Femtosecond Time‐Resolved Photoelectron Spectroscopy

Stolow, Albert; Bragg, Arthur E.; Neumark, Daniel M.

doi:10.1002/chin.200424292

Cited by 12 publications

(15 citation statements)

References 112 publications

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“…Our results underline the importance of a detailed knowledge about these resonances for a proper interpretation of transient signals of molecular dynamics subject to nuclear and electronic relaxation effects. At the same time, the direct comparison to SPI directly demonstrates the higher sensitivity of resonance-enhanced MPI as a probe in time-resolved dynamical studies.The conversion of photon energy into other forms of energy is often happening with high selectivity and effi ciency [1], Time-resolved photoelectron (PE) and photoion (PI) spectroscopy have proven to he important tools for the investigation of photoinduced relaxation processes in isolated molecules [2][3][4], since their observables can be simulated from theoretical investigations with high accuracy and thus directly compared [5,6]. The molecular relaxation generally leads to an increased ionization potential [7].…”

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confidence: 99%

“…The conversion of photon energy into other forms of energy is often happening with high selectivity and effi ciency [1], Time-resolved photoelectron (PE) and photoion (PI) spectroscopy have proven to he important tools for the investigation of photoinduced relaxation processes in isolated molecules [2][3][4], since their observables can be simulated from theoretical investigations with high accuracy and thus directly compared [5,6]. The molecular relaxation generally leads to an increased ionization potential [7].…”

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confidence: 99%

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Understanding the modulation mechanism in resonance-enhanced multiphoton probing of molecular dynamics

2015

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Time-resolved spectroscopy on isolated molecules gives fundamental insight into the conversion of light energy to other degrees of freedom. Probing of the photoinduced dynamics can be accomplished by ionization, via a single-photon or multiphoton transition. In this Rapid Communication we directly contrast transient spectra on the molecule perylene obtained with multiphoton ionization (MPI) to single-photon ionization (SPI). The photoinduced nuclear geometry relaxation modulates the MPI transient with a decay time constant of 0.9 ± 0.2 ps. In contrast, the SPI transient completely lacks any indication for relaxation. We attribute this difference to a change in resonance enhancement of the MPI probe as the molecular geometry changes. Our results underline the importance of a detailed knowledge about these resonances for a proper interpretation of transient signals of molecular dynamics subject to nuclear and electronic relaxation effects. At the same time, the direct comparison to SPI directly demonstrates the higher sensitivity of resonance-enhanced MPI as a probe in time-resolved dynamical studies.The conversion of photon energy into other forms of energy is often happening with high selectivity and effi ciency [1], Time-resolved photoelectron (PE) and photoion (PI) spectroscopy have proven to he important tools for the investigation of photoinduced relaxation processes in isolated molecules [2][3][4], since their observables can be simulated from theoretical investigations with high accuracy and thus directly compared [5,6]. The molecular relaxation generally leads to an increased ionization potential [7]. In order to detect the dynamics via a single-photon ionization (SPI) scheme, increased probe photon energies in the vacuum ultraviolet (VUV) [8][9][10][11][12][13] have been recently applied. Ex perimentally less demanding and therefore widely used is multiphoton ionization (MPI) [2,4,14,15], as shown for metal carbonyls [16,17] or nucleobases [18][19][20][21], As pointed out before, the transient MPI signal can be enhanced by resonant excited molecular states [14][15][16][17]. However, the role that the resonances play in actively shaping the observable transient in a pump-MPI-probe experiment has not been investigated. In this paper, we fill this gap by comparing SPI and MPI for identical molecules and excitation conditions finding stark differences in the transient spectra obtained by the two processes. The comparison of the SPI and MPI transients together with laser intensity characteristics directly reveals the active influence of the resonances on the observable in MPI probing. Figure 1 shows a sketch of the important processes in time-resolved PE and PI spectroscopy. An excitation (pump) laser pulse promotes the molecule from the ground state So into an electronically excited state S|. A second ultrashort laser (probe) pulse interacts with the excited molecule after a controlled delay. It can ionize the excited molecules either via SPI or MPI. In order to ionize the molecule via SPI, the photon energy ...

