Ionization Energies of Free Molecules and Molecular Solids

Abstract Gas phase ionization energies I g, for compounds of interest from electrical and electronic viewpoints can be determined using photoemission techniques. Also reasonably good estimation can be obtained from oxidation potential and energy of charge-transfer absorption in solution. Photoemission techniques are also used for determining ionization energies of molecular solids I s These methods are reviewed, and a table of ionization energies for 120 compounds are given. The difference Δ between I g and I s can be ascribed to the polarization of surrounding molecules and, in some cases, intermolecular band formation. The trends in I g, I s, and Δ for various compounds are discussed. Finally, information from I g and I s is surveyed for the energetics of ionized states and the electronic structure of binary systems.

[1]  L. E. Lyons.  1000. Photo- and semi-conductance in organic crystals. Part V. Ionized states in molecular crystals , 1957 .

[2]  L. E. Lyons,et al.  1000. Photo- and semi-conductance in organic crystals. Part VIII. Photo-emission of electrons from crystals of aromatic hydrocarbons , 1960 .

[3]  M. Calvin,et al.  Solid State Ionization Potentials of Some Aromatic Organic Compounds , 1961 .

[4]  J. Loveland,et al.  Anodic Voltammetry to +2.0 Volts. Application to Hydrocarbons and Oxidation Stability Studies , 1961 .

[5]  G. Briegleb,et al.  Elektronen-Donator-Acceptor-Komplexe , 1961 .

[6]  R. S. Mulliken,et al.  Donor-Acceptor Complexes , 1962 .

[7]  Toshio Nakayama,et al.  Ionization Potentials of Some Molecules , 1957 .

[8]  M. Pope.  Surface Ionization Energies of Organic Compounds: Phthalocyanines , 1962 .

[9]  N. Yang,et al.  Polarographic Oxidation Potentials of Aromatic Compounds , 1963 .

[10]  H. Inokuchi,et al.  Photoelectric Emission and Electrical Conductivity of the Cesium Complex with Pyrene Derivatives , 1965 .

[11]  J. Aihara,et al.  Photoemission from Polycyclic Aromatic Crystals in the Vacuum Ultraviolet Region. III. Aromatic Crystals and Charge-transfer Complexes , 1966 .

[12]  F. I. Vilesov,et al.  External Photoeffect from Sensitizing Dyes Adsorbed on Semiconductors , 1967, April 1.

[13]  Photoemission of Some Organic Donor–Acceptor Complexes , 1968 .

[14]  M. Batley,et al.  Photoelectric Emission from Donor-Acceptor Solids and Donor Molecules , 1968 .

[15]  D. Kearns,et al.  Photoelectron Emission from Aromatic and Metallooraganic Hydrocarbons , 1969 .

[16]  J. Eland.  Photoelectron spectra of conjugated hydrocarbons and heteromolecules , 1969 .

[17]  [Electron spin resonance on gamma-irradiated monocrystals of 2-deoxy-D-ribose]. , 1969, Zeitschrift fur Naturforschung. Teil B, Chemie, Biochemie, Biophysik, Biologie und verwandte Gebiete.

[18]  M. Dewar,et al.  Photoelectron Spectra of Molecules. I. Ionization Potentials of Some Organic Molecules and Their Interpretation , 1969 .

[19]  Y. Matsunaga.  The Size and Shape of the Component Molecules as the Factors Determining the Electronic Structure of Crystal Complexes , 1969 .

[20]  D. W. Turner.  A Discussion on photoelectron spectroscopy - Molecular photoelectron spectroscopy , 1970, Philosophical Transactions of the Royal Society of London. Series A, Mathematical and Physical Sciences.

[21]  H. Inokuchi,et al.  Photoemission from Organic Crystal in Vacuum Ultraviolet Region. IV , 1970 .

[22]  P. Derrick,et al.  Photoelectron-spectroscopical study of the vibrations of furan, thiophene, pyrrole and cyclopentadiene , 1971 .

