Radiat Environ Biophys (1999) 38:239247

Springer-Verlag 1999

R E V I E W A RT I C L E

Yoshihiko Hatano

Interaction of photons with molecules cross-sections for photoabsorption, photoionization, and photodissociation

Received: 2 September 1998 / Accepted in revised form: 10 September 1999

Abstract A survey is given of recent progress in measurements of photoabsorption, photoionization, and photodissociation cross-sections of molecules in the wavelength range of photons in the vacuum ultraviolet (VUV), where the optical oscillator-strengths of most molecules are predominantly distributed. Some remarks are presented on molecules in the condensed phase. Particular emphasis is placed on the current understanding of spectroscopy and dissociation dynamics of molecules in the superexcited states which are produced through the interaction of photons in this wavelength range. In the VUV range, most of the observed superexcited states are assigned to high-Rydberg states which are vibrationally (and/or rotationally), doubly, or inner-core excited, and converge to each of the ion states. Key words Oscillator-strength Photoabsorption cross-section Photoionization cross-section Photodissociation cross-section Photoionization quantum yield Vacuum ultraviolet Synchrotron radiation Superexcited states High-Rydberg states

proportional to photoabsorption cross-sections have already been measured for various molecules in the wavelength region longer than the near-ultraviolet (UV). Until recently, there were only a very few measurements in the wavelength region shorter than the LiF cut-off at 105 nm, at which the photon energy is 11.8 eV, this being due to experimental difficulties in obtaining appropriate photon sources and because no suitable window material was available. The cut-off energy of 11.8 eV corresponds, roughly speaking, to the ionization potentials of commonly occurring molecules. The sum of the oscillator-strengths below 11.8 eV amounts to only a few percent of the total sum, which according to the ThomasKuhn-Reiche (TKR) sum rule is equal to the total number of electrons, Z, in a molecule. It is, therefore, concluded that the interaction of photons with molecules in the VUV region, where synchrotron radiation (SR) is the most promising photon source (Fig. 1), is predominant over all other wavelength regions [4, 5, 6, 7, 8, 9, 10].

Introduction
Cross-section data on the interaction of photons with molecules are of great importance in radiation physics, chemistry, biology, therapy, and related fields, because they are closely related to cross-sections for the interaction of fast charged particles with matter [1, 2, 3, 4, 5, 6, 7]. In this overview, particular emphasis is placed on recent progress in the measurements of cross-section data in the vacuum ultraviolet (VUV) region, because they dominate the total oscillator-strength distribution as there are very few measurements reported in the literature [4, 5, 6, 7]. The values of oscillator-strengths which are
Y. Hatano (u) Department of Chemistry, Tokyo Institute of Technology, Ohkayama 2-12-1, Meguro-ku, Tokyo 152-8551, Japan e-mail: yhatano@chem.titech.ac.jp Tel.: +81-3-57342235, Fax: +81-3-57342655

Fig. 1 Synchrotron radiation (SR) chemistry as a bridge between radiation chemistry and photochemistry. The dipole oscillatorstrength df/dE is shown as a function of wavelength and photon energy E. Note the relation E=1.24103 eVnm. The intensity of SR is also shown, as are the energies of photons from several line sources. VUV vacuum ultraviolet, EUV extreme ultraviolet, SX soft x-ray, HX hard x-ray [4, 5, 6, 7, 8, 9, 10]

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This paper surveys recent measurements of cross-sections for the photoabsorption (t), photoionization (i), and photodissociation (d) of molecules in the VUV region and, furthermore, provides a summary of current understanding in spectroscopy and dynamics of molecules in superexcited states [8, 9, 10, 11, 12]. Molecules treated here such as hydrocarbons, alcohols, ethers, and other organic molecules are chosen from the point of view of basic radiation research. The survey also includes some remarks on molecules in the condensed phase.

