spatial-separation-of-molecular-conformers-and-clusters

Spatial Separation of Molecular Conformers and Clusters

Gas-phase molecular physics and physical chemistry experiments commonly use supersonic expansions through pulsed valves for the production of cold ...

The nature of the repulsive Coulomb barrier in isolated molecular polyanions is studied by means of the photodetachment dynamics of the S(1) excited state of the fluorescein dianion which is bound solely by the repulsive Coulomb barrier. Photoelectron spectra reveal a feature at a constant electron kinetic energy, regardless of the excitation energy. This is explained by using an adiabatic tunneling picture for electron loss through successive repulsive Coulomb barriers correlating to vibrationally excited states. This physical picture is supported by time-resolved photoelectron spectra, showing that the tunneling lifetime is also invariant with excitation energy.

Effect of internal energy on the repulsive Coulomb barrier of polyanions.

The photoelectron spectrum of the 7,7,8,8-tetracyanoquinodimethane (TCNQ) radical anion has been measured at 3.1 eV. Additionally, the ultrafast relaxation dynamics of the first excited state (1(2)B(3u)) of TCNQ(-) have been studied using time-resolved photoelectron spectroscopy, which reveals that it undergoes internal conversion back to the ground state ((2)B(2g)) with an associated lifetime of 650 fs and shows evidence of coherent nuclear motion.

Spectroscopy and dynamics of the 7,7,8,8-tetracyanoquinodimethane radical anion.

Time-resolved photoelectron imaging of the 7,7,8,8-tetracyanoquinodimethane (TCNQ) radical anion is presented. Photoelectron angular distributions (PADs) are qualitatively analyzed in terms of the simple s-p model that is based on symmetry arguments. The internal conversion dynamics from the first excited state (1(2)B(3u)) to the ground state ((2)B(2g)) may be observed through temporal changes in the PADs of the spectrally overlapping photoelectron features arising from photodetachment of the ground state and the excited state. A formulism for extracting the population dynamics from the β(2) anisotropy parameter of overlapping spectroscopic features is presented. This is used to extract the lifetime of the first excited state, which is in good agreement with that observed in the time-resolved photoelectron spectra.

Ultrafast relaxation dynamics observed through time-resolved photoelectron angular distributions.

The spectroscopy and ultrafast relaxation dynamics of excited states of the radical anion of a representative charge-transfer acceptor molecule, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, have been studied in the gas phase using time-resolved photoelectron spectroscopy. The photoelectron spectra reveal that at least two anion excited states are bound. Time-resolved studies show that both excited states are very short-lived and internally convert to the anion ground state, with the lower energy state relaxing within 200 fs and a near-threshold valence-excited state relaxing on a 60 fs time scale. These excited states, and in particular the valence-excited state, present efficient pathways for electron-transfer reactions in the highly exergonic inverted region which commonly displays rates exceeding predictions from electron-transfer theory.

Excited states in electron-transfer reaction products: ultrafast relaxation dynamics of an isolated acceptor radical anion.

The spectroscopy and dynamics of near-threshold excited states of the isolated chloranil radical anion are investigated using photoelectron imaging. The photoelectron images taken at 480 nm clearly indicate resonance-enhanced photodetachment via a bound electronic excited state. Time-resolved photoelectron imaging reveals that the excited state rapidly decays on a timescale of 130 fs via internal conversion. The ultrafast relaxation dynamics of excited states near threshold are pertinent to common electron acceptor molecules based on the quinone moiety and may serve as doorway states that enable efficient electron transfer in the highly exergonic inverted regime, despite the presence of large free energy barriers.

Time-resolved photoelectron imaging of the chloranil radical anion: ultrafast relaxation of electronically excited electron acceptor states.

A photoelectron spectroscopy study of the anionic model chromophore of the green fluorescent protein is presented. From the photoelectron spectra taken at 3.496 eV, 4.62 eV, and 6.15 eV the vertical and adiabatic detachment energies are determined to be 2.8 ± 0.1 eV and 2.6 ± 0.2 eV, respectively. The vertical detachment energy is higher than the S(1) ← S(0) absorption maximum (2.57 eV) and indicates that the S(1) state is bound with respect to electron detachment in the Franck-Condon region. The photoelectron spectrum taken at 6.15 eV, together with TD-DFT calculations, are used to assign a number of excited states in the neutral radical that correspond to electron loss from occupied orbitals in the anion. The photoelectron spectrum at 2.58 eV shows evidence for electrons formed by thermionic emission, suggesting that internal conversion is the dominant relaxation pathway following S(1) ← S(0) excitation.

Photoelectron spectroscopy of the model GFP chromophore anion.

We present a velocity-map imaging (VMI) setup for photoelectron imaging that utilizes low electric extraction fields. This avoids any complications that could arise from electrostatic interactions between the extraction field and the molecular properties that are probed and has a minimal effect on the trajectory of ions in ion beam experiments. By using an attractive potential supplied to the detector, and keeping the electrodes at ground (zero) potential, we show that fringe fields between the VMI arrangement and the vacuum chamber can be eliminated, which is important in experiments on ions.

