong; Kim, Seong Keun

doi:10.1063/1.1580104

Cited by 68 publications

(122 citation statements)

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“…3,5,[8][9][10][11]15,16 Internal conversion can populate the S 1 (nπ*) state, as proposed by theory 21 and spectroscopic and dynamic measurements. 3,6,22 The strong mixing of ππ* and nπ* states was confirmed by timeresolved photoelectron spectroscopy 8,9 and by rotational band contour analysis. 23 Internal conversion time scales were reported to be 40-100 fs at excitation energies of e267 nm.…”

Section: Introductionmentioning

confidence: 87%

“…Research into the UV photophysics of DNA is receiving increasing interest because it is assumed that DNA must have some inherent photoprotection mechanisms. 1,2 Studies targeting small, isolated DNA constituents [3][4][5][6][7][8][9][10][11] complement work on DNA multimers in the liquid phase 12 in terms of understanding the complex photophysics of DNA in its natural biological environment. Small molecular clusters in the gas phase can mimic important structural elements of DNA and thus help to extend the power of gas-phase spectroscopic methods to increasingly complex systems.…”

Section: Introductionmentioning

confidence: 99%

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Electronic Structure of Adenine and Thymine Base Pairs Studied by Femtosecond Electron−Ion Coincidence Spectroscopy

et al. 2007

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/jp076800eAccess and use of this website and the material on it are subject to the Terms and Conditions set forth at Electronic structure of adenine and thymine base pairs studied by femtosecond electron-ion coincidence spectroscopy Gador, Niklas; Samoylova, Elena; Smith, Valoris Reid; Stolow, Albert; Rayner, David M.; Radloff, Wolfgang; Hertel, Ingolf Volker; Schultz, Thomas http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/droits L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site LISEZ CES CONDITIONS ATTENTIVEMENT AVANT D'UTILISER CE SITE WEB. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=db4ea838-d64b-464c-aa0b-a7edab815e24 http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=db4ea838-d64b-464c-aa0b-a7edab815e24 Sciences, National Research Council, 100 Sussex DriVe, Ottawa, K1A 0R6 Canada, and Max Born Institute, 12489 Berlin-Adlershof, Germany ReceiVed: August 24, 2007; In Final Form: September 6, 2007 Femtosecond pump-probe spectroscopy was combined with photoelectron-photoion coincidence detection to investigate the electronic structure and dynamics of isolated adenine (A) and thymine (T) dimers and the adenine-thymine (AT) base pair. The photoelectron spectra show that ππ* and nπ* states are only weakly perturbed in the hydrogen-bound dimers as compared to the monomers. For cationic base pairs with internal energies greater than 1 eV, we observed considerable cluster fragmentation into protonated monomers. This process selectively removed signals from the nπ* f n -1 ionization channel in all dimers. The photoelectron spectra are compared to time-resolved mass spectra and confirm the assignment of short-lived ππ* and nπ* populations in the adenine, thymine, and mixed AT dimers.

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Section: Introductionmentioning

confidence: 87%

Section: Introductionmentioning

confidence: 99%

Electronic Structure of Adenine and Thymine Base Pairs Studied by Femtosecond Electron−Ion Coincidence Spectroscopy

et al. 2007

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“…[18][19][20] The excited-state lifetimes have been reported recently using many different techniques. [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39] These studies report lifetimes on the order of femtoseconds and suggest that nonradiative relaxation proceeds on an ultrafast time scale to the ground state, with the extra energy being transformed into heat.…”

Section: Introductionmentioning

confidence: 99%

Three-State Conical Intersections in Nucleic Acid Bases

2005

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The involvement of three-state conical intersections in the photophysics and radiationless decay processes of the nucleobases has been investigated using multireference configuration interaction methods. Three-state conical intersections have been located for the pyrimidine base, uracil, and the purine base, adenine. In uracil, a three-state degeneracy between the S 0 , S 1 , and S 2 states has been located at 6.2 eV above the ground-state minimum energy. This energy is 0.4 eV higher than vertical excitation to S 2 and at least 1.3 eV higher than the two-state conical intersections found previously. In adenine, two different three-state degeneracies between the S 1 , S 2 , and S 3 states have been located at energies close to the vertical excitation energies. The energetics of these three-state conical intersections suggest they can play a role in a radiationless decay pathway present in adenine. The existence of two different seams of three-state conical intersections indicates that these features are common and complicate the potential energy surfaces of adenine and possibly many other aromatic molecules.

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“…Although it is not fully documented experimentally, the CI concept is routinely invoked in rather complex situations where the molecule or the molecular group that lead to the CI are embedded in a surrounding medium, a solvent [17,34] or a protein [12, 1 13]. It may be conceived that the passage of the wavepacket at the CI is affected by the presence of the surrounding medium.…”

mentioning

confidence: 99%

“…It mostly concerns gas phase, femtosecond pump-probe investigations in organic molecules documenting ultrafast energy relaxation processes [15][16][17][18][19][20][21], isomerisation reactions [22][23][24][25] and ring opening reactions [26][27][28][29][30][31]. Ethylene [18,32], substituted ethylene compounds [18][19][20][21] and polyenes [22] received a particular attention.…”

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confidence: 99%

Dynamics of excited tetrakis(dimethylamino)ethylene solvated by argon atoms

et al. 2004

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The supersonic expansion of a mixture of the title molecule (TDMAE) with argon generates a beam carrying a log-normal distribution of TDAME(Ar) n clusters, broadly centered atn ≈ 60. The femtosecond pump-probe technique is used to investigate the excited state dynamics of these clusters up to a 220 ps delay between the pump and the probe. This documents the effect of the argon environment on the TDMAE dynamics. The TDMAE molecule is excited in the valence state V within the cluster by the pump laser at 266 nm. It undergoes deformation in the excited potential energy surface that brings the initial wavepacket to a conical intersection (CI) where the electronic configuration of the molecule switches to a Zwitterionic configuration Z. Compared to the behaviour of free TDMAE, the effect of the argon environment is a slow down of the wavepacket movement and an increase of the time scale of the V-Z energy transfer from 300 fs to 400 ± 50 fs. This slow down effect, that we call a chistera effect, differs from a standard cage effect. Here, the deforming molecule does not experience a hard sphere collision with the argon cage, rather it pushes it away. Furthermore, umbrella oscillations of the dimethylamino groups are excited when the initial wavepacket passes the CI region. Because of the argon environment, the sharp 250 fs oscillation period of the free molecules is transformed into a broad structure of 40 fs width (FWHM) centred at about 240 fs. In addition, breathing oscillations of the argon environment with respect to the TDMAE molecule are observed with a period of 410 ± 40 fs. Finally, long delays between the pump and the probe lasers allow us to investigate the non radiative energy transfer from the Z electronic configuration of TDMAE(Ar) n to a charge transfer state. The effect of the evaporation of argon atoms in the neutral and the ionised clusters has been taken into account, as its time scale accompanies that of the observed phenomena.

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Publisher’s Note: “Mechanism for ultrafast internal conversion of adenine” [J. Chem. Phys. 118, 6717 (2003)]

Cited by 68 publications

References 0 publications

Electronic Structure of Adenine and Thymine Base Pairs Studied by Femtosecond Electron−Ion Coincidence Spectroscopy

Electronic Structure of Adenine and Thymine Base Pairs Studied by Femtosecond Electron−Ion Coincidence Spectroscopy

Three-State Conical Intersections in Nucleic Acid Bases

Dynamics of excited tetrakis(dimethylamino)ethylene solvated by argon atoms

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