Time-resolved multi-mass ion imaging: Femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera

Forbes, Ruaridh; Makhija, Varun; Veyrinas, K.; Stolow, Albert; Lee, Jason W. L.; Burt, Michael; Brouard, M.; Vallance, Claire; Wilkinson, Iain; Lausten, Rune; Hockett, Paul

doi:10.1063/1.4978923

Cited by 23 publications

(23 citation statements)

References 57 publications

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“…The TRPES experiments utilized a standard pump-probe spectroscopy scheme [68]. A seeded supersonic beam injected CH 2 I 2 molecules through a pulsed valve into the interaction region of an electron velocity map imaging (VMI) spectrometer [69], where they interacted with the fs UV-pump and VUV-probe pulses.…”

Section: A Trpes Experimentsmentioning

confidence: 99%

“…The gas-phase UED and TRPES experimental apparatuses have been described in detail previously [52,68]. Here, we expand on the discussion in the main text to describe experimental conditions for the two measurements in some more detail.…”

Section: Trpes and Ued Experimental Detailsmentioning

confidence: 99%

“…The details of this VUV generation setup can be found in Refs. [19,68]. Photoelectrons produced from the pump-probe laser interaction were velocity map imaged using electrostatic lenses onto a conventional microchannel plate (MCP) and phosphor-based (P47) detector setup.…”

Section: Trpes and Ued Experimental Detailsmentioning

confidence: 99%

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Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

et al. 2020

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Pump-probe measurements aim to capture the motion of electrons and nuclei on their natural timescales (femtoseconds to attoseconds) as chemical and physical transformations take place, effectively making "molecular movies" with short light pulses. However, the quantum dynamics of interest are filtered by the coordinate-dependent matrix elements of the chosen experimental observable. Thus, it is only through a combination of experimental measurements and theoretical calculations that one can gain insight into the internal dynamics. Here, we report on a combination of structural (relativistic ultrafast electron diffraction, or UED) and spectroscopic (time-resolved photoelectron spectroscopy, or TRPES) measurements to follow the coupled electronic and nuclear dynamics involved in the internal conversion and photodissociation of the polyatomic molecule, diiodomethane (CH 2 I 2). While UED directly probes the 3D nuclear dynamics, TRPES only serves as an indirect probe of nuclear dynamics via Franck-Condon factors, but it is sensitive to electronic energies and configurations, via Koopmans' correlations and photoelectron angular distributions. These two measurements are interpreted with trajectory surface hopping calculations, which are capable of simulating the observables for both measurements from the same dynamics calculations. The measurements highlight the nonlocal dynamics captured by different groups of trajectories in the calculations. For the first time, both UED and TRPES are combined with theory capable of calculating the observables in both cases, yielding a direct view of the structural and nonadiabatic dynamics involved.

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Section: A Trpes Experimentsmentioning

confidence: 99%

Section: Trpes and Ued Experimental Detailsmentioning

confidence: 99%

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Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

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“…The femtosecond VUV pulse generation scheme employed in these experiments was described in detail previously. 25 In short, the laser system (Coherent Legend Elite Duo) employed throughout these experiments delivered 7.5 mJ pulses at 1 kHz, with a central frequency of 800 nm. A 3.25 mJ component of the total laser output was split to generate the pump and probe arms.…”

Section: A Experimentalmentioning

confidence: 99%

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

Coates

Larsen

Forbes

et al. 2018

The Journal of Chemical Physics

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The vacuum-ultraviolet photoinduced dynamics of cyclopropane (C 3 H 6) were studied using timeresolved photoelectron spectroscopy (TRPES) in conjunction with ab initio quantum dynamics simulations. Following excitation at 160.8 nm, and subsequent probing via photoionization at 266.45 nm, the initially prepared wave packet is found to exhibit a fast decay (<100 fs) that is attributed to the rapid dissociation of C 3 H 6 to ethylene (C 2 H 4) and methylene (CH 2). The photodissociation process proceeds via concerted ring opening and CC bond cleavage in the excited state. Ab initio multiple spawning simulations indicate that ring-opening occurs prior to dissociation. The dynamics simulations were subsequently employed to simulate a TRPES spectrum, which was found to be in excellent agreement with the experimental result. On the basis of this agreement, the fitted time constants of 35 ± 20 and 57 ± 35 fs were assigned to prompt (i) dissociation on the lowest-lying excited state, prepared directly by the pump pulse, and (ii) non-adiabatic relaxation from higher-lying excited states that lead to delayed dissociation, respectively.

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“…The experimental set-up used for the VUV-UV pumpprobe photoelectron velocity-map imaging (VMI) measurements at 133 nm reported herein was almost identical to that previously reported for work using 160 nm radiation [25], and the reader is referred to that work for further details of the experimental apparatus beyond the outline sketched here. A similar VUV-UV pump-probe VMI experimental configuration has also been previously reported by Suzuki (see ref.…”

Section: A Vuv-uv Photoelectron Imagingmentioning

confidence: 92%

Quantum-beat photoelectron-imaging spectroscopy of Xe in the VUV

et al. 2018

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Time-resolved pump-probe measurements of Xe, pumped at 133 nm and probed at 266 nm, are presented.The pump pulse prepared a long-lived hyperfine wavepacket, in the Xe.57 eV). The wavepacket was monitored via single-photon ionization, and photoelectron images measured. The images provide angle-and timeresolved data which, when obtained over a large time-window (900 ps), constitute a precision quantum beat spectroscopy measurement of the hyperfine state splittings. Additionally, analysis of the full photoelectron image stack provides a quantum beat imaging modality, in which the Fourier components of the photoelectron images correlated with specific beat components can be obtained. This may also permit the extraction of isotope-resolved photoelectron images in the frequency domain, in cases where nuclear spins (hence beat components) can be uniquely assigned to specific isotopes (as herein), and also provides phase information. The information content of both raw, and inverted, image stacks is investigated, suggesting the utility of the Fourier analysis methodology in cases where images cannot be inverted.

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Time-resolved multi-mass ion imaging: Femtosecond UV-VUV pump-probe spectroscopy with the PImMS camera

Cited by 23 publications

References 57 publications

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

Spectroscopic and Structural Probing of Excited-State Molecular Dynamics with Time-Resolved Photoelectron Spectroscopy and Ultrafast Electron Diffraction

Vacuum ultraviolet excited state dynamics of the smallest ring, cyclopropane. II. Time-resolved photoelectron spectroscopy and ab initio dynamics

Quantum-beat photoelectron-imaging spectroscopy of Xe in the VUV

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