Electron affinity and excited states of methylglyoxal

Yerbolat Dauletyarov, Andrew R. Dixon, Adam A. Wallace, Andrei M Sanov

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A′), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A′) = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A′ state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A′ ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

Original languageEnglish (US)
Article number013934
JournalJournal of Chemical Physics
Volume147
Issue number1
DOIs
StatePublished - Jul 7 2017

Fingerprint

Pyruvaldehyde
Electron affinity
electron affinity
Excited states
photodetachment
Anions
excitation
Electronic states
anions
Ground state
Glyoxal
ground state
Photoelectrons
electronics
detachment
atomic energy levels
Equations of motion
attachment
energy
equations of motion

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Electron affinity and excited states of methylglyoxal. / Dauletyarov, Yerbolat; Dixon, Andrew R.; Wallace, Adam A.; Sanov, Andrei M.

In: Journal of Chemical Physics, Vol. 147, No. 1, 013934, 07.07.2017.

Research output: Contribution to journalArticle

Dauletyarov, Yerbolat ; Dixon, Andrew R. ; Wallace, Adam A. ; Sanov, Andrei M. / Electron affinity and excited states of methylglyoxal. In: Journal of Chemical Physics. 2017 ; Vol. 147, No. 1.
@article{52a76de93b134512a2f17b8d35ebbd59,
title = "Electron affinity and excited states of methylglyoxal",
abstract = "Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A′), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A′) = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A′ state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A′ ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.",
author = "Yerbolat Dauletyarov and Dixon, {Andrew R.} and Wallace, {Adam A.} and Sanov, {Andrei M}",
year = "2017",
month = "7",
day = "7",
doi = "10.1063/1.4982948",
language = "English (US)",
volume = "147",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "1",

}

TY - JOUR

T1 - Electron affinity and excited states of methylglyoxal

AU - Dauletyarov, Yerbolat

AU - Dixon, Andrew R.

AU - Wallace, Adam A.

AU - Sanov, Andrei M

PY - 2017/7/7

Y1 - 2017/7/7

N2 - Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A′), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A′) = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A′ state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A′ ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

AB - Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A′), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A′) = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A′ state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A′ ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

UR - http://www.scopus.com/inward/record.url?scp=85019267691&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85019267691&partnerID=8YFLogxK

U2 - 10.1063/1.4982948

DO - 10.1063/1.4982948

M3 - Article

AN - SCOPUS:85019267691

VL - 147

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 1

M1 - 013934

ER -