Electronic structure of some pyridylacetylenes studied by he I photoelectron spectroscopy: A weak orbital interaction between the nonbonding electron pair on the nitrogen atom and the in-plane π orbital in the ethynyl group

Jun Okubo, Hiraku Shinozakia, Mari Kubota, Tsunetoshi Kobayashi

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The He I photoelectron spectra (PES) of 2- and 4-ethynylpyridine were measured, and the origin of each ionization band was clarified. For instance, 4-ethynylpyridine shows five PES bands at 9.58, 9.9, 10.0, 10.75 and 11.84 eV in the lower energy region, the 9.9 eV and 10.75 eV bands in particular being assigned to the ionizations from the atn orbital of the pyridyl group and the in-plane b2π orbital of the ethynyl group, respectively. Furthermore, with the aid of first order perturbation theory, the 10.59 eV band of 2-ethynylpyridine has been ascribed to the ionization from the a2-like π orbital, and the 10.8 eV band to that from the in-plane b2-like π one. Through the process of the band assignments for the ethynylpyridines, it has been revealed that there is a weak interaction between the n orbital on the ortho-substituted nitrogen atom and the in-plane π orbital localized on the ethynyl group of 2-ethynylpyridine. The photoelectron spectra of 1,4-bis(2-pyridyl)-1,3-butadiyne and 1,4-bis(4-pyridyl)-1,3-butadiyne, whose π-electron systems are regarded electronically as double ones of the corresponding ethynylpyridines, were also measured, and we have succeeded in making band assignments of these compounds on the ground of the correlation energy diagram with the ethynylpyridines.

Original languageEnglish
Pages (from-to)267-276
Number of pages10
JournalJournal of Electron Spectroscopy and Related Phenomena
Volume77
Issue number3
DOIs
Publication statusPublished - 1996 Apr 30

Fingerprint

Photoelectron spectroscopy
Photoelectrons
nitrogen atoms
Ionization
Electronic structure
Nitrogen
photoelectron spectroscopy
electronic structure
orbitals
Atoms
Electrons
electrons
interactions
photoelectrons
ionization
ethynylpyridine
perturbation theory
diagrams
energy

Keywords

  • Bis(pyridyl)butadiyne
  • Ethynylpyridine
  • Non-bonding electron pair
  • Photoelectron spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics
  • Surfaces and Interfaces

Cite this

@article{81fffd27d3e04f91be947fcccecf4d3c,
title = "Electronic structure of some pyridylacetylenes studied by he I photoelectron spectroscopy: A weak orbital interaction between the nonbonding electron pair on the nitrogen atom and the in-plane π orbital in the ethynyl group",
abstract = "The He I photoelectron spectra (PES) of 2- and 4-ethynylpyridine were measured, and the origin of each ionization band was clarified. For instance, 4-ethynylpyridine shows five PES bands at 9.58, 9.9, 10.0, 10.75 and 11.84 eV in the lower energy region, the 9.9 eV and 10.75 eV bands in particular being assigned to the ionizations from the atn orbital of the pyridyl group and the in-plane b2π orbital of the ethynyl group, respectively. Furthermore, with the aid of first order perturbation theory, the 10.59 eV band of 2-ethynylpyridine has been ascribed to the ionization from the a2-like π orbital, and the 10.8 eV band to that from the in-plane b2-like π one. Through the process of the band assignments for the ethynylpyridines, it has been revealed that there is a weak interaction between the n orbital on the ortho-substituted nitrogen atom and the in-plane π orbital localized on the ethynyl group of 2-ethynylpyridine. The photoelectron spectra of 1,4-bis(2-pyridyl)-1,3-butadiyne and 1,4-bis(4-pyridyl)-1,3-butadiyne, whose π-electron systems are regarded electronically as double ones of the corresponding ethynylpyridines, were also measured, and we have succeeded in making band assignments of these compounds on the ground of the correlation energy diagram with the ethynylpyridines.",
keywords = "Bis(pyridyl)butadiyne, Ethynylpyridine, Non-bonding electron pair, Photoelectron spectroscopy",
author = "Jun Okubo and Hiraku Shinozakia and Mari Kubota and Tsunetoshi Kobayashi",
year = "1996",
month = "4",
day = "30",
doi = "10.1016/0368-2048(95)02549-9",
language = "English",
volume = "77",
pages = "267--276",
journal = "Journal of Electron Spectroscopy and Related Phenomena",
issn = "0368-2048",
publisher = "Elsevier",
number = "3",