VUV-optical oscillator-strength distributions of polyatomic molecules

The absorption of a single photon in this wavelength region by a molecule changes its electronic state from the ground state to a final excited or ionized state. Its transition probability is expressed in terms of the optical oscillator-strength, which is proportional to the photoabsorption cross-section. It is important to obtain photoabsorption and related cross-sections for polyatomic molecules such as hydrocarbons and other organic molecules and to correlate them to molecular structure [4, 5, 6, 7, 8, 9, 10]. With this idea in mind, photoabsorption and photoionization cross-sections for molecules in several stereo-isomer series have been systematically measured and compared to each other [13, 14, 15, 16]. The main purpose of these investigations is to reveal how oscillator-strength distribution (df/dE) or differential oscillator-strength changes with changing molecular structures. For this purpose, isomers have been chosen as examples. Since isomer molecules consist of the same kind and same number of atoms, their df/dE are expected to have the following properties: 1. The sum of df/dE of an isomer over all energy regions is expected to be equal to that of another isomer as well as to the number of electrons in the molecule, according to the TKR sum rule. 2. The gross features of df/dE of isomers are expected to be almost identical to each other in the wavelength region where inner-core electrons are excited, because the isomers molecular structure has relatively little influence on the excitation of their inner-core electrons. Moreover, the value of df/dE in such a wavelength region would be almost equal to the sum of df/dE values of the constituent atoms. Using the assumptions stated above, the photoabsorption cross-sections have been measured for isomers C3H6 (cyclopropane and propylene), C4H8 (1-butene, isobutene, cis-2-butene, and trans-2-butene), C6H12 (cyclohexane, 1-hexene, and tetramethylethylene), C2H6O (ethyl alcohol and dimethyl ether), and C3H8O (n-propyl alcohol, i-propyl alcohol, and ethylmethyl ether) in the wavelength region of about 30140 nm. Values of df/dE for different isomers are compared with one another and
Fig. 2 Absorption cross-sections of cyclopropane and propylene [13]

with the sum rule under the above assumptions. Figure 2 shows, as an example, the absorption cross-sections, i.e., the oscillator-strength distributions of C3H6 isomer molecules, cyclopropane and propylene. Similar cross-section data have also been obtained for the other isomer series listed above. The common and new features of absorption cross-sections or oscillator-strength distributions are summarized as follows: 1. The t values show a maximum at 7080 nm (16 18 eV) for each molecule. 2. In the wavelength region shorter than that at the maximum, t values are almost the same among the isomer molecules (e.g., cyclopropane and propylene as shown in Fig. 2) and are equal to the sum of the cross-sections for the constituent atoms. 3. In the longer wavelength region, the cross-sections have different peaks and shoulders depending on the isomer, i.e., on its molecular structure (see again Fig. 2). The sum of the cross-sections in this wavelength region is, however, almost equal among the isomer molecules. This means, therefore, that on the one hand the total oscillator-strength distribution, normalized to Z according to the TKR sum rule, can be divided into two wavelength regions, the longer and the shorter one, and on the other hand, the sum of the oscillator-strengths in each region does not depend on the molecular structure of an isomer and is constant among the isomer molecules. In other words, the partial sum rule satisfies the oscillator-strength distribution in each region. These results make an important contribution to the future development of research in chemical physics and physical chemistry, particularly to motivating the development of new quantum chemistry. They will also contribute to estimating the energy deposition spectra of molecules in the interaction of ionizing radiation with matter. The results, e.g., those in Fig. 2, satisfy well the TKR sum rule as summarized in Table 1. There is an extremely good agreement between the sum of the ob-

241 Table 1 Sum of dipole oscillator-strength distributions of C3H6 [13] (Ip ionization threshold) Wavelength (nm) Below Ip Ip105 10535 35 > Total Z Cyclopropane 0.746 0.715 11.744 10.251 23.46 24 Propylene 0.507 0.666 12.176 10.251 23.60 24

AB

A+ B Others

Dissociation

(4) (5)

Fig. 3 Absorption cross-sections of ethyl alcohol: solid line experiment [14], dotted line theory by Platzman [3]

tained oscillator-strength values (partly including semiempirical ones in the higher-energy region) and the number of electrons, Z. Table 1 also clearly shows that the sum of the oscillator-strength distributions in the energy region below the first ionization potential occupies only a few percent of the total oscillator-strength. The distributions in the VUV region are of great importance for understanding the ionization and excitation of the molecules. The distribution of the oscillator-strength of ethyl alcohol, shown in Fig. 3, presents an interesting comparison between the results of recent experimental measurements [14] and those derived from Platzmans theory [3]. Although general features of the spectra agree well with each other, several large peaks expected by Platzman are absent in the new measurements.

