The Threshold Photoelectron Spectrum of Fulvenone: A Reactive Ketene Derivative in Lignin Valorization

Patrick Hemberger; Zeyou Pan; Andras Bodi; Jeroen A. van Bokhoven; Thomas K. Ormond; G. Barney Ellison; Nadav Genossar; Joshua H. Baraban

doi:10.1002/cphc.202000477

The Threshold Photoelectron Spectrum of Fulvenone: A Reactive Ketene Derivative in Lignin Valorization

Patrick Hemberger, Zeyou Pan, Andras Bodi, Jeroen A. van Bokhoven, Thomas K. Ormond, G. Barney Ellison, Nadav Genossar, Joshua H. Baraban

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

Unveiling reaction mechanisms by isomer-selective detection of reactive intermediates requires advanced spectroscopic knowledge. We study the photoionization of fulvenone (c-C₅H₄=C=O), a reactive ketene species relevant in catalytic pyrolysis of lignin, which was generated by pyrolysis of 2-methoxy acetophenone. The high-resolution threshold photoelectron spectrum (TPES) with vacuum ultraviolet synchrotron radiation revealed well-resolved vibrational transitions, assigned to ring deformation modes of the cyclopentadiene moiety. The adiabatic ionization energy was determined to be 8.25±0.01 eV and is assigned to the (Formula presented.) ²A₂← (Formula presented.) ¹A₁ transition. A broad and featureless band arising at 9 eV is associated with the (Formula presented.) ²B₁← (Formula presented.) ¹A₁ excitation. A conical intersection is responsible for the ultrafast relaxation of the fulvenone cation from the (Formula presented.) into the (Formula presented.) state resulting in a featureless and lifetime broadened band. These insights will increase the detection capabilities for fulvenone and thereby help to elucidate reaction mechanisms in lignin catalytic pyrolysis.

Original language	English
Pages (from-to)	2217-2222
Number of pages	6
Journal	ChemPhysChem
Volume	21
Issue number	19
DOIs	https://doi.org/10.1002/cphc.202000477
State	Published - 2 Oct 2020

Keywords

Catalysis
ketene
lignin
photoelectron spectroscopy
reactive intermediates

ASJC Scopus subject areas

Atomic and Molecular Physics, and Optics
Physical and Theoretical Chemistry

Access to Document

10.1002/cphc.202000477

Cite this

@article{41baf44b1d824a8c9d4ba73543d20732,

title = "The Threshold Photoelectron Spectrum of Fulvenone: A Reactive Ketene Derivative in Lignin Valorization",

abstract = "Unveiling reaction mechanisms by isomer-selective detection of reactive intermediates requires advanced spectroscopic knowledge. We study the photoionization of fulvenone (c-C5H4=C=O), a reactive ketene species relevant in catalytic pyrolysis of lignin, which was generated by pyrolysis of 2-methoxy acetophenone. The high-resolution threshold photoelectron spectrum (TPES) with vacuum ultraviolet synchrotron radiation revealed well-resolved vibrational transitions, assigned to ring deformation modes of the cyclopentadiene moiety. The adiabatic ionization energy was determined to be 8.25±0.01 eV and is assigned to the (Formula presented.) 2A2← (Formula presented.) 1A1 transition. A broad and featureless band arising at 9 eV is associated with the (Formula presented.) 2B1← (Formula presented.) 1A1 excitation. A conical intersection is responsible for the ultrafast relaxation of the fulvenone cation from the (Formula presented.) into the (Formula presented.) state resulting in a featureless and lifetime broadened band. These insights will increase the detection capabilities for fulvenone and thereby help to elucidate reaction mechanisms in lignin catalytic pyrolysis.",

keywords = "Catalysis, ketene, lignin, photoelectron spectroscopy, reactive intermediates",

