The overlooked role of excited anion states in NiO2- photodetachment.

Photodetachment spectra of anionic species provide significant insights into the energies and nature of ground and excited states of both the anion and resultant neutral molecules. Direct detachment of the excess electron to the continuum may occur via formally allowed or forbidden transitions (perhaps as the result of intensity borrowing through vibronic coupling). However, alternate indirect pathways are also possible and often overlooked. Here, we report a two-dimensional photoelectron spectral study, combined with correlated electronic structure calculations, to elucidate the nature of photodetachment from NiO2-. The spectra are comprised of allowed and forbidden transitions, in excellent agreement with previously reported slow electron velocity mapped imaging spectra of the same system, which were interpreted in terms of direct detachment. In the current work, the contributions of indirect processes are revealed. Measured oscillations in the branching ratios of the spectral channels clearly indicate non-direct detachment processes, and the electronic structure calculations suggest that excited states of the appropriate symmetry and degeneracy lie slightly above the neutral ground state. Taken together, the results suggest that the origin of the observed forbidden transitions is the result of anion excited states mediating the electron detachment process.

Same but Different: Dipole-Stabilized Shape Resonances in CuF(-) and AgF(.).

Electron attachment to closed-shell molecules is a gateway to various important processes in the gas and condensed phases. The properties of an electron-attached state, such as its energy and lifetime as well as the character of the molecular orbital to which the electron is attached, determine the fate of the anion. In this experimental and theoretical study of copper and silver fluoride anions, we introduce a new type of metastable anionic state. Abrupt changes in photoelectron angular distributions point to the existence of autodetaching states. Equation-of-motion coupled-cluster singles and doubles calculations augmented by a complex absorbing potential identify some of these states as Σ and Π dipole-stabilized resonances, a new type of shape resonance. In addition, these molecules support valence and dipole-bound states and a Σ resonance of charge-transfer character. By featuring five different types of anionic states, they provide a vehicle for studying fundamental properties of anions and for validating new theoretical approaches for metastable states.

The effect of the dipole bound state on AgF⁻ vibrationally resolved photodetachment cross sections and photoelectron angular distributions.

The first photoelectron spectra of AgF(-) are recorded over the energy range 1.61-1.85 eV using the velocity map imaging technique. The resolved vibrational structure of the AgF X', v' ← AgF(-) X″, v″ = 0 band yields an AgF electron affinity of 1.46 ± 0.01 eV and vibrational frequency of 500 ± 40 cm(-1). For the v' = 2, 3, 4 channels, the photodetachment cross sections and angular distributions undergo rapid changes over a narrow electron kinetic energy range in the region of 50 meV (approximately 13 meV below the opening of the next vibrational channel). This is consistent with Fano-like behavior indicating autodetachment following excitation to a resonant anion state lying in the detachment continuum. EOM-CCSD calculations reveal this to be a dipole bound state. The consistency of the detachment data with the vibrational autodetachment propensity rule Δv = -1 shows that the autodetachment results from breakdown of the Born-Oppenheimer approximation, coupling the vibrational and electronic degrees of freedom.

Photoelectron angular distributions as probes of cluster anion structure: I(-)·(H2O)2 and I(-)·(CH3CN)2.

The use of photoelectron angular distributions to provide structural details of cluster environments is investigated. Photoelectron spectra and angular distributions of I(-)·(H2O)2 and I(-)·(CH3CN)2 cluster anions are recorded over a range of photon energies. The anisotropy parameter (ß) for electrons undergoes a sharp change (Δßmax) at photon energies close to a detachment channel threshold. I(-)·(H2O)2 results show the relationship between dipole moment and Δßmax to be similar to that observed in monosolvated I(-) detachment. The Δßmax of the 4.0 eV band in the I(-)·(CH3CN)2 photoelectron spectrum suggests a dipole moment of 5-6 D. This is consistent with predictions of a hydrogen bonded conformer of the I(-)·(CH3CN)2 cluster anion [Timerghazin, Q. K.; Nguyen, T. N.; Peslherbe, G. H. J. Chem. Phys. 2002, 116, 6867-6870].

Photodetachment and photodissociation of the linear OCuO- molecular anion: energy and time dependence of Cu- production.

A photodissociative study of CuO2(-) is presented using a combination of energy and time domain photoelectron spectroscopy. Ion source conditions are used that solely produce linear OCuO(-). Photodissociation of this isomer to produce Cu(-) + O2 is conclusively demonstrated at wavelengths between 765 and 340 nm. Nanosecond pulsed photoexcitation at wavelengths shorter than 340 nm produces single photon detachment transitions from the first excited state of CuO2(-). At longer wavelengths narrow Cu(-) fragment transitions are observed as a result of a sequential two photon process. In addition, the longer wavelengths produce a weak, broad two photon dependent signal, the result of detachment of the dissociating linear isomer. Time resolved pump-probe measurements reveal a long timescale growth (up to 150 ps) of the Cu(-) fragment yield, consistent with the unfavorable starting geometry for the dissociative process and indicating a potential energy surface which has one or more substantial barriers to dissociation.

