Zero electron kinetic energy and photoelectron spectroscopy of the XeI− anion

Lenzer, Thomas; Furlanetto, Michael R.; Asmis, Knut R.; Neumark, Daniel M.

doi:10.1063/1.477774

Cited by 45 publications

(63 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…20 Furthermore, this value is reasonable for the magnitude of interaction of a charge on a polarizable atom-for example, consider the gas-phase I Ϫ /Xe interaction energy is ϳ800 cm Ϫ1 at the potential minimum. 27 This result, and the very physical values of the required potential parameters, shows that the time-resolved detachment of iodide can be well fit with diffusion equations once the stabilization of the caged pair is included. Both primary and secondary recombination are simulated, as opposed to the fit obtained from the competing kinetics model ͓Eq.…”

Section: A Nature Of the Caged Pairmentioning

confidence: 79%

Time-resolved scavenging and recombination dynamics from I:e− caged pairs

Kloepfer¹,

Vilchiz²,

Lenchenkov³

et al. 2002

The Journal of Chemical Physics

130

View full text Add to dashboard Cite

The competition between geminate recombination of electrons with their parent radicals and electron scavenging with H+ is directly time resolved with ∼100 fs resolution at several acid concentrations. Electrons were produced from iodide photodetachment or two-photon ionization of H2O. With regards to those produced from iodide photodetachment, the separation between primary and secondary I:e− recombination is established using a full numerical solution to the diffusion equation. Electron ejection is found to be short range and a potential well of ∼3kbT depth stabilizing the solvent caged pair is required to yield a satisfactory fit to experiment. From time-resolved scavenging data up to 5 M HCl, it is shown that the electron can be scavenged both inside and outside the caged pair by H+ with nearly equal efficiency. The steady-state scavenging yield as a function of scavenger concentration is then predicted based on the determined time-dependent recombination function. Reassessment of several benchmark scavenging experiments from the 1960’s leads to the conclusion that the primary yield of electrons after excitation of iodide is near unity.

show abstract

Section: A Nature Of the Caged Pairmentioning

confidence: 79%

Time-resolved scavenging and recombination dynamics from I:e− caged pairs

Kloepfer¹,

Vilchiz²,

Lenchenkov³

et al. 2002

The Journal of Chemical Physics

130

View full text Add to dashboard Cite

show abstract

“…Both states correspond to the degenerate P 3/2 spin-orbit component of atomic iodine, which is split by interaction with the weakly bound water molecule. This splitting is well-known from anion-ZEKE-spectra of iodide noble gas complexes 24,25 and is expected to lie in the range 200-300 cm -1 . The second spin-orbit component of atomic iodine gives rise to the II 1/2 electronic state of iodine water, which lies 7800 cm -1 above the X 1/2 ground state.…”

Section: Methodsmentioning

confidence: 93%

Anion ZEKE-Spectroscopy of the Weakly Bound Iodine Water Complex

2010

View full text Add to dashboard Cite

Zero kinetic electron energy photodetachment spectroscopy of I(-)·H(2)O and I(-)·D(2)O has been performed from 27 660 to 28 500 cm(-1) and from 27 660 to 35 900 cm(-1), respectively. The I(-)·D(2)O spectral data and theoretical studies resulted in a reassignment of earlier anion-ZEKE spectra of iodide water ( Bässmann , C. ; et al. Int. J. Mass Spectrom. Ion Processes 1996 , 159 , 153 ). In opposite to the I(-)·H(2)O, the I(-)·D(2)O spectrum reveals a regular progression of the iodine-water van der Waals stretching mode and a short progression of even quanta of the van der Waals rocking mode. A rough estimation delivers dissociation thresholds of the anionic and of the lower and the upper spin-orbit component of the neutral van der Waals complex. A high resolution ZEKE spectrum of the van der Waals stretching mode (v = 1) reveals significant fine structure, which is found again in a former photodissociation spectrum of the anionic complex ( Ayotte , P. ; et al. J. Phys. Chem. A 1998 , 102 , 3067 ). Our assignments are supported by theoretical calculations of molecular structures and vibrational motions. Vibrational frequencies and isotope effects are reproduced very satisfyingly by these calculations.

show abstract

“…Examples include the studies of Cheshnovsky and co-workers on X Ϫ ͑H 2 O͒ n (X Ϫ ϭCl Ϫ , Br Ϫ , I Ϫ ) 27 and Xe n I Ϫ , 28,29 Bowen and co-workers on Ar n O Ϫ , 30 and Arnold et al on X Ϫ ͑CO 2 ͒ n (X Ϫ ϭBr Ϫ , I Ϫ ) and I Ϫ ͑N 2 O͒ n . 31,32 However, two problems arise when one tries to extract information on nonadditive forces from such studies: ͑1͒ the pair potentials needed for the anion and neutral are usually not known very accurately, and ͑2͒ depending on the type of energy analyzer used, the resolution of conventional anion PES is typically between 70 [31][32][33] and 480 cm Ϫ1 . 28,29 Due to this limited resolution anion PES experiments are, at best, sensitive to the largest nonadditive effects.…”

Section: Introductionmentioning

confidence: 99%

Zero electron kinetic energy and threshold photodetachment spectroscopy of XenI− clusters (n=2–14): Binding, many-body effects, and structures

Lenzer

Furlanetto

Pivonka

et al. 1999

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

Origins and modeling of many-body exchange effects in van der Waals clustersXe n I Ϫ van der Waals clusters have been investigated by anion zero electron kinetic energy ͑ZEKE͒ and partially discriminated threshold photodetachment ͑PDTP͒ spectroscopy. The experiments yield size-dependent electron affinities ͑EAs͒ and electronic state splittings between the X, I, and II states accessed by photodetachment. Cluster minimum energy structures have been determined by extensive simulated annealing molecular dynamics calculations using Xe-I ͑Ϫ͒ pair potentials from anion ZEKE spectroscopy and various nonadditive terms. The EAs calculated without many-body effects overestimate the experimental EAs by up to 3000 cm Ϫ1 . Repulsive many-body induction in the anion clusters is found to be the dominant nonadditive effect, though the attractive interaction between the iodide charge and the Xe 2 exchange quadrupole is also important. Unique global minimum energy structures for the anion clusters arise from the influence of the many-body terms, yielding, e.g., arrangements with a closed shell of xenon atoms around the iodide anion for the clusters with nϭ12-14. The specific dependence of the EA curve on cluster size allows us to refine the absolute Xe-I bond lengths for the anion, X, I, and II state diatomic potentials to within Ϯ0.05 Å.

show abstract

Zero electron kinetic energy and photoelectron spectroscopy of the XeI− anion

Cited by 45 publications

References 60 publications

Time-resolved scavenging and recombination dynamics from I:e− caged pairs

Time-resolved scavenging and recombination dynamics from I:e− caged pairs

Anion ZEKE-Spectroscopy of the Weakly Bound Iodine Water Complex

Zero electron kinetic energy and threshold photodetachment spectroscopy of XenI− clusters (n=2–14): Binding, many-body effects, and structures

Contact Info

Product

Resources

About