Pulse-shaping assisted multidimensional coherent electronic spectroscopy

Abstract

Understanding nuclear and electronic dynamics of molecular systems has advanced considerably by probing their nonlinear responses with a suitable sequence of pulses. Moreover, the ability to control crucial parameters of the excitation pulses, such as duration, sequence, frequency, polarization, slowly varying envelope, or carrier phase, has led to a variety of advanced time-resolved spectroscopic methodologies. Recently, two-dimensional electronic spectroscopy with ultrashort pulses has become a more and more popular tool since it allows to obtain information on energy and coherence transfer phenomena, line broadening mechanisms, or the presence of quantum coherences in molecular complexes. Here, we present a high fidelity two-dimensional electronic spectroscopy setup designed for molecular systems in solution. It incorporates the versatility of pulse-shaping methods to achieve full control on the amplitude and phase of the individual exciting and probing pulses. Selective and precise amplitude- and phase-modulation is shown and applied to investigate electronic dynamics in several reference molecular systems.

Effect of Pulse Shaping on Observing Coherent Energy Transfer in Single Light-Harvesting Complexes

“…Recently, the pulse-shaping method has been applied in 2D spectroscopic studies using the pump-probe configuration and phase cycling methods, − wherein the amplitude of the laser spectrum is also modified. It is thus expected that similar approaches to generate appropriate two-color pulses could be useful for further experimental studies of coherent EET in single photosynthetic LH complexes.…”

Fourier transform spectral interferometry with non-phase stable setups by broadband single shot detection of fs and ps pulses

“…6 So far UV and visible FT-FWM spectrographs have been implemented by conceiving a design to preserve passively the phase stability [8][9][10]23 or based on the pulse-shaping technology. 3,[12][13][14] This makes the extension of such schemes to shorter wavelengths or higher orders of wave mixing hard or even impossible. Conversely the innovation of our approach concerns essentially how signals are acquired and analysed, so it does not need any special detection geometry or optical design.…”

“…13 However, it sacrifices the ability to adapt delay and intensity of the local oscillator to optimize the signal and limits to few ps the range of variability for the delays between pulses. 13,14 More advanced setups combine the benefits of boxcar geometry and pulse shaping by using a phase mask in combination with a two-dimensional pulse shaper, to create four phase stable pulses where the spectral amplitude, the phase, and the interpulse delay of each pulse can be precisely and individually controlled. 13,14 The current efforts in the field of FT-FWM are aimed at extending these techniques to shorter spectral wavelengths to access aromatic amino acids and DNA nucleotide bases 15 and wide gap materials like TiO 2 or even core transitions.…”

“…13,14 More advanced setups combine the benefits of boxcar geometry and pulse shaping by using a phase mask in combination with a two-dimensional pulse shaper, to create four phase stable pulses where the spectral amplitude, the phase, and the interpulse delay of each pulse can be precisely and individually controlled. 13,14 The current efforts in the field of FT-FWM are aimed at extending these techniques to shorter spectral wavelengths to access aromatic amino acids and DNA nucleotide bases 15 and wide gap materials like TiO 2 or even core transitions. 16 These experiments are now conceivable because of the development of new sources for broadband deep-UV-pulses, 17,18 EUV by high harmonics generation, 19 and soft and hard X-ray by free-electron-lasers.…”