Photoelectron spectroscopy of the deprotonated tryptophan anion: the contribution of deprotomers to its photodetachment channels.

Photoelectron spectroscopy and electronic structure calculations are used to investigate the electronic structure of the deprotonated anionic form of the aromatic amino acid tryptophan, and its chromophore, indole. The photoelectron spectra of tryptophan, recorded at different wavelengths across the UV, consist of two direct detachment channels and thermionic emission, whereas the hν = 4.66 eV spectrum of indole consists of two direct detachment features. Electronic structure calculations indicate that two deprotomers of tryptophan are present in the ion beam; deprotonation of the carboxylic acid group (Trp(I)-) or the N atom on the indole ring (Trp(II)-). Strong similarities are observed between the direct detachment channels in the photoelectron spectra of tryptophan and indole, which in conjunction with electronic structure calculations, indicate that electron loss from Trp(II)- dominates this portion of the spectra. However, there is some evidence that direct detachment of Trp(I)- is also observed. Thermionic emission is determined to predominantly arise from the decarboxylation of Trp(I)-, mediated by the ππ* excited state near λ = 300 nm, which results in an anionic fragment with a negative electron affinity that readily autodetaches.

Dynamics of Anions: From Bound to Unbound States and Everything In Between.

Gas-phase anions present an ideal playground for the exploration of excited-state dynamics. They offer control in terms of the mass, extent of solvation, internal temperature, and conformation. The application of a range of ion sources has opened the field to a vast array of anionic systems whose dynamics are important in areas ranging from biology to star formation. Here, we review recent experimental developments in the field of anion photodynamics, demonstrating the detailed insight into photodynamical and electron-capture processes that can be uncovered. We consider the electronic and nuclear ultrafast dynamics of electronically bound excited states along entire reaction coordinates; electronically unbound states showing that photochemical concepts, such as chromophores and Kasha's rule, are transferable to electron-driven chemistry; and nonvalence states that straddle the interface between bound and unbound states. Finally, we consider likely developments that are sure to keep the field of anion dynamics buoyant and impactful. Expected final online publication date for the Annual Review of Physical Chemistry, Volume 75 is April 2024. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Spectroscopy and dynamics of the hydrated electron at the water/air interface.

The hydrated electron, e-(aq), has attracted much attention as a central species in radiation chemistry. However, much less is known about e-(aq) at the water/air surface, despite its fundamental role in electron transfer processes at interfaces. Using time-resolved electronic sum-frequency generation spectroscopy, the electronic spectrum of e-(aq) at the water/air interface and its dynamics are measured here, following photo-oxidation of the phenoxide anion. The spectral maximum agrees with that for bulk e-(aq) and shows that the orbital density resides predominantly within the aqueous phase, in agreement with supporting calculations. In contrast, the chemistry of the interfacial hydrated electron differs from that in bulk water, with e-(aq) diffusing into the bulk and leaving the phenoxyl radical at the surface. Our work resolves long-standing questions about e-(aq) at the water/air interface and highlights its potential role in chemistry at the ubiquitous aqueous interface.

Photodissociation of permanganate (MnO4-) produces the manganese dioxide anion (MnO2-) in an excited triplet state.

Photoelectron imaging, electron action spectroscopy and electronic structure calculations are used to probe the structure and dynamics of MnO4-. Following excitation to the first bright absorption band of MnO4- (11T2), photodetachment, via ground state electron loss, and photodissociation, to produce MnO2-, are both observed to occur simultaneously. MnO2- is produced in an excited electronic state, identified as a triplet state, which indicates that the dissociation proceeds on singlet potential energy surfaces via spin conservation. Furthermore, electronic structure calculations indicate that both photodetachment and photodissociation are multiple photon processes that are mediated by the same 11T2 excited state. Taken together this data indicates that photodissociation of MnO4- occurs via a statistical dissociation on the MnO4- ground state at visible wavelengths.

Alkylated green fluorescent protein chromophores: dynamics in the gas phase and in aqueous solution.