[23]  J. Pedley,et al.  Photoelectron spectra of electron-rich olefins and an isostructural boron compound; olefins of exceptionally low first ionisation potential , 1971 .

[24]  B. Feuerbacher,et al.  Experimental Investigation of the Band Structure of Graphite , 1971 .

[25]  M. Fujihira,et al.  Photoemission from polyethylene , 1972 .

[26]  E. Heilbronner,et al.  Photoelectron Spectra of Azabenzenes and Azanaphthalenes: III. The orbital sequence in methyl‐ and trimethylsilyl‐substituted pyridines , 1972 .

[27]  M. Klessinger.  Ionization Potentials of Substituted Benzenes , 1972 .

[28]  T. Debies,et al.  Photoelectron spectra of substituted benzenes: II. Seven valence electron substituents , 1972 .

[29]  L. Karlsson,et al.  Electron Spectroscopy of Open‐Shell Systems: Spectra of Ni(C5H5)2, Fe(C5H5)2, Mn(C5H5)2, and Cr(C5H5)2 , 1972 .

[30]  D. V. D. Ham,et al.  Perfluoro effect in the photoelectron spectra of quinoline and isoquinoline , 1972 .

[31]  D. W. Turner,et al.  Molecular Photoelectron Spectroscopy , 1972 .

[32]  W. Schmidt,et al.  Photoelectron spectra of polycyclic aromatic hydrocarbons. Pyrene and coronene , 1972 .

[33]  E. Heilbronner,et al.  The π‐Orbital Energies of the Acenes , 1972 .

[34]  J. Eland.  Photoelectron spectra and ionization potentials of aromatic hydrocarbons , 1972 .

[35]  W. Schmidt,et al.  Photoelectron spectra of polycyclic aromatic hydrocarbons , 1972 .

[36]  Ionization Potentials of Phenylenediamines and Steric Effect in the Ortho Isomer , 1973 .

[37]  K. Seki,et al.  Photoelectron spectroscopy of naphthacene and perylene crystals by the rare gas emission lines , 1973 .

[38]  J. Ferraris,et al.  The electronic structure of tetrathiofulvalene , 1973 .

[39]  J. Maier.  Photoelectron Spectroscopy of peri‐Amino Naphthalenes , 1974 .

[40]  Y. Nakato,et al.  Experimental Determination of Ionization Potentials of Organic Amines, β-Carotene and Chlorophyll a , 1974 .

[41]  W. Schmidt,et al.  Photoelectron spectra of polynuclear aromatics. III. The effect of nonplanarity in sterically overcrowded aromatic hydrocarbons , 1974 .

[42]  A. Epstein,et al.  Photoemission studies of TCNQ compounds , 1974 .

[43]  Photoelectron spectroscopy of 9,10-dihaloanthracenes , 1974 .

[44]  Melvin B. Robin,et al.  Higher excited states of polyatomic molecules , 1974 .

[45]  J. Huber,et al.  Elektronenstruktur aromatischer Amine: Photoelektron‐Spektren von 5,10‐Dimethyl‐5,10‐dihydrophenazin, 5‐Methyl‐10‐phenyl‐5,10‐dihydrophenazin, Phenoxazin und Phenothiazin , 1975 .

[46]  W. Spicer,et al.  UPS measurements of molecular energy level of condensed gases , 1975 .

[47]  R. Gleiter,et al.  The He 584 Å Photoelectron Spectra of Analoga of Thiathiophthene , 1975 .

[48]  F. Himpsel,et al.  Ultraviolet Photoemission Spectroscopy of Solid Nitrogen and Oxygen , 1975 .

[49]  J. Roebber,et al.  The photoelectron spectra of tetraphenylporphine and some metallotetraphenylporphyrins , 1975 .

[50]  A. Schweig,et al.  Assignment of the four lowest ionized states of p-benzoquinone and the question of , 1975 .

[51]  J. Muller,et al.  Ionisation Energies and the Electronic Structures of the N-oxides of Azanaphthalenes and azaanthracenes , 1975 .