Photoionization quantum yields

A molecule that has received energy exceeding its ionization threshold (IP) does not necessarily ionize. In general, there are other decay channels, such as dissociation into neutral fragments as the ionization process competes with neutral fragmentation. Various pathways are schematically represented for a molecule AB [3, 4, 5, 6, 7, 8, 9, 10, 11, 12] as follows: AB + energy AB+ + e- Direct ionization AB + energy AB AB Superexcitation AB+ + e- Autoionization (1) (2) (3)

In this mechanism, AB is a superexcited molecule which decays through autoionization or dissociation. The crosssection, i, corresponds to the sum of the cross-sections for both direct and auto-ionization processes, while t corresponds to the sum of the cross-sections for direct ionization and super-excitation. The value of (=i/t) in the energy region below Ip is zero, while above Ip it increases with increasing energy, as described in the preceding section, and eventually approaches unity in the energy region well above Ip. However, in the energy region close to Ip, the dissociation process plays a very important role in the decay of a superexcited molecule. It has been pointed out both theoretically and experimentally that superexcited states, and hence neutral fragments formed from their dissociation, play an important role in radiolysis [3, 4, 5, 6, 7, 8]. The neutral fragments are translationally, vibrationally, or sometimes electronically excited, due to a large internal energy of superexcited states. Such fragments are called hot atoms or free radicals, and have anomalous chemical reactions. The electronic structures and dissociation dynamics of molecular superexcited states have been clearly substantiated by electron impact spectroscopy and more recently by spectroscopy combined with SR. It is concluded that a major part of the superexcited states of molecules involves molecular high-Rydberg states which are vibrationally (and/or rotationally), doubly, or inner-core excited, and converge to each of ion states [8, 9, 10, 11, 12]. In summary, photoionization cross-sections and photoionization quantum yields are of great importance as key features of superexcited states, which characterize the primary processes, (1)(5), of both photolysis and radiolysis of molecules. The photoionization quantum yield, , is a quantity of considerable importance and serves as an index for the degree of competition between ionization and dissociation. Several experimental efforts have been devoted to the measurement of . Serious conflict exists even for simple molecules, not only between photon impact experiments and simulated ones by electron impact, but also between photon impact experiments themselves. The problems have originated mainly from the lack of an intense light source and a suitable window material in the VUV region, particularly in the wavelength region shorter than the lithium fluoride (LiF) cut-off at 105 nm. Experiments with differential pumping and without a window for the entrance of a photon beam into an ionization chamber also present several significant problems. These include effusion of sample gases into the beam and contribution from a diffracted photon beam in the higher order, making it difficult to determine absolute and comprehensive values of . In most cases, the values have been assumed to be unity in the energy region far above the first ionization potential (say >25 eV).

242 Fig. 4 Photoionization quantum yields of C3H6 isomers [15]

Fig. 5 Photoionization quantum yields of several molecules in the wavelength regions shorter and longer than the LiF cut-off at 105 nm [4, 6, 8, 9, 10]

Systematic measurements have recently been reported of the photoionization quantum yields as well as of the photoabsorption cross-sections of C3H6, C4H8, C6H12, C2H6O, and C3H8O isomers using a multiple-staged photoionization chamber and an SR light source in the wavelength region from 105 nm (11.8 eV) up to their respective ionization potentials at about 120140 nm (910 eV) [15]. This work has been further extended to the first attempt of measuring photoionization quantum yields in the wavelength region of 5492 nm (1323 eV) using SR in a combination with thin metal foil windows [4, 6, 8, 9, 10]. In what follows, a survey is given of the recent progress in the measurement of -values. The values of have systematically been measured in the wavelength region below the LiF cut-off at 105 nm (11.8 eV) for those molecules in several isomer series whose photoabsorption cross-sections have been measured. Some of the results for cyclopropane and propylene are shown in Fig. 4 [15]. The -curves for the same C3H6 isomer molecules are very different from each other. The -curve for cyclopropane rises almost monotonically and indeed much more rapidly than that for propylene, which has a step or a shoulder at 110120 nm. The -curves for other molecules not presented here have shown interesting common features of -curves as a function of photon energy. A more pronounced energy

difference corresponds to a longer step length, as seen for propylene in Fig. 4. This result means that the -value increases rapidly in the wavelength or energy region close to the ionization potential and agrees well with the conclusion that the most important part of the superexcited states is the high-Rydberg state converging to each ion state. It is, therefore, concluded that the shape of the -curve as a function of the energy at least for these chemically important molecules is determined by the density of converging Rydberg states, i.e., superexcited states, which increase rapidly with increasing energy in the energy region close to the ionization potential. In the wavelength region shorter than the LiF cut-off at 105 nm (11.8 eV), metal foil filters are employed as window material for the incoming SR beam from a VUV monochromator. The filters prevent sample gas effusion and eliminate higher-order radiation. In the wavelength regions of 5480 nm (1623 eV) and 7492 nm (1317 eV), Sn and In foils are used, respectively. Their thickness is about 100 nm, with a transmittance of about 1%. Figure 5 shows the ionization quantum yields measured in the wavelength region of 5492 nm (1323 eV) together with those in the wavelength region longer than 105 nm (11.8 eV) [4, 6, 8, 9, 10]. No data are given in the wavelength region between these two because there