Fluorescent labelling of macromolecular samples, including using the green fluorescent protein (GFP), has revolutionised the field of bioimaging. The ongoing development of fluorescent proteins require a detailed understanding of the photophysics of the biochromophore, and how chemical derivatisation influences the excited state dynamics. Here, we investigate the photophysical properties associated with the S1 state of three alkylated derivatives of the chromophore in GFP, in the gas phase using time-resolved photoelectron imaging, and in water using femtosecond fluorescence upconversion. The gas-phase lifetimes (1.6-10 ps), which are associated with the intrinsic (environment independent) dynamics, are substantially longer than the lifetimes in water (0.06-3 ps), attributed to stabilisation of both twisted intermediate structures and conical intersection seams in the condensed phase. In the gas phase, alkylation on the 3 and 5 positions of the phenyl ring slows the dynamics due to inertial effects, while a 'pre-twist' of the methine bridge through alkylation on the 2 and 6 positions significantly shortens the excited state lifetimes. Formation of a minor, long-lived (≫ 40 ps) excited state population in the gas phase is attributed to intersystem crossing to a triplet state, accessed because of a T1/S1 degeneracy in the so-called P-trap potential energy minimum associated with torsion of the single-bond in the bridging unit connecting to the phenoxide ring. A small amount of intersystem crossing is supported through TD-DFT molecular dynamics trajectories and MS-CASPT2 calculations. No such intersystem crossing occurs in water at T = 300 K or in ethanol at T ≈ 77 K, due to a significantly altered potential energy surface and P-trap geometry.

Unraveling the decarboxylation dynamics of the fluorescein dianion with fragment action spectroscopy.

The decarboxylation dynamics of the doubly deprotonated fluorescein dianion, Fl2-, are investigated by recording fragment action spectra for the anion, Fl-, and its decarboxylated analog, Fl-CO2-, using a new reflectron secondary mass spectrometer. The formation of the anion, Fl-, is directly investigated by photoelectron imaging. The Fl- and Fl-CO2- action spectra indicate that, for λ < 400 nm, one-photon dissociative photodetachment, i.e., simultaneous decarboxylation and electron loss, competes with photodetachment, whereas for λ > 400 nm, decarboxylation only proceeds following electron loss via a sequential two-photon process. The primary decarboxylation pathway is the ready loss of CO2 from the relatively short-lived intermediate excited state, Fl-[D1], which is formed by electron loss from the dianion via resonant tunneling through the repulsive Coloumb barrier associated with a high-lying excited dianion state, Fl2-[S2].

Low-Energy Shape Resonances of a Nucleobase in Water.

When high-energy radiation passes through aqueous material, low-energy electrons are produced which cause DNA damage. Electronic states of anionic nucleobases have been suggested as an entrance channel to capture the electron. However, identifying these electronic resonances have been restricted to gas-phase electron-nucleobase studies and offer limited insight into the resonances available within the aqueous environment of DNA. Here, resonance and detachment energies of the micro-hydrated uracil pyrimidine nucleobase anion are determined by two-dimensional photoelectron spectroscopy and are shown to extrapolate linearly with cluster size. This extrapolation allows the corresponding resonance and detachment energies to be determined for uracil in aqueous solution as well as the reorganization energy associated with electron capture. Two shape resonances are clearly identified that can capture low-energy electrons and subsequently form the radical anion by solvent stabilization and internal conversion to the ground electronic state. The resonances and their dynamics probed here are the nucleobase-centered doorway states for low-energy electron capture and damage in DNA.

Allophycocyanin A is a carbon dioxide receptor in the cyanobacterial phycobilisome.

Light harvesting is fundamental for production of ATP and reducing equivalents for CO2 fixation during photosynthesis. However, electronic energy transfer (EET) through a photosystem can harm the photosynthetic apparatus when not balanced with CO2. Here, we show that CO2 binding to the light-harvesting complex modulates EET in photosynthetic cyanobacteria. More specifically, CO2 binding to the allophycocyanin alpha subunit of the light-harvesting complex regulates EET and its fluorescence quantum yield in the cyanobacterium Synechocystis sp. PCC 6803. CO2 binding decreases the inter-chromophore distance in the allophycocyanin trimer. The result is enhanced EET in vitro and in live cells. Our work identifies a direct target for CO2 in the cyanobacterial light-harvesting apparatus and provides insights into photosynthesis regulation.

Kasha's Rule and Koopmans' Correlations for Electron Tunnelling through Repulsive Coulomb Barriers in a Polyanion.

The long-range electronic structure of polyanions is defined by the repulsive Coulomb barrier (RCB). Excited states can decay by resonant electron tunnelling through RCBs, but such decay has not been observed for electronically excited states other than the first excited state, suggesting a Kasha-type rule for resonant electron tunnelling. Using action spectroscopy, photoelectron imaging, and computational chemistry, we show that the fluorescein dianion, Fl2-, partially decays through electron tunnelling from the S2 excited state, thus demonstrating anti-Kasha behavior, and that resonant electron tunnelling adheres to Koopmans' correlations, thus disentangling different channels.

Resonances in nitrobenzene probed by the electron attachment to neutral and by the photodetachment from anion.