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confidence: 99%

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Understanding the modulation mechanism in resonance-enhanced multiphoton probing of molecular dynamics

2015

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“…Leveraging the receive-only advantage, streak cameras have been widely used in a variety of applications such as fluorescence lifetime imaging microscopy [42,43], ultrafast photography [44,45], and time-resolved spectroscopy [46]. However, because the field of view (FOV) is limited to a line, to acquire a 2D image, a streak camera must scan in the direction that is perpendicular to its entrance slit.…”

Section: Compressed Ultrafast Photography (Cup)mentioning

confidence: 99%

Ultrafast optical imaging technology: principles and applications of emerging methods

2016

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High-speed optical imaging is an indispensable technology for blur-free observation of fast transient dynamics in virtually all areas including science, industry, defense, energy, and medicine. High temporal resolution is particularly important for microscopy as even a slow event appears to occur "fast" in a small field of view. Unfortunately, the shutter speed and frame rate of conventional cameras based on electronic image sensors are significantly constrained by their electrical operation and limited storage. Over the recent years, several unique and unconventional approaches to high-speed optical imaging have been reported to circumvent these technical challenges and achieve a frame rate and shutter speed far beyond what can be reached with the conventional image sensors. In this article, we review the concepts and principles of such ultrafast optical imaging methods, compare their advantages and disadvantages, and discuss an entirely new class of applications that are possible using them.

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“…PE spectra for peptides and proteins were recently reported (Matheis et al, 2008;Vonderach et al, 2011b) and helped to discriminate between direct and delayed electron emissions (Matheis et al, 2008). The coupling of time-resolved PE experiments (Stolow, Bragg, & Neumark, 2004;Ehrler & Neumark, 2009) and photoelectron photoion coincidence (PEPICO) spectroscopy (Baer, Booze, & Weitzel, 1991;Gaie-Levrel et al, 2011) may allow a deeper insight into the electron emission dynamics. Finally, combination of ion-mobility spectrometry and PE spectroscopy has also been proposed to probe electron photodetachment in relation to protein conformational changes (Fromherz, Gantefor, & Shvartsburg, 2002;Vonderach et al, 2011a,b).…”

Section: Fundamental Aspects In Electron Photodetachmentmentioning

confidence: 99%

Electron photodetachment dissociation for structural characterization of synthetic and bio‐polymer anions

Antoine

Lemoine

Dugourd

2013

Mass Spectrometry Reviews

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Tandem mass spectrometry (MS-MS) is a generic term evoking techniques dedicated to structural analysis, detection or quantification of molecules based on dissociation of a precursor ion into fragments. Searching for the most informative fragmentation patterns has led to the development of a vast array of activation modes that offer complementary ion reactivity and dissociation pathways. Collisional activation of ions using atoms, molecules or surface resulting in unimolecular dissociation of activated ions still plays a key role in tandem mass spectrometry. The discovery of electron capture dissociation (ECD) and then the development of other electron-ion or ion/ion reaction methods, constituted a significant breakthrough, especially for structural analysis of large biomolecules. Similarly, photon activation opened promising new frontiers in ion fragmentation owing to the ability of tightly controlled internal energy deposition and easy implementation on commercial instruments. Ion activation by photons includes slow heating methods such as infrared multiple photon dissociation (IRMPD) and black-body infrared radiative dissociation (BIRD) and higher energy methods like ultra-violet photodissociation (UVPD) and electron photo detachment dissociation (EPD). EPD occurs after UV irradiation of multiply negatively charged ions resulting in the formation of oxidized radical anions. The present paper reviews the hypothesis regarding the mechanisms of electron photo-detachment, radical formation and direct or activated dissociation pathways that support the observation of odd and even electron product ions. Finally, the value of EPD as a complementary structural analysis tool is illustrated through selected examples of synthetic polymers, oligonucleotides, polypeptides, lipids, and polysaccharides.

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Femtosecond Time‐Resolved Photoelectron Spectroscopy

Cited by 12 publications

References 112 publications

Understanding the modulation mechanism in resonance-enhanced multiphoton probing of molecular dynamics

Understanding the modulation mechanism in resonance-enhanced multiphoton probing of molecular dynamics

Ultrafast optical imaging technology: principles and applications of emerging methods

Electron photodetachment dissociation for structural characterization of synthetic and bio‐polymer anions

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