author = "Patrick Hemberger and Zeyou Pan and Andras Bodi and {van Bokhoven}, {Jeroen A.} and Ormond, {Thomas K.} and Ellison, {G. Barney} and Nadav Genossar and Baraban, {Joshua H.}",

note = "Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

year = "2020",

month = oct,

day = "2",

doi = "10.1002/cphc.202000477",

language = "English",

volume = "21",

pages = "2217--2222",

journal = "ChemPhysChem",

issn = "1439-4235",

publisher = "Wiley-VCH Verlag",

number = "19",

}

TY - JOUR

T1 - The Threshold Photoelectron Spectrum of Fulvenone

T2 - A Reactive Ketene Derivative in Lignin Valorization

AU - Hemberger, Patrick

AU - Pan, Zeyou

AU - Bodi, Andras

AU - van Bokhoven, Jeroen A.

AU - Ormond, Thomas K.

AU - Ellison, G. Barney

AU - Genossar, Nadav

AU - Baraban, Joshua H.

PY - 2020/10/2

Y1 - 2020/10/2

N2 - Unveiling reaction mechanisms by isomer-selective detection of reactive intermediates requires advanced spectroscopic knowledge. We study the photoionization of fulvenone (c-C5H4=C=O), a reactive ketene species relevant in catalytic pyrolysis of lignin, which was generated by pyrolysis of 2-methoxy acetophenone. The high-resolution threshold photoelectron spectrum (TPES) with vacuum ultraviolet synchrotron radiation revealed well-resolved vibrational transitions, assigned to ring deformation modes of the cyclopentadiene moiety. The adiabatic ionization energy was determined to be 8.25±0.01 eV and is assigned to the (Formula presented.) 2A2← (Formula presented.) 1A1 transition. A broad and featureless band arising at 9 eV is associated with the (Formula presented.) 2B1← (Formula presented.) 1A1 excitation. A conical intersection is responsible for the ultrafast relaxation of the fulvenone cation from the (Formula presented.) into the (Formula presented.) state resulting in a featureless and lifetime broadened band. These insights will increase the detection capabilities for fulvenone and thereby help to elucidate reaction mechanisms in lignin catalytic pyrolysis.

AB - Unveiling reaction mechanisms by isomer-selective detection of reactive intermediates requires advanced spectroscopic knowledge. We study the photoionization of fulvenone (c-C5H4=C=O), a reactive ketene species relevant in catalytic pyrolysis of lignin, which was generated by pyrolysis of 2-methoxy acetophenone. The high-resolution threshold photoelectron spectrum (TPES) with vacuum ultraviolet synchrotron radiation revealed well-resolved vibrational transitions, assigned to ring deformation modes of the cyclopentadiene moiety. The adiabatic ionization energy was determined to be 8.25±0.01 eV and is assigned to the (Formula presented.) 2A2← (Formula presented.) 1A1 transition. A broad and featureless band arising at 9 eV is associated with the (Formula presented.) 2B1← (Formula presented.) 1A1 excitation. A conical intersection is responsible for the ultrafast relaxation of the fulvenone cation from the (Formula presented.) into the (Formula presented.) state resulting in a featureless and lifetime broadened band. These insights will increase the detection capabilities for fulvenone and thereby help to elucidate reaction mechanisms in lignin catalytic pyrolysis.

KW - Catalysis

KW - ketene

KW - lignin

KW - photoelectron spectroscopy

KW - reactive intermediates

UR - http://www.scopus.com/inward/record.url?scp=85090065614&partnerID=8YFLogxK

U2 - 10.1002/cphc.202000477

DO - 10.1002/cphc.202000477

M3 - Article

C2 - 32628323

AN - SCOPUS:85090065614

SN - 1439-4235

VL - 21

SP - 2217

EP - 2222

JO - ChemPhysChem

JF - ChemPhysChem

IS - 19

ER -

The Threshold Photoelectron Spectrum of Fulvenone: A Reactive Ketene Derivative in Lignin Valorization

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this