Uncovering molecular relaxation processes with nonlinear spectroscopies in the deep UV

West, Brantley A.; Molesky, Brian P.; Giokas, Paul G.; Moran, Andrew M.

doi:10.1016/j.chemphys.2013.06.027

Cited by 19 publications

(16 citation statements)

References 159 publications

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“…These techniques often offer complementary but limited information about the relaxation pathways. More recently, four-wave mixing spectroscopies in the deep-UV [107,192] and time-resolved photoelectron spectroscopy [133] have been applied, but there are still technical challenges to overcome with these approaches [252]. Even so, the ever-close synergism between experimentalists and theoreticians in this field is expected to continue to throw light on our understanding of the photochemistry of nucleic acids and their analogues for years to come.…”

Section: Final Remarks and Future Perspectivementioning

confidence: 98%

Photochemistry of Nucleic Acid Bases and Their Thio- and Aza-Analogues in Solution

Pollum

Martínez‐Fernández

Crespo‐Hernández

2014

Topics in Current Chemistry

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The steady-state and time-resolved photochemistry of the natural nucleic acid bases and their sulfur- and nitrogen-substituted analogues in solution is reviewed. Emphasis is given to the experimental studies performed over the last 3-5 years that showcase topical areas of scientific inquiry and those that require further scrutiny. Significant progress has been made toward mapping the radiative and nonradiative decay pathways of nucleic acid bases. There is a consensus that ultrafast internal conversion to the ground state is the primary relaxation pathway in the nucleic acid bases, whereas the mechanism of this relaxation and the level of participation of the (1)πσ*, (1) nπ*, and (3)ππ* states are still matters of debate. Although impressive research has been performed in recent years, the microscopic mechanism(s) by which the nucleic acid bases dissipate excess vibrational energy to their environment, and the role of the N-glycosidic group in this and in other nonradiative decay pathways, are still poorly understood. The simple replacement of a single atom in a nucleobase with a sulfur or nitrogen atom severely restricts access to the conical intersections responsible for the intrinsic internal conversion pathways to the ground state in the nucleic acid bases. It also enhances access to ultrafast and efficient inter-system crossing pathways that populate the triplet manifold in yields close to unity. Determining the coupled nuclear and electronic pathways responsible for the significantly different photochemistry in these nucleic acid base analogues serves as a convenient platform to examine the current state of knowledge regarding the photodynamic properties of the DNA and RNA bases from both experimental and computational perspectives. Further investigations should also aid in forecasting the prospective use of sulfur- and nitrogen-substituted base analogues in photochemotherapeutic applications.

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Section: Final Remarks and Future Perspectivementioning

confidence: 98%

Photochemistry of Nucleic Acid Bases and Their Thio- and Aza-Analogues in Solution

Pollum

Martínez‐Fernández

Crespo‐Hernández

2014

Topics in Current Chemistry

111

200

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“…As a result, we have designed a simple system to control the time delay with high resolution, while using all-reflective optics. The use of supercontinuum light sources in 2DES is now allowing access to broader spectral regions and even ultraviolet 2DES [14,17,40–43]. …”

Section: Introductionmentioning

confidence: 99%

Dispersion-free continuum two-dimensional electronic spectrometer

et al. 2014

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Electronic dynamics span broad energy scales with ultrafast time constants in the condensed phase. Two-dimensional (2D) electronic spectroscopy permits the study of these dynamics with simultaneous resolution in both frequency and time. In practice, this technique is sensitive to changes in nonlinear dispersion in the laser pulses as time delays are varied during the experiment. We have developed a 2D spectrometer that uses broadband continuum generated in argon as the light source. Using this visible light in phase-sensitive optical experiments presents new challenges in implementation. We demonstrate all-reflective interferometric delays using angled stages. Upon selecting an ~180 nm window of the available bandwidth at ~10 fs compression, we probe the nonlinear response of broadly absorbing CdSe quantum dots and electronic transitions of Chlorophyll a.

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“…Two-dimensional UV spectroscopy has been applied to nucleic acid bases and nucleotides, and holds promise for exploring transfer of vibrational energy and the migration and localization of excitons in DNA [92][93][94][95][96]. These processes are pertinent to understanding how DNA avoids photodamage.…”

Section: Two-dimensional Electronic and Vibrational Spectroscopymentioning

confidence: 99%

Pump-Probe Spectroscopy, Photon Echoes and Vibrational Wavepackets

Parson

2015

Modern Optical Spectroscopy

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Uncovering molecular relaxation processes with nonlinear spectroscopies in the deep UV

Cited by 19 publications

References 159 publications

Photochemistry of Nucleic Acid Bases and Their Thio- and Aza-Analogues in Solution

Photochemistry of Nucleic Acid Bases and Their Thio- and Aza-Analogues in Solution

Dispersion-free continuum two-dimensional electronic spectrometer

Pump-Probe Spectroscopy, Photon Echoes and Vibrational Wavepackets

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