Photoelectron Spectroscopy of Biacetyl and Its Cluster Anions

Yerbolat Dauletyarov, Adam A. Wallace, Christopher C. Blackstone, Andrei M Sanov

Research output: Contribution to journalArticle

Abstract

Photoelectron spectroscopy of the biacetyl (dimethylglyoxal) anion reveals the properties of the ground singlet and lowest triplet electronic states of the neutral biacetyl (BA) molecule. Due to the broad and congested nature of the singlet transition, which peaks at a vertical detachment energy VDE = 1.12(5) eV, only an upper bound of the adiabatic electron affinity of BA could be determined: EA(BA) < 0.7 eV. A narrower and more structured triplet band peaking at VDE = 3.17(2) eV reveals the adiabatic electron binding energy of the triplet to be 3.05(2) eV. These results are in good agreement with ab initio (coupled-cluster) calculations. The lowest-energy structures of the anion, singlet, and triplet states of biacetyl are characterized by different orientations of the methyl groups within the molecular frame. In the ground singlet state of neutral BA, the methyl torsion is offset by ∼60° compared to that of the anion, while in the triplet the methyl orientation is similar to that of the anion. Photoelectron spectra of the cluster anions reveal that the intermolecular interactions in the homogeneously solvated (BA) n - clusters are significantly stronger than the interactions of BA - with N 2 O or even of BA - with H 2 O. To account for these observations, π-πbonded structures of the dimer and trimer anions of biacetyl are proposed based on density-functional theory calculations. The analysis of the proposed structures indicates that the negative charge in the (BA) n - cluster anions, at least in the dimer and the trimer, is significantly delocalized between all BA moieties present and there is a significant degree of covalent bonding within the cluster.

Original languageEnglish (US)
Pages (from-to)4158-4167
Number of pages10
JournalJournal of Physical Chemistry A
Volume123
Issue number19
DOIs
StatePublished - May 16 2019

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Diacetyl
Photoelectron spectroscopy
Anions
photoelectron spectroscopy
anions
trimers
dimers
Dimers
electron affinity
detachment
atomic energy levels
torsion
photoelectrons
binding energy
interactions
density functional theory
Electron affinity
ground state
Electronic states
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Photoelectron Spectroscopy of Biacetyl and Its Cluster Anions. / Dauletyarov, Yerbolat; Wallace, Adam A.; Blackstone, Christopher C.; Sanov, Andrei M.

In: Journal of Physical Chemistry A, Vol. 123, No. 19, 16.05.2019, p. 4158-4167.

Research output: Contribution to journalArticle

Dauletyarov, Yerbolat ; Wallace, Adam A. ; Blackstone, Christopher C. ; Sanov, Andrei M. / Photoelectron Spectroscopy of Biacetyl and Its Cluster Anions. In: Journal of Physical Chemistry A. 2019 ; Vol. 123, No. 19. pp. 4158-4167.
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N2 - Photoelectron spectroscopy of the biacetyl (dimethylglyoxal) anion reveals the properties of the ground singlet and lowest triplet electronic states of the neutral biacetyl (BA) molecule. Due to the broad and congested nature of the singlet transition, which peaks at a vertical detachment energy VDE = 1.12(5) eV, only an upper bound of the adiabatic electron affinity of BA could be determined: EA(BA) < 0.7 eV. A narrower and more structured triplet band peaking at VDE = 3.17(2) eV reveals the adiabatic electron binding energy of the triplet to be 3.05(2) eV. These results are in good agreement with ab initio (coupled-cluster) calculations. The lowest-energy structures of the anion, singlet, and triplet states of biacetyl are characterized by different orientations of the methyl groups within the molecular frame. In the ground singlet state of neutral BA, the methyl torsion is offset by ∼60° compared to that of the anion, while in the triplet the methyl orientation is similar to that of the anion. Photoelectron spectra of the cluster anions reveal that the intermolecular interactions in the homogeneously solvated (BA) n - clusters are significantly stronger than the interactions of BA - with N 2 O or even of BA - with H 2 O. To account for these observations, π-πbonded structures of the dimer and trimer anions of biacetyl are proposed based on density-functional theory calculations. The analysis of the proposed structures indicates that the negative charge in the (BA) n - cluster anions, at least in the dimer and the trimer, is significantly delocalized between all BA moieties present and there is a significant degree of covalent bonding within the cluster.

AB - Photoelectron spectroscopy of the biacetyl (dimethylglyoxal) anion reveals the properties of the ground singlet and lowest triplet electronic states of the neutral biacetyl (BA) molecule. Due to the broad and congested nature of the singlet transition, which peaks at a vertical detachment energy VDE = 1.12(5) eV, only an upper bound of the adiabatic electron affinity of BA could be determined: EA(BA) < 0.7 eV. A narrower and more structured triplet band peaking at VDE = 3.17(2) eV reveals the adiabatic electron binding energy of the triplet to be 3.05(2) eV. These results are in good agreement with ab initio (coupled-cluster) calculations. The lowest-energy structures of the anion, singlet, and triplet states of biacetyl are characterized by different orientations of the methyl groups within the molecular frame. In the ground singlet state of neutral BA, the methyl torsion is offset by ∼60° compared to that of the anion, while in the triplet the methyl orientation is similar to that of the anion. Photoelectron spectra of the cluster anions reveal that the intermolecular interactions in the homogeneously solvated (BA) n - clusters are significantly stronger than the interactions of BA - with N 2 O or even of BA - with H 2 O. To account for these observations, π-πbonded structures of the dimer and trimer anions of biacetyl are proposed based on density-functional theory calculations. The analysis of the proposed structures indicates that the negative charge in the (BA) n - cluster anions, at least in the dimer and the trimer, is significantly delocalized between all BA moieties present and there is a significant degree of covalent bonding within the cluster.

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