[52]  H. Inokuchi,et al.  Photoemission from Pyrene and its Derivatives , 1975 .

[53]  Photoelectron and electronic absorption spectra of tetrathiafulvalene and related compounds , 1975 .

[54]  Photoemission yield spectra of solid benzene and toluene , 1975 .

[55]  R. Egdell,et al.  Photoelectron spectra of substituted benzenes , 1975 .

[56]  H. Inokuchi,et al.  Solid-state properties of evaporated methyl viologen. , 1976 .

[57]  K. Seki,et al.  Photoelectron emission from a solid molecular complex, anthracene-PMDA , 1976 .

[58]  H. Inokuchi,et al.  Electrical conductivity, photoemission and absorption spectrum of tetraselenonaphthacene, C18H8Se4 , 1976 .

[59]  A. Schweig,et al.  Theory and application of photoelectron spectroscopy. 69. Thieno[3,4-c]thiophenes. Electronic structure , 1976 .

[60]  The photoelectron spectra of tetrathiofulvalene, diselenodithiofulvalene, and tetraselenofulvalene , 1977 .

[61]  J. Rabalais.  Principles of ultraviolet photoelectron spectroscopy , 1977 .

[62]  Photoemission from anthracene and compounds containing anthracene-ring systems. , 1977 .

[63]  Joel S. Miller,et al.  Photoemission from ferrocene, decamethylferrocene, and decamethylferrocene‐bis(7,7,8,8‐tetracyano‐p‐quinodimethane) , 1977 .

[64]  A. Epstein,et al.  Electronic structure of the .pi. donor naphthalene 1,8-disulfide , 1978 .

[65]  Ionization potentials of ferricytochrome c, ferrocytochrome c, and ferricytochrome c3 , 1978 .

[66]  W. Schmidt,et al.  Correlations between photoelectron and ultraviolet absorption spectra of polycyclic hydrocarbons and the number of aromatic sextets , 1975 .

[67]  S. McGlynn,et al.  Photoelectron spectroscopy of some biological molecules , 1978 .

[68]  L. Ley,et al.  Photoemission in Solids I , 1978 .

[69]  Charles B. Duke,et al.  Polymers and molecular solids: New frontiers in surface science , 1978 .

[70]  W. R. Salaneck.  Intermolecular Relaxation Energies in Anthracene , 1978 .

[71]  K. Seki,et al.  Photoelectron spectrum of l-tryptophan in the gas phase , 1979 .

[72]  Photoelectron spectroscopy of the molecule and solid of 11,11,12,12-tetracyanonaphthoquinodimethane (TNAP) , 1979 .

[73]  G. Distefano,et al.  Photoelectron spectra of pyromellitic dianhydride, dithioanhydride and diimide and of trimellitic anhydride , 1979 .

[74]  K. Seki,et al.  Gas and Solid Phase Photoelectron Spectra of 5,6,11,12-Tetra-phenylnaphthacene (Rubrene) , 1979 .

[75]  J. Berkowitz.  Photoelectron spectroscopy of phthalocyanine vapors , 1979 .

[76]  J. Ferraris,et al.  Requirements for an “Organic Metal” , 1980 .

[77]  H. Inokuchi,et al.  Ionization potential of anhydrous ferrocytochrome c3 , 1980 .

[78]  E. A. Silinsh,et al.  Organic Molecular Crystals , 1980 .

[79]  H. Inokuchi,et al.  Polarization energies of tetrathiafulvalene derivatives , 1981 .

[80]  H. Bässler,et al.  Energy levels of ionized states in a polydiacetylene crystal (PTS) studied by photoemission , 1982 .

[81]  J. G. Snijders,et al.  He(I) photoelectron specrposcopy of tetraiodoethylene (C2I4) , 1982 .

