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New view of the ICN A continuum using photoelectron spectroscopy of ICN−

Authors: Elisa M, Miller; Leonid, Sheps; Yu-Ju, Lu; Amanda S, Case; Anne B, McCoy; W Carl, Lineberger;

New view of the ICN A continuum using photoelectron spectroscopy of ICN−

Abstract

Negative-ion photoelectron spectroscopy of ICN− (${\rm \tilde X}$X̃ 2Σ+) reveals transitions to the ground electronic state (${\rm \tilde X}$X̃ 1Σ+) of ICN as well as the first five excited states (3Π2, 3Π1, $\sideset{^3}{_{0^-}}{\Pi}$Π0−3, $\sideset{^3}{_{0^+}}{\Pi}$Π0+3, and 1Π1) that make up the ICN A continuum. By starting from the equilibrium geometry of the anion, photoelectron spectroscopy characterizes the electronic structure of ICN at an elongated I–C bond length of 2.65 Å. Because of this bond elongation, the lowest three excited states of ICN (3Π2, 3Π1, and $\sideset{^3}{_{0^-}}{\Pi}$Π0−3) are resolved for the first time in the photoelectron spectrum. In addition, the spectrum has a structured peak that arises from the frequently studied conical intersection between the $\sideset{^3}{_{0^+}}{\Pi}$Π0+3 and 1Π1 states. The assignment of the spectrum is aided by MR-SO-CISD calculations of the potential energy surfaces for the anion and neutral ICN electronic states, along with calculations of the vibrational levels supported by these states. Through thermochemical cycles involving spectrally narrow transitions to the excited states of ICN, we determine the electron affinity, EA(ICN), to be 1.345 (+0.04/−0.02) eV and the anion dissociation energy, D0(${\rm \tilde X}$X̃ 2Σ+ I–CN−), to be 0.83 (+0.04/−0.02) eV.

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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
12
Average
Average
Top 10%
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