Coherent two-dimensional ultraviolet spectroscopy in fully noncollinear geometry

Selig, Ulrike; Schleußner, Carl-Friedrich; Foerster, Michael; Langhojer, Florian; Nuernberger, Patrick; Brixner, Tobias

doi:10.1364/ol.35.004178

Cited by 74 publications

(68 citation statements)

References 23 publications

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“…Pulses with a spectral width large enough to cover the transitions to a multitude of vibronic or even electronic states are therefore an essential requirement. In contrast to 2D-Vis [32,33], where a bandwidth up to 150 nm can be reached, experimental realizations in the UV are so far limited to about 5 nm [34][35][36].…”

Section: Application: Collinear Two-dimensional Spectroscopy On Pyrenementioning

confidence: 99%

Pulse Compression of Ultrashort UV Pulses by Self-Phase Modulation in Bulk Material

2013

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Abstract:The bandwidth of ultrafast pulses in the UV is limited by the finite acceptance bandwidth of the nonlinear crystals used for their generation. For fundamental laser pulses it is well established that spectral broadening can be used to overcome intrinsic bandwidth limits. We show that self-phase modulation of UV pulses in bulk materials leads to large spectral broadening and allows for a significant reduction of the pulse duration. We find that for pulse energies in the range of a few μJ, a thin crystal is favorable due to the strong dispersion in the UV and the limitations set by self-focusing. In contrast to spectral broadening in gaseous media, the self-focus has to lie outside the crystal to avoid beam break up. We focus UV pulses into a 1 mm thick CaF 2 crystal. For moderately short input pulses, a shortening factor up to 2.4 is achieved: the 120 fs long third harmonic output of a Ti:sapphire amplifier is compressed down to 50 fs FWHM. For a central wavelength of 315 nm, we generate pulses as short as 14.9 fs after compression with an UV pulse shaper. In both cases the resulting beam shape is close to Gaussian and fully usable for spectroscopic experiments. We use the pulses in a collinear 2D-UV experiment and clearly resolve vibronic off-diagonal peaks of the S 2 1 B 2u vibronic progression of pyrene.

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Section: Application: Collinear Two-dimensional Spectroscopy On Pyrenementioning

confidence: 99%

Pulse Compression of Ultrashort UV Pulses by Self-Phase Modulation in Bulk Material

2013

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“…Extending the technique to electronic transitions in the ultraviolet (UV) spectral regime (2DUV) has been achieved only very recently. 4–8 In particular, the ππ* transitions of protein residues with aromatic side chains (Phenylalanine (Phe), Tyrosine (Tyr) and Tryptophan (Trp)) generate signals in the near-UV (NUV) range (250–300 nm) 9 , providing native “local” probes for tracking protein dynamics in solution with femtosecond time resolution. 2DUV electronic spectroscopy can target the ππ* transitions of aromatic residues in oligopeptides and proteins without isotopic labeling.…”

Section: Introductionmentioning

confidence: 99%

Tracking Conformational Dynamics of Polypeptides by Nonlinear Electronic Spectroscopy of Aromatic Residues: A First‐Principles Simulation Study

et al. 2014

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The ability of non-linear electronic spectroscopy to track folding/unfolding processes of proteins in solution by monitoring aromatic interactions is investigated by first-principle simulations of two-dimensional (2D) electronic spectra of a model peptide. A dominant reaction pathway approach is employed to determine the unfolding pathway of a tetrapeptide, connecting the initial folded configuration with stacked aromatic side chains and the final unfolded state with distant non-interacting aromatic residues. π-stacking and excitonic coupling effects are included via ab-initio simulations based on multiconfigurational methods within a hybrid QM/MM scheme. We show that linear absorption spectroscopy in the ultraviolet (UV) is unable to resolve the unstacking dynamics characterized by the three-step process: T-shaped→twisted offset stacking→unstacking. Conversely, pump-probe spectroscopy can be used to resolve aromatic interactions by probing in the visible (Vis) the excited state absorptions (ESA) that involve charge transfer (CT) states. 2DUV spectroscopy offers the highest sensitivity to the unfolding process, providing the disentanglement of ESA signals belonging to different aromatic chromophores and high correlation between the conformational dynamics and the quartic splitting.

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“…The multidimensional optical counterparts of these techniques have been traditionally developed in the 600–800 nm regime limited by laser sources, are now becoming feasible in the UV 23–28 . The broad bandwidth of the optical or ionizing probe pulses lacks selectivity for the underlying vibrational dynamics.…”

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confidence: 99%

Monitoring Nonadiabatic Dynamics of the RNA Base Uracil by UV Pump–IR Probe Spectroscopy

Fingerhut

Dorfman

Mukamel

2013

J. Phys. Chem. Lett.

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Resolving the excited state dynamics of DNA- and RNA- nucleobases has attracted considerably attention. UV irradiation of the isolated nucleobases leads to the population of an electronic excited state which is quenched by internal conversion mediated by conical intersections on an ultrafast timescale. We present non-adiabatic on-the-fly molecular dynamics simulations of the UV-pump-IR-probe signal of the pyrimidine nucleobase uracil using a novel semiclassical protocol which takes into account the path integral over the excited state vibrational dynamics and properly describes the joint temporal and spectral resolution of the technique. Simulations of vibrational motions of carbonyl fingerprint modes in the electronically excited states reveal clear signatures of different relaxation pathways on a timescale of hundreds of femtoseconds which arise from an ultrafast branching in the excited state. We show that the inherent temporal and spectral resolution of the technique is not purely instrumental but also depends on the vibrational fluctuation timescale.

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Coherent two-dimensional ultraviolet spectroscopy in fully noncollinear geometry

Cited by 74 publications

References 23 publications

Pulse Compression of Ultrashort UV Pulses by Self-Phase Modulation in Bulk Material

Pulse Compression of Ultrashort UV Pulses by Self-Phase Modulation in Bulk Material

Tracking Conformational Dynamics of Polypeptides by Nonlinear Electronic Spectroscopy of Aromatic Residues: A First‐Principles Simulation Study

Monitoring Nonadiabatic Dynamics of the RNA Base Uracil by UV Pump–IR Probe Spectroscopy

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