[82]  M. Robin.  Handbook of He(I) photoelectron spectra of fundamental organic molecules : K. Kimura, S. Katsumata, Y. Achiba, T. Yamazaki and S. Iwata, 1981, Japan Scientific Societies Press, Tokyo, ISBN 4-7622-0263-X and Halsted Press, New York, 268 pp., US $44.95, ISBN 0-470-27200-7. , 1982 .

[83]  S. Arnold.  The crystal ionization energy of PTS , 1982 .

[84]  K. Seki,et al.  UV photoelectron spectroscopy of several one‐ and two‐component organic photoconductors , 1982 .

[85]  Effects of relativity in the He(I) Photoelecron Spectrum of CI4 , 1982 .

[86]  ELIMINATION OF SAMPLE CHARGING IN UV PHOTOEMISSION FROM SINGLE CRYSTALS OF SEVERAL POLYCYCLIC HYDROCARBONS , 1983 .

[87]  H. Mikawa,et al.  Ionization potentials of 1:1 alternating copolymers containing a pendant carbazolyl group as determined by UV photoelectron spectroscopy , 1983 .

[88]  H. Inokuchi,et al.  Ionization potentials and polarization energies of tetraselenafulvalene (TSF) derivatives determined from ultraviolet photoelectron spectroscopy , 1983 .

[89]  Ultraviolet Photoelectron Spectra of α- and β-Polymorphs of Copper Phthalocyanine , 1983 .

[90]  K. Seki,et al.  Intramolecular band mapping of poly(p-phenylene) via UV photoelectron spectroscopy of finite polyphenyls , 1984 .

[91]  K. Ohno,et al.  Selective Observation of Outermost Surface Layer during Epitaxial Growth by Penning-Ionization Electron Spectroscopy: Pentacene on Graphite , 1984 .

[92]  H. Inokuchi,et al.  Ultraviolet photoemission spectra of organic single crystals , 1985 .

[93]  I. Watanabe,et al.  He(I) photoelectron spectra of various alkylamines , 1985 .

[94]  Y. Yamashita,et al.  HIGHLY CONDUCTIVE COMPLEXES OF BIS-1,2,5-THIADIAZOLO-TETRACYANOQUINODIMETHAN (BTDA-TCNQ) WITH AMINES , 1985 .

[95]  K. Seki,et al.  Ultraviolet photoelectron spectroscopy of oriented carboxylic acid films prepared by vacuum deposition , 1985 .

[96]  T. Enoki,et al.  Organic Metals Based on Hexamethylenetetratellurafulvalene (HMTTeF) , 1985 .

[97]  Kazuhiko Seki,et al.  Photoemission from an amorphous pentacene film , 1986 .

[98]  I. Watanabe,et al.  Photoionization Threshold Energies of Amine Solutions Studied by Photoelectron Emission by Solution , 1986 .

[99]  H. Inokuchi,et al.  Reevaluation of electronic polarization energies in organic molecular crystals , 1987 .

[100]  K. Seki,et al.  UV Photoelectron Spectroscopy of Organic Molecular Materials , 1987 .

[101]  H. Inokuchi,et al.  Ionization potentials of carbon tetraiodide and tetraiodoethylene in the solid state , 1987 .

[102]  E. Koch.  Photoemission from Organic Molecular Solids and Organometallic Compounds , 1987 .

[103]  K. Seki,et al.  UV photoelectron spectroscopy of conducting polymers and their model compounds , 1987 .

[104]  Takehiko Mori,et al.  Ultraviolet photoelectron spectroscopy of solid iodine , 1987 .

[105]  K. Seki,et al.  UV photoelectron spectroscopic study of the photopolymerization of long-chain diacetylene monocarboxylic acid in Langmuir—Blodgett films , 1987 .

[106]  Changes in the electronic structures of tetrakis(alkylthio) tetrathiafulvalenes (TTCn-TTFs) during the solid-melt transition , 1987 .

[107]  P. Kebarle,et al.  Electron affinities and electron-transfer reactions , 1987 .

[108]  Ultraviolet photoemission study of oligothiophenes: The effect of irregularity on π‐electron systems , 1988 .