We probe resonances (transient anions) in nitrobenzene with the focus on the electron emission from these. Experimentally, we populate resonances in two ways: either by the impact of free electrons on the neutral molecule or by the photoexcitation of the bound molecular anion. These two excitation means lead to transient anions in different initial geometries. In both cases, the anions decay by electron emission and we record the electron spectra. Several types of emission are recognized, differing by the way in which the resulting molecule is vibrationally excited. In the excitation of specific vibrational modes, distinctly different modes are visible in electron collision and photodetachment experiments. The unspecific vibrational excitation, which leads to the emission of thermal electrons following the internal vibrational redistribution, shows similar features in both experiments. A model for the thermal emission based on a detailed balance principle agrees with the experimental findings very well. Finally, a similar behavior in the two experiments is also observed for a third type of electron emission, the vibrational autodetachment, which yields electrons with constant final energies over a broad range of excitation energies. The entrance channels for the vibrational autodetachment are examined in detail, and they point to a new mechanism involving a reverse valence to non-valence internal conversion.

Photooxidation of the Phenolate Anion is Accelerated at the Water/Air Interface.

Molecular photodynamics can be dramatically affected at the water/air interface. Probing such dynamics is challenging, with product formation often probed indirectly through its interaction with interfacial water molecules using time-resolved and phase-sensitive vibrational sum-frequency generation (SFG). Here, the photoproduct formation of the phenolate anion at the water/air interface is probed directly using time-resolved electronic SFG and compared to transient absorption spectra in bulk water. The mechanisms are broadly similar, but 2 to 4 times faster at the surface. An additional decay is observed at the surface which can be assigned to either diffusion of hydrated electrons from the surface into the bulk or due to increased geminate recombination at the surface. These overall results are in stark contrast to phenol, where dynamics were observed to be 104 times faster and for which the hydrated electron was also a photoproduct. Our attempt to probe phenol showed no electron signal at the interface.

Photoelectron Imaging Study of the Diplatinum Iodide Dianions [Pt2I6]2- and [Pt2I8]2.

Photoelectron spectroscopy has been used to study the electronic structure, photodetachment, and photodissociation of the stable diplatinum iodide dianions [Pt2I6]2- and [Pt2I8]2-. Photoelectron spectra over a range of photon energies show the characteristic absence of low kinetic energy photoelectrons expected for dianions as a result of the repulsive Coulomb barrier (RCB). Vertical detachment energies of ∼1.6 and ∼1.9 eV and minimum RCBs of ∼1.2 and ∼1.3 eV are reported for [Pt2I6]2- and [Pt2I8]2-, respectively. Both of the diplatinum halides exhibit three direct detachment channels with distinct anisotropies, analogous to the previously reported spectra for PtI2- and PtI-, suggesting a platinum-centered molecular core that dominates the photodetachment. Additionally, evidence for two-photon photodissociation and subsequent photodetachment channels producing I- are observed for both dianions. Finally, an unexplained feature is observed at photon energies around 3 eV, whose origin is considered. Our work highlights the complex electronic structure of the heavy platinum-halide dianions that are characterized by a dense manifold of electronic states.

Photoelectron imaging of PtI2 - and its PtI- photodissociation product.

The photoelectron imaging of PtI2 - is presented over photon energies ranging from hν = 3.2 to 4.5 eV. The electron affinity of PtI2 is found to be 3.4 ± 0.1 eV, and the photoelectron spectrum contains three distinct peaks corresponding to three low-lying neutral states. Using a simple d-block model and the measured photoelectron angular distributions, the three states are tentatively assigned. Photodissociation of PtI2 - is also observed, leading to the formation of I- and of PtI-. The latter allows us to determine the electron affinity of PtI to be 2.35 ± 0.10 eV. The spectrum of PtI- is similarly structured with three peaks which, again, can be tentatively assigned using a similar model that agrees with the photoelectron angular distributions.

Effect of Microhydration on the Temporary Anion States of Pyrene.

The influence of incremental hydration (≤4) on the electronic resonances of the pyrene anion is studied using two-dimensional photoelectron spectroscopy. The photoexcitation energies of the resonances do not change; therefore, from the anion's perspective, the resonances remain the same, but from the neutral's perspective of the electron-molecule reaction, the resonances decrease in energy by the binding energy of the water molecules. The autodetachment of the resonances shows that hydration has very little effect, showing that even the dynamics of most of the resonances are not impacted by hydration. Two specific resonances do show changes that are explained by the closing of specific autodetachment channels. The lowest-energy resonance leads to efficient electron capture as observed through thermionic emission and evaporation of water molecules (dissociative electron attachment). The implications of low-energy electron capture in dense molecular interstellar clouds are discussed.

Photochemistry of the pyruvate anion produces CO2, CO, CH3-, CH3, and a low energy electron.