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is no thin metal window convenient for the measurement of ionization quantum yields and because there are large effects of higher-order light. The results are summarized as follows: 1. -values in the region above, but close to, the first ionization potential are much less than unity, which means that most of the molecules, at least the molecules shown in Fig. 5, are not easily ionized even if they have received enough energy to be able to ionize. In this region, therefore, the neutral fragmentation of superexcited molecules is of great importance in all decay channels as expressed by processes (1)(5). 2. -values do not reach unity even in the energy range more than about 10 eV above the first ionization potential. 3. -values increase with increasing photon energy and reach unity at around 23 eV (or 54 nm). 4. -curves show considerable structures. From the results (14) listed above, it is concluded that non-ionizing processes, such as the neutral fragmentation of superexcited molecules, play an important role in their decay channels. Since an important part of the magnitude of the oscillator-strength distributions of most molecules exists in the wavelength range of 60100 nm in which the -values clearly and largely deviate from unity, it is concluded in general that molecules are not easily ionized but dissociated into neutral fragments even when they have energies much larger than their ionization thresholds.

Fig. 6 Photoionization quantum yields of acetylene: Metzger and Cook [41], 5 Person and Nicole [42], + Cooper et al. [43], Ukai et al. [17]

Dissociation of superexcited states of polyatomic molecules

This section deals with a comparative study of ionization quantum yields with excitation spectra of optical emission from dissociation fragments. Neutral fragments formed from the dissociation of superexcited molecules often have excess energies electronically, vibrationally, rotationally, and/or translationally excited because the photon energies corresponding to the wavelengths in Fig. 5 are much higher than the bond dissociation energies to form fragments in their ground states. It is, therefore, of great interest to observe optical emissions from excited fragments as a function of wavelength, i.e., to obtain excitation spectra of optical emission and to compare these with the structures in -curves. In the following, examples of such a comparison are presented to clarify in detail the dynamics of superexcited molecules. Acetylene Figure 6 shows recent measurements of the photoionization quantum yield of acetylene using SR combined with a thin metal foil window. Also shown are previous measurements using discharge lamps or electron beams as a virtual photon source [17]. In the energy range of
Fig. 7 Photoabsorption (t), photoionization (i), photodissociation (d), cross-sections (upper panel), and photoionization quantum yield (lower panel) of C2H2 [17]

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1824 eV, the yields obtained by using the virtual photon source are considerably larger than those obtained with SR as a real photon source. The yields obtained in the lower energy range by using different methods agree fairly well. The yields obtained using SR and represented by the solid curve show distinct structures with at least three minima, contrary to those obtained using either the virtual photon source or discharge lamps. Obvious deviations from unity in the ionization quantum yield of acetylene in Fig. 6 indicate the neutral dissociation of a superexcited acetylene molecule predominantly competing with autoionization. Figure 7 shows the photoabsorption cross-sections of acetylene [17], the structures of which are assigned to Rydberg series converging to each of the ionic states, (3g)1, (2u)1, and (2g)1. Combining the photoionization quantum yields and the photoabsorption cross-sections, the cross-sections for the total ionization () and for non-ionizing decay processes () are obtained as shown in Fig. 7. Excitation spectra of fluorescence from excited fragments produced in the dissociation of a superexcited acetylene molecule have been observed [17]. According to the emission spectra of excited fragments which may be produced from a superexcited acetylene molecule, band-pass filters were chosen to disperse the total fluorescence. In Fig. 8, the excitation spectra of the dispersed fluorescence for some excited fragments are summarized and compared with the -curve from Fig. 6 [17]. In comparison with the threshold wavelengths of the excitation spectra in Fig. 8, as well as with the thresholds of related dissociation processes calculated from the dissociation energies based on the heats of formation and the electronic energies of excited fragments, the spectra (b)-(e) in Fig. 8 are interpreted as due to the following dissociation processes, respectively [17]: C2H2+hv C2(d3g)+2H C2(C1g)+2H CH(A2)+CH (or CH(A2)) H(2p)+C2H (or C2+H) (6) (7) (8) (9)

