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New view of the ICN A continuum using photoelectron spectroscopy of ICN
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10.1063/1.3679170
/content/aip/journal/jcp/136/4/10.1063/1.3679170
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/4/10.1063/1.3679170

Figures

Image of FIG. 1.
FIG. 1.

(a) Potential energy (V) is plotted as a function of the I to CN center of mass (COM) distance, R(I–CNCOM), in the linear (θ = 0°) geometry. The red circle highlights the conical intersection region between the 1Π1 and states. (b) V is plotted as a function of the angle between the R vector and CN axis, θ, for R(I–CNCOM) = 3.2 Å. In both panels, the ground-state wave function for the anion, Ψ(R, θ), is shown (dotted trace), and the grey box represents the Franck-Condon region. Also, the electronic ground state of the anion has been shifted by −0.4 eV to have better agreement with the measured transitions to the 3Π2 and 3Π1 states.

Image of FIG. 2.
FIG. 2.

Composite photoelectron spectrum of ICN. The broad peak at ∼ 3.2 eV corresponds to high-lying vibrational levels of the ground electronic state, 1Σ+. The ground-state origin lies more than 1 eV lower in binding energy and is not observed. The next three sharp features are the first three excited states of ICN (3Π2, 3Π1, and ). The broad asymmetric peak at ∼ 5.25 eV consists of transitions to the conical intersection (CI) region (1Π1 and ) and has some overlap with the dissociative electronic state. For comparison, the inset shows the photoelectron spectrum of IBr.25

Image of FIG. 3.
FIG. 3.

Composite photoelectron spectra of ICN (black) and ICN·Ar (red) showing transitions to the 3Π2 and 3Π1 states. Solvation by Ar results in a 30 meV shift to higher binding energy and a sharpening of the peaks for both electronic states. The shoulder on the higher binding energy side of the 3Π2 feature becomes more prominent in the ICN·Ar spectrum and lies ∼20 meV above the main peak, which is consistent with the calculated I–CN stretch frequency of the 3Π2 state.

Image of FIG. 4.
FIG. 4.

Thermochemical cycles used to determine EA(ICN) and D0(2Σ+ I–CN). The two thermochemical cycles involve either EA(CN) (Ref. 45) or D0(1Σ+ I–CN) (Ref. 21) values from previous measurements, along with the measured VDE(3Π1 ICN) and calculated D0(3Π1 I–CN) values from this work.

Tables

Generic image for table
Table I.

Calculated spectroscopic properties of ICN (2Σ+) and ICN (1Σ+, 3Π2, and 3Π1) from this work, along with previously measured values for ICN (1Σ+).

Generic image for table
Table II.

Summary of experimentally determined values: dissociation energy (D0), adiabatic electron affinity (EA), and term energies (T0).

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/content/aip/journal/jcp/136/4/10.1063/1.3679170
2012-01-30
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: New view of the ICN A continuum using photoelectron spectroscopy of ICN−
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/4/10.1063/1.3679170
10.1063/1.3679170
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