Velocity-map imaging at low extraction fields.

Quinones feature prominently as electron acceptors in nature. Their electron-transfer reactions are often highly exergonic, for which Marcus theory predicts reduced electron-transfer rates because of a free-energy barrier that occurs in the inverted region. However, the electron-transfer kinetics that involve quinones can appear barrierless. Here, we consider the intrinsic properties of the para-benzoquinone radical anion, which serves as the prototypical electron-transfer reaction product involving a quinone-based acceptor. Using time-resolved photoelectron spectroscopy and ab initio calculations, we show that excitation at 400 and 480 nm yields excited states that are unbound with respect to electron loss. These excited states are shown to decay on a sub-40 fs timescale through a series of conical intersections with lower-lying excited states, ultimately to form the ground anionic state and avoid autodetachment. From an isolated electron-acceptor perspective, this ultrafast stabilization mechanism accounts for the ability of para-benzoquinone to capture and retain electrons.

Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor.

A photoelectron imaging study of the gas-phase dianion of pyrromethene-556 is presented. The photoelectron spectra and angular distributions following resonant excitation of the S1 excited state with nanosecond and femtosecond laser pulses are compared, and the influence of the repulsive Coulomb barrier (RCB) in both cases evaluated. Photoelectron angular distributions show the effect of molecular alignment due to an allowed electronic excitation and can be understood qualitatively based on the calculated RCB surface using the Local Static Approximation. Comparison between femtosecond and nanosecond excitation reveals marked differences in the photoelectron spectra. While femtosecond experiments confirm that tunneling through the RCB is adiabatic, nanosecond experiments show a broad photoelectron feature peaking near the RCB maximum. This is explained in terms of the lifetime of internal conversion, which has been determined by time-resolved photoelectron spectroscopy to be ~120 ps: as this is faster than the nanosecond laser pulses, multiple photons can be absorbed through the S1 ← S0 transition which leads to large amounts of internal energy and enables electron detachment directly above the RCB. Fragmentation and detachment from the monoanion are also inferred by the presence of photoelectrons emitted at very low kinetic energy. Our results highlight the difficulty in interpreting photoelectron spectra of polyanions in which a resonant state is excited.

Influence of the repulsive Coulomb barrier on photoelectron spectra and angular distributions in a resonantly excited dianion.

The photoelectron imaging of the indigo carmine dianion is used to demonstrate the effects of resonance excitation, pulse duration and pulse intensity on the photoelectron spectra and angular distributions of a dianion. Excitation of the S1 state leads to an aligned distribution of excited state dianions. The photoelectron angular distribution following subsequent photodetachment within a femtosecond laser pulse is primarily determined by the repulsive Coulomb barrier. Extending the timescale for photodetachment to nanoseconds leads to dramatic changes in both the spectral and angular distributions. These observations are explained in terms of statistical detachment of electrons, either from the monoanion, or from the ground state of the dianion following a number of photon cycles through the S1 ← S0 transition. At high intensity, new electron emission channels open up, leading to emission below the repulsive Coulomb barrier. This has been assigned to strong-field induced detachment and the effect of an electric field on the Coulomb barrier is discussed in terms of the photoelectron spectra and angular distributions.

Article	Year
Effect of internal energy on the repulsive Coulomb barrier of polyanions. Physical review letters\| PubMed ID: 22463527	2012
Spectroscopy and dynamics of the 7,7,8,8-tetracyanoquinodimethane radical anion. Physical chemistry chemical physics : PCCP\| PubMed ID: 20396813	2010
Ultrafast relaxation dynamics observed through time-resolved photoelectron angular distributions. The journal of physical chemistry. A\| PubMed ID: 20961158	2010
Excited states in electron-transfer reaction products: ultrafast relaxation dynamics of an isolated acceptor radical anion. The journal of physical chemistry. A\| PubMed ID: 21682320	2011
Time-resolved photoelectron imaging of the chloranil radical anion: ultrafast relaxation of electronically excited electron acceptor states. Physical chemistry chemical physics : PCCP\| PubMed ID: 21971531	2011
Photoelectron spectroscopy of the model GFP chromophore anion. Physical chemistry chemical physics : PCCP\| PubMed ID: 22614441	2012
Velocity-map imaging at low extraction fields. The Review of scientific instruments\| PubMed ID: 22755609	2012
Ultrafast above-threshold dynamics of the radical anion of a prototypical quinone electron-acceptor. Nature chemistry\| PubMed ID: 23881504	2013
Influence of the repulsive Coulomb barrier on photoelectron spectra and angular distributions in a resonantly excited dianion. The Journal of chemical physics\| PubMed ID: 24006992	2013
Effects of resonant excitation, pulse duration and intensity on photoelectron imaging of a dianion. Physical chemistry chemical physics : PCCP\| PubMed ID: 24092279	2013

Daniel Horke

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