}

TY - JOUR

T1 - Electronic structure of some pyridylacetylenes studied by he I photoelectron spectroscopy

T2 - A weak orbital interaction between the nonbonding electron pair on the nitrogen atom and the in-plane π orbital in the ethynyl group

AU - Okubo, Jun

AU - Shinozakia, Hiraku

AU - Kubota, Mari

AU - Kobayashi, Tsunetoshi

PY - 1996/4/30

Y1 - 1996/4/30

N2 - The He I photoelectron spectra (PES) of 2- and 4-ethynylpyridine were measured, and the origin of each ionization band was clarified. For instance, 4-ethynylpyridine shows five PES bands at 9.58, 9.9, 10.0, 10.75 and 11.84 eV in the lower energy region, the 9.9 eV and 10.75 eV bands in particular being assigned to the ionizations from the atn orbital of the pyridyl group and the in-plane b2π orbital of the ethynyl group, respectively. Furthermore, with the aid of first order perturbation theory, the 10.59 eV band of 2-ethynylpyridine has been ascribed to the ionization from the a2-like π orbital, and the 10.8 eV band to that from the in-plane b2-like π one. Through the process of the band assignments for the ethynylpyridines, it has been revealed that there is a weak interaction between the n orbital on the ortho-substituted nitrogen atom and the in-plane π orbital localized on the ethynyl group of 2-ethynylpyridine. The photoelectron spectra of 1,4-bis(2-pyridyl)-1,3-butadiyne and 1,4-bis(4-pyridyl)-1,3-butadiyne, whose π-electron systems are regarded electronically as double ones of the corresponding ethynylpyridines, were also measured, and we have succeeded in making band assignments of these compounds on the ground of the correlation energy diagram with the ethynylpyridines.

AB - The He I photoelectron spectra (PES) of 2- and 4-ethynylpyridine were measured, and the origin of each ionization band was clarified. For instance, 4-ethynylpyridine shows five PES bands at 9.58, 9.9, 10.0, 10.75 and 11.84 eV in the lower energy region, the 9.9 eV and 10.75 eV bands in particular being assigned to the ionizations from the atn orbital of the pyridyl group and the in-plane b2π orbital of the ethynyl group, respectively. Furthermore, with the aid of first order perturbation theory, the 10.59 eV band of 2-ethynylpyridine has been ascribed to the ionization from the a2-like π orbital, and the 10.8 eV band to that from the in-plane b2-like π one. Through the process of the band assignments for the ethynylpyridines, it has been revealed that there is a weak interaction between the n orbital on the ortho-substituted nitrogen atom and the in-plane π orbital localized on the ethynyl group of 2-ethynylpyridine. The photoelectron spectra of 1,4-bis(2-pyridyl)-1,3-butadiyne and 1,4-bis(4-pyridyl)-1,3-butadiyne, whose π-electron systems are regarded electronically as double ones of the corresponding ethynylpyridines, were also measured, and we have succeeded in making band assignments of these compounds on the ground of the correlation energy diagram with the ethynylpyridines.

KW - Bis(pyridyl)butadiyne

KW - Ethynylpyridine

KW - Non-bonding electron pair

KW - Photoelectron spectroscopy

UR - http://www.scopus.com/inward/record.url?scp=0008447686&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0008447686&partnerID=8YFLogxK

U2 - 10.1016/0368-2048(95)02549-9

DO - 10.1016/0368-2048(95)02549-9

M3 - Article

AN - SCOPUS:0008447686

VL - 77

SP - 267

EP - 276

JO - Journal of Electron Spectroscopy and Related Phenomena

JF - Journal of Electron Spectroscopy and Related Phenomena

SN - 0368-2048

IS - 3

ER -