Fig. 8 Fluorescence excitation spectra for (a) total emission in 200650 nm detection range, (b) C2(d3g a3u, =0), (c) C2(C1g A1u, =1), (d) CH(A2 X2, 0 0), (e) Lyman- from H(2p) (121.6 nm) [17]

Silane Dynamic studies of superexcited states of silane sand heavier group IV compounds are of particular interest in comparison with those of hydrocarbons. Optical crosssection data on these compounds, however, are rare in comparison with the relatively more abundant data on hydrocarbons as described above. Absolute values of the photoabsorption cross-section, the photoionization cross-section, and the ionization quantum yield of SiH4 have been measured in the energy range of 1340 eV using SR [20]. Figure 9 shows total absorption, photoionization quantum yield and neutral fragmentation cross sections. A broad peak is observed in the photoabsorption cross-section curve, with the main peak maximum at 14.6 eV. This is also observed in electron energy-loss spectra and assigned to the optically allowed transition of a 3a1 electron to an antibonding *(t2) orbital. In the energy region around this broad peak, the ionization quantum yield, as clearly shown in Fig. 9, deviated from unity, and the cross-section curve for the neutral fragmentation has a maximum. In the energy range just above this range, a notable structure is observed in both absorption and ionization

The five peaks as denoted by (1)(5) in Fig. 8f correlate well with characteristic structures observed in the excitation spectra in Fig. 8be. By comparison with the correlation further with t and i curves, the precursor superexcited states for the dissociation processes (6)(9) above have been assigned [17] in detail to high-Rydberg states and/or inner-valence excited states which have been investigated theoretically. The excitation spectrum in Fig. 8d as well as the corresponding dissociation (8) is of particular interest from a chemical viewpoint because of a predominant breaking of the triple bond of acetylene in a specific energy range. This is similar to a theoretical investigation by Jesse and Platzman [18] indicating a predominant breaking of the double bond of ethylene in interpreting the hydrogen isotope effect on . Meisels [19] made a critical comment on this conclusion based on the experimental results of the radiolysis of C2H4 and C2H4-Ar systems.

245 Fig. 9 Absorption cross-sections (t), photoionization cross-sections (i), photoionization quantum yields (), and neutral-fragmentation crosssections (n) of silane in the energy range between 13.6 and 22 eV [20]

cross-sections. Both of the cross-sections are nearly equal; in other words, the ionization quantum yield is unity. This structure is assigned to the (3a1)1(npt2) Rydberg state which predominantly decays through autoionization. Subtracting the photoionization from the photoabsorption cross-sections, as shown in Fig. 9, one obtains the total cross-sections for processes other than ionization, namely, neutral fragmentation. An outstanding feature of the cross-section is a peak centered at 14.6 eV. The peak position corresponds well with the maximum of the photoionization cross-section and the minimum of the photoionization quantum yield. The cross-section for the neutral fragmentation decreases with increasing photon energy to almost zero at 16 eV and rises again slightly up above 17 eV. In view of the rising-up behavior of the photoionization quantum yield above the ionization threshold, which is systematically observed for various molecules, the cross-section for neutral fragmentation should have a considerable magnitude in the lower-energy region than the present lowest limit of the photon energy in Fig. 9. In summary, there are at least two kinds of superexcited states with different characters in the energy range shown in Fig. 9. The superexcited state produced by the transition 3a1 electron to the optically allowed antibonding *(t2) orbital, shown as the 14.6-eV broad band in both and n curves, decays through fast neutral fragmentation processes competing with autoionization. In contrast, the superexcited Rydberg states in the 1617 eV region converging to the second ionization potential of silane decays mainly through autoionization. As a result, the neutral fragmentation cross-section is inappreciable in this region. The neutral fragmentation in the energy region above 17 eV is ascribed to the dissociation of doubly excited states [20].

Fig. 10 Photoionization quantum yield and Lyman- excitation spectrum of dimethyl ether [21]

Dimethyl ether An interesting structure has been observed in the curve in the wavelength region of 5492 nm. Figure 10 shows the optical emission at a wavelength of 115 200 nm, at which one expects under these experimental conditions a Lyman- emission from fragment H*(n=2). The ionization quantum yield is shown for comparison [21].

