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.

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.

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].

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.

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.

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.

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.

Photoelectron spectroscopy of the protoporphyrin IX dianion.

Two-dimensional photoelectron spectroscopy using nanosecond and femtosecond lasers has been used to study the protopophyrin IX dianion at photon energies between 1.8-4.1 eV. The photoelectron spectra indicated the presence of two direct detachment channels, tunnelling through the repulsive Coulomb barrier (RCB) and thermionic emission from monoanions. A direct detachment feature suggested a near 0 eV electron affinity, which may be attributable to the repulsive through space interaction of the unshielded carboxylate groups. The minimum height of the repulsive Coulomb barrier (RCB) was found to be between 1.4-1.9 eV. Adiabatic tunnelling through the RCB was seen to occur on a timescale faster than rotational dephasing of the molecule. The observation of thermionic emission below the RCB in the nanosecond spectra originated from monoanions, which were produced via photon-cycling of the dianion.