The photochemistry of pyruvic acid has attracted much scientific interest because it is believed to play critical roles in atmospheric chemistry. However, under most atmospherically relevant conditions, pyruvic acid deprotonates to form its conjugate base, the photochemistry of which is essentially unknown. Here, we present a detailed study of the photochemistry of the isolated pyruvate anion and uncover that it is extremely rich. Using photoelectron imaging and computational chemistry, we show that photoexcitation by UVA light leads to the formation of CO2, CO, and CH3-. The observation of the unusual methide anion formation and its subsequent decomposition into methyl radical and a free electron may hold important consequences for atmospheric chemistry. From a mechanistic perspective, the initial decarboxylation of pyruvate necessarily differs from that in pyruvic acid, due to the missing proton in the anion.

A Hückel Model for the Excited-State Dynamics of a Protein Chromophore Developed Using Photoelectron Imaging.

Chemistry can be described as the movement of nuclei within molecules and the concomitant instantaneous change in electronic structure. This idea underpins the central chemical concepts of potential energy surfaces and reaction coordinates. To experimentally capture such chemical change therefore requires methods that can probe both the nuclear and electronic structure simultaneously and on the time scale of atomic motion. In this Account, we show how time-resolved photoelectron imaging can do exactly this and how it can be used to build a detailed and intuitive understanding of the electronic structure and excited-state dynamics of chromophores. The chromophore of the photoactive yellow protein (PYP) is used as a case study. This chromophore contains a para-substituted phenolate anion, where the substituent, R, can be viewed as an acrolein derivative. It is shown that the measured photoelectron angular distribution can be directly related to the electronic structure of the para-substituted phenolate anion. By incrementally considering differing R groups, it is also shown that these photoelectron angular distributions are exquisitely sensitive to the conformational flexibility of R and that when R contains a π-system the excited states of the chromophore can be viewed as a linear combination of the π* molecular orbitals on the phenolate (πPh*) and the R substituent (πR*). Such Hückel treatment shows that the S1 state of the PYP chromophore has predominantly πR* character and that it is essentially the same as the chromophore of the green fluorescent protein (GFP). The S1 excited-state dynamics of the PYP chromophore probed by time-resolved photoelectron imaging clearly reveals both structural (nuclear) dynamics through the energy spectrum and electronic dynamics through the photoelectron angular distributions. Both motions can be accurately assigned using quantum chemical calculations, and these are consistent with the intuitive Hückel treatment presented. The photoactive protein chromophores considered here are examples of where a chemists' intuitive Hückel view for ground-state chemistry appears to be transferable to the prediction of photochemical excited-state reactivity. While elegant and insightful, such models have limitations, including nonadiabatic dynamics, which is present in a related PYP chromophore, where a fraction of the S1 state population forms a nonvalence (dipole-bound) state of the anion.

Photo-isomerization of the isolated photoactive yellow protein chromophore: what comes before the primary step?

Photoactive proteins typically rely on structural changes in a small chromophore to initiate a biological response. While these changes often involve isomerization as the "primary step", preceding this is an ultrafast relaxation of the molecular framework caused by the sudden change in electronic structure upon photoexcitation. Here, we capture this motion for an isolated model chromophore of the photoactive yellow protein using time-resolved photoelectron imaging. It occurs in <150 fs and is apparent from a spectral shift of ∼70 meV and a change in photoelectron anisotropy. Electronic structure calculations enable the quantitative assignment of the geometric and electronic structure changes to a planar intermediate from which the primary step can then proceed.

Nonadiabatic Dynamics between Valence, Nonvalence, and Continuum Electronic States in a Heteropolycyclic Aromatic Hydrocarbon.

Internal conversion between valence-localized and dipole-bound states is thought to be a ubiquitous process in polar molecular anions, yet there is limited direct evidence. Here, photodetachment action spectroscopy and time-resolved photoelectron imaging with a heteropolycyclic aromatic hydrocarbon (hetero-PAH) anion, deprotonated 1-pyrenol, is used to demonstrate a subpicosecond (τ1 = 160 ± 20 fs) valence to dipole-bound state internal conversion following excitation of the origin transition of the first valence-localized excited state. The internal conversion dynamics are evident in the photoelectron spectra and in the photoelectron angular distributions (ß2 values) as the electronic character of the excited state population changes from valence to nonvalence. The dipole-bound state subsequently decays through mode-specific vibrational autodetachment with a lifetime τ2 = 11 ± 2 ps. These internal conversion and autodetachment dynamics are likely common in molecular anions but difficult to fingerprint due to the transient existence of the dipole-bound state. Potential implications of the present excited state dynamics for interstellar hetero-PAH anion formation are discussed.