Inter-channel effects in monosolvated atomic iodide cluster anion detachment: correlation of the anisotropy parameter with solvent dipole moment.

Photoelectron imaging results are presented for I(-)[middle dot]X cluster anions (X = CO(2), C(4)H(5)N [pyrrole], (CH(3))(2)CO, CH(3)NO(2)). The available detachment channels are labeled according to the neutral iodine atom states produced (channel I ≡ (2)P(3/2) and channel II ≡ (2)P(1/2)). At photon energies in the vicinity of the channel II threshold these data are compared to previously reported results for I(-)[middle dot]X (X = CH(3)CN, CH(3)Cl, CH(3)Br, and H(2)O). In particular, these results show a strong connection between the dipole moment of the solvent molecule and the behavior of the channel I photoelectron angular distributions in this region, which is consistent with an electronic autodetachment process. The evolution of the channel II:channel I branching ratios in this excitation regime supports this contention.

Near threshold Cl(-)·CH3I photodetachment: apparent 2P1/2 channel suppression and enhanced 2P3/2 channel vibrational excitation.

Cl(-)·CH(3)I cluster anion photoelectron images are recorded over a range of detachment wavelengths in the immediate post threshold region. The photoelectron spectral features fall into two categories. A number of weak, photon energy dependent transitions are observed and attributed to atomic anion fragmentation products. Several more intense, higher electron binding energy transitions result from single photon cluster anion detachment. Comparison with I(-)·CH(3)I suggests that the detachment process is more complicated for Cl(-)·CH(3)I. The single photon transition spacing is consistent with CH(3)I ν(3) mode excitation, but the two distinct vibronic bands of I(-)·CH(3)I detachment are not easily distinguished in the Cl(-)·CH(3)I spectra. Similarly, while the spectral intensities for both cluster anions show non-Franck Condon behavior, the level of vibrational excitation appears greater for Cl(-)·CH(3)I detachment. These observations are discussed in terms of low lying electronic states of CH(3)I along the C-I coordinate, and the influence of the CH(3)I moiety on the neutral halogen atom states.

Rapid changes in shear stress induce dissociation of a G alpha(q/11)-platelet endothelial cell adhesion molecule-1 complex.

It has been recently shown that endothelial platelet endothelial cell adhesion molecule-1 (PECAM-1) expression is pro-atherogenic. PECAM-1 is involved in sensing rapid changes in fluid shear stress but the mechanisms for activating signalling complexes at the endothelial cell junction have yet to be elucidated. Additional studies suggest the activation of membrane-bound G proteins G alpha(q/11) also mediate flow-induced responses. Here, we investigated whether PECAM-1 and G alpha(q/11) could act in unison to rapidly respond to fluid shear stress. With immunohistochemistry, we observed a co-localization of G alpha(q/11) and PECAM-1 at the cell-cell junction in the atheroprotected section of mouse aortae. In contrast, G alpha(q/11) was absent from junctions in atheroprone areas as well as in all arterial sections of PECAM-1 knockout mice. In primary human endothelial cells, temporal gradients in shear stress led to a rapid dissociation of the G alpha(q/11)-PECAM-1 complex within 30 s and a partial relocalization of the G alpha(q/11) staining to perinuclear areas within 150 min, whereas transitioning fluid flow devoid of temporal gradients did not disrupt the complex. Inhibition of G protein activation eliminated temporal gradient flow-induced G alpha(q/11)-PECAM-1 dissociation. These results allow us to conclude that G alpha(q/11)-PECAM-1 forms a mechanosensitive complex and its localization suggests the G alpha(q/11)-PECAM-1 complex is a critical mediator of vascular diseases.

Ketamine-induced loss of phenotype of fast-spiking interneurons is mediated by NADPH-oxidase.

Abuse of the dissociative anesthetic ketamine can lead to a syndrome indistinguishable from schizophrenia. In animals, repetitive exposure to this N-methyl-d-aspartate-receptor antagonist induces the dysfunction of a subset of cortical fast-spiking inhibitory interneurons, with loss of expression of parvalbumin and the gamma-aminobutyric acid-producing enzyme GAD67. We show here that exposure of mice to ketamine induced a persistent increase in brain superoxide due to activation in neurons of reduced nicotinamide adenine dinucleotide phosphate (NADPH) oxidase. Decreasing superoxide production prevented the effects of ketamine on inhibitory interneurons in the prefrontal cortex. These results suggest that NADPH oxidase may represent a novel target for the treatment of ketamine-induced psychosis.