Frontier electronic structure in gas-phase epoxy and hydroxy cyclohexenes by means of photoelectron and electron transmission spectroscopies

被引:6
|
作者
Scagnolari, F
Modelli, A
Bottoni, A
Jones, D
Lazzari, D
机构
[1] UNIV BOLOGNA,DIPARTIMENTO CHIM G CIAMICIAN,I-40126 BOLOGNA,ITALY
[2] CNR,IST COMPOSTI CARBONIO CONTENENTI ETEROATOM & LORO,I-40129 BOLOGNA,ITALY
来源
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS | 1996年 / 92卷 / 09期
关键词
D O I
10.1039/ft9969201447
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Ionisation energy (E(i)) and electron affinity (E(a)) values in benzene oxide, benzene hydrate, the corresponding monoenes and other related molecules have been measured by means of UV photoelectron spectroscopy and electron transmission spectroscopy. The valence filled levels do not show evidence for strong sigma(co)-pi or oxygen lone pair-pi mixing in the alcohols nor in the epoxides. Although the energy perturbations, caused by the hydroxy and epoxy substituents, to adjacent filled pi orbitals are small, the electron transmission spectra show that the empty pi* orbitals are affected to very different extents, the epoxy substituent producing a sizeable electron affinity increase. This finding indicates the occurrence of strong interaction between the empty pi* orbitals and low-energy empty sigma* orbitals localised at the three-membered cycle. The experimental data have been compared with the orbital energies predicted by ab initio 3-21G calculations.
引用
收藏
页码:1447 / 1453
页数:7
相关论文
共 50 条
  • [41] Gas-phase photoelectron spectroscopy as a tool for understanding the electronic structures of components in electronic devices: Metalloporphyrins and metallophthalocyanines.
    Gruhn, NE
    Lichtenberger, DL
    Walker, FA
    Armstrong, NR
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2001, 221 : U349 - U350
  • [42] STRUCTURE OF ZINC PHTHALOCYANINE BY GAS-PHASE ELECTRON-DIFFRACTION
    MIHILL, A
    BUELL, W
    FINK, M
    JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (09) : 6416 - 6420
  • [43] STRUCTURE OF DICHROMIUM TETRAACETATE BY GAS-PHASE ELECTRON-DIFFRACTION
    KETKAR, SN
    FINK, M
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (02) : 338 - 340
  • [44] Molecular structure of tetravinylmethane from gas-phase electron diffraction
    Schultz, G
    Hargittai, I
    JOURNAL OF MOLECULAR STRUCTURE, 1998, 445 (1-3) : 47 - 53
  • [45] Probing the electronic structure of N-heterocyclic carbenes through gas-phase photoelectron spectroscopy and density functional calculations.
    Bill, TG
    Lichtenberger, DL
    Trnka, TM
    Grubbs, RH
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2002, 223 : A70 - A70
  • [46] THE ULTRAVIOLET PHOTOELECTRON-SPECTRA AND ELECTRONIC-STRUCTURE OF GAS-PHASE AND CONDENSED SNF2 AND PBF2
    NOVAK, I
    POTTS, AW
    JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1983, (10): : 2211 - 2213
  • [47] UPS and DFT investigation of the electronic structure of gas-phase trimesic acid
    Reisberg, L.
    Parna, R.
    Kikas, A.
    Kuusik, I.
    Kisand, V.
    Hirsimaki, M.
    Valden, M.
    Nommiste, E.
    JOURNAL OF ELECTRON SPECTROSCOPY AND RELATED PHENOMENA, 2016, 213 : 11 - 16
  • [48] The CeO2+ cation: Gas-phase reactivity and electronic structure
    Heinemann, C
    Cornehl, HH
    Schroder, D
    Dolg, M
    Schwarz, H
    INORGANIC CHEMISTRY, 1996, 35 (09) : 2463 - 2475
  • [49] Gas-phase generation and electronic structure investigation of chlorosulfanyl thiocyanate, CISSCN
    Yao, Li
    Ge, Maofa
    Wang, Weigang
    Zeng, Xiaoqing
    Sun, Zheng
    Wang, Dianxun
    INORGANIC CHEMISTRY, 2006, 45 (15) : 5971 - 5975
  • [50] NEGATIVE-IONS IN THE GAS-PHASE OBSERVED IN ELECTRON TRANSMISSION AND ELECTRON-ATTACHMENT SPECTROSCOPY
    HENI, M
    KWIATKOWSKI, G
    ILLENBERGER, E
    BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 1984, 88 (07): : 670 - 675