Probing chemical dynamics with negative ions

Neumark, Daniel M.

doi:10.1063/1.2216709

Cited by 54 publications

(53 citation statements)

References 240 publications

(139 reference statements)

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“…[55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70] The development of new high resolution techniques expanded the applicability of photodetachment experiments to include electronic structure determination of unstable and excited states, photodetachment ultrafast dynamics, anion reactivity, and intermolecular interactions in cluster anions. 3,8,[71][72][73][74] On the theory side, several models of varying complexity have been developed, 54,[75][76][77] and the applications revealed their capabilities and limitations. Most importantly, testing the predictions of these models against the experimental measurements helped quantify the relative importance of different effects and interactions involved in the photoionization process.…”

Section: Introductionmentioning

confidence: 99%

Cross sections and photoelectron angular distributions in photodetachment from negative ions using equation-of-motion coupled-cluster Dyson orbitals

Oana

Krylov

2009

The Journal of Chemical Physics

177

226

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We report total and differential cross sections for photodetachment from negative ions using Dyson orbitals calculated from equation-of-motion coupled-cluster wave functions and free wave description of the detached electron. The energy dependence of the cross sections is reproduced well, however, the accuracy of absolute values varies. For F(-), C(-), NH(2)(-), and H(-), the calculated cross sections are within the error bars from the experimental values, whereas the errors for Li(-) and OH(-) are about 20%. The largest errors are observed for O(-) and O(2)(-) for which the calculated cross sections differ from the experimental ones by factors of 3 and 2, respectively. Calculated anisotropy parameters for atomic anions exhibit too slow decrease, which suggests that the diffuseness of the computed Dyson orbitals is underestimated. Moreover, in the asymptotic region, the orbitals exhibit artifactual oscillations probably due to the limitations of Gaussian basis sets. The analysis of the trends in the experimental anisotropy parameters suggests that the interaction of the detached electron with the core, which is neglected in the present model, is important.

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Section: Introductionmentioning

confidence: 99%

Cross sections and photoelectron angular distributions in photodetachment from negative ions using equation-of-motion coupled-cluster Dyson orbitals

Oana

Krylov

2009

The Journal of Chemical Physics

177

226

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“…1,2 Simplification of the local environment by using gas phase cluster ions provides one the chance to study these influences and gain a fundamental understanding of the effects solvation has on molecules. 1,2 Simplification of the local environment by using gas phase cluster ions provides one the chance to study these influences and gain a fundamental understanding of the effects solvation has on molecules.…”

Section: Introductionmentioning

confidence: 99%

A combined experimental/theoretical investigation of the near-infrared photodissociation of IBr−(CO2)n

Thompson

Martin

Darr

et al. 2008

The Journal of Chemical Physics

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We report the collaborative experimental and theoretical study of the time-resolved recombination dynamics of photodissociated IBr(-)(CO(2))(n) clusters. Excitation of the bare anionic chromophore to the dissociative A(') (2)Pi(1/2) state yields only I(-) and Br products. Interestingly, however, the addition of a few solvent molecules promotes recombination of the dissociating chromophore on the X (2)Sigma(1/2)(+) ground state, which correlates asymptotically with Br(-) and I products. This process is studied experimentally using time-resolved, pump-probe techniques and theoretically via nonadiabatic molecular dynamics simulations. In sharp contrast to previous I(2)(-) studies where more kinetic energy was released to the photofragments, the observed recombination times increase from picoseconds to nanoseconds with increasing cluster size up to n=10. The recombination times then drop dramatically back to picoseconds for cluster sizes n=11-14. This trend, seen both in experiment and theory, is explained by the presence of a solvent-induced well on the A(') state, the depth of which directly corresponds to the asymmetry of the solvation about the chromophore. The results seen for both the branching ratios and recombination times from experiment and theory show good qualitative agreement.

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“…The phenomenon reported here may prove to be general for molecular anions in which the dominant photodetachment channel above threshold produces free electrons with a nonzero angular momentum. The work should be of general interest as it may open new avenues for the study of electron-neutral interactions and the manipulation of chemically important transient neutral species produced by the photodetachment of anion precursors [3].…”

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confidence: 99%

Alignment of a Molecular Anion via a Shape Resonance in Near-Threshold Photodetachment

Continetti

2007

Phys. Rev. Lett.

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One-color-two-photon photodetachment of HOCO- at E hnu=1.60 eV accompanied by a measurement of the photoelectron angular distribution (PAD) is used to illustrate a novel approach to the alignment of a molecular anion. A quantitative analysis of the PAD reveals this alignment process is associated with a temporary anion formed by a p-wave shape resonance and the PAD in the two-photon signal is a result of interfering s- and d-partial waves within the atomic approximation. The extracted intensity and phase shift of the partial waves are consistent with the Wigner threshold law for photodetachment.

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Probing chemical dynamics with negative ions

Abstract: .

Cited by 54 publications

References 240 publications

Cross sections and photoelectron angular distributions in photodetachment from negative ions using equation-of-motion coupled-cluster Dyson orbitals

Cross sections and photoelectron angular distributions in photodetachment from negative ions using equation-of-motion coupled-cluster Dyson orbitals

A combined experimental/theoretical investigation of the near-infrared photodissociation of IBr−(CO2)n

Alignment of a Molecular Anion via a Shape Resonance in Near-Threshold Photodetachment

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