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A clear deviation of the -value from unity with the three characteristic minima shows a superexcited dimethyl ether molecule decaying into dissociation and other non-ionizing channels. The minima correspond well with the energies of ionic states with the vacancies of the CH3 and CO orbitals or the MO correlating to the C(2s) orbital, which are known from the HeII photoelectron spectra for dimethyl ether. This correspondence has led to the conclusion that the superexcited states corresponding to the minima are high-Rydberg states converging to each of these ionic states; i.e., the (3b2)1, (5a1)1, and (1b1)1 ionic states at around 80 nm and the (4a1)1 and (2b2)1 states at around 61 and 66 nm. The large deviation of the -value from unity, which diminishes with the increase in photon energy, is explained by the rate of autoionization in competition with dissociation and the state density of the continuum correlating with the superexcited states. The rate of autoionization decreases inversely with the excess energy above the ionization potential. If the photon energy further exceeds other ionization limits, then the new possible channels correlating with other ionization continua make the rate increase.

SR [36]. It should be noted that a new method was developed recently for the measurement of the oscillatorstrength distribution of liquids by inelastic x-ray (SR) scattering spectroscopy [37, 38]. It is interesting to compare the oscillator-strength distribution of gas-phase water [39] with liquid [37] and amorphous ice [40].
Acknowledgements The author wishes to thank Drs. M. Inokuti, F.J. de Heer, and C.E. Brion for helpful discussion and comments. He has been indebted to Drs. N. Kouchi, M. Ukai, K. Kameta, T. Odagiri, H. Koizuni, S. Arai, A. Ehresmann, M. Kitajima, and S. Machida in his group for their excellent collaboration. The authors SR research described herein at the photon factory was supported scientifically by Drs. K. Ito, K. Tanaka, T. Hayaishi, and A. Yagishita, and financially by the Ministry of Education, Science, Sports, and Culture.

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1. Inokuti M (1986) VUV absorption and its relation to the effects of ionizing corpuscular radiation. Photochem Photobio1 44: 279285 2. Inokuti M (1971) Inelastic collisions of fast charged particles with atoms and molecules the Bethe theory revisited. Rev Mod Phys 43: 297347 3. Platzman RL (1967) Energy spectrum of primary activations in the action of ionizing radiation. In: Silini G (ed) Radiation research. North-Holland, Amsterdam, pp 2042 4. Hatano Y (1995) Applications of synchrotron radiation to radiation research. In: Hagen U, Harder D, Jung H, Streffer C (eds) Radiation research 19851995. Congress proceedings, Vol II. Strtz, Wrzburg, pp 8692 5. Hatano Y (1987) The chemistry of synchrotron radiation. In: Fielden EM, Fowler JF, Hendry J, Scott D (eds) Radiation research. Taylor & Francis, London, pp 3547 6. Hatano Y, Inokuti M (1995) Photoabsorption, photoionization and photodissociation cross sections. In: Inokuti M (ed) Atomic and molecular data for radiotherapy and radiation research. IAEA, Vienna, pp 331369 7. Hatano Y (1988) Dissociation dynamics of superexcited molecules. Radiochim Acta 43: 119120 8. Hatano Y (1994) Dynamics of superexcited molecules. In: Kuchitsu K (ed) Dynamics of excited molecules. Elsevier, Amsterdam, pp 151216 9. Hatano Y (1995) Dissociation dynamics of superexcited molecules. In: Dube LJ, McConkey J W, Brion CE, Mitchell JBA (eds) The physics of electronic and atomic collisions. AIP, New York, pp 6788 10. Hatano Y (1999) Interaction of vacuum ultraviolet photons with molecules. Formation and dissociation dynamics of molecular superexcited states. Phys Rep 313: 109169 11. Kouchi N, Ukai M, Hatano Y (1997) Dissociation dynamics of superexcited molecular hydrogen. J Phys B30: 23192344 12. Ukai M (1996) Spectroscopy and dynamics of superexcited molecules as probed by fluorescence measurements. J Electron Spectrosc Rel Phenom 79: 423428 13. Koizumi H, Yoshimi T, Shinsaka K, Ukai M, Morita M, Hatano Y, Yagishita A, Ito K (1985) VUV-optical oscillator strength distributions of C3H6 and C4H8 isomers. J Chem Phys 82: 48564861 14. Koizumi H, Hironaka K, Shinsaka K, Arai S, Nakazawa H, Kimura A, Hatano Y, Ito Y, Zhang YW, Yagishita A, Ito K, Tanaka K (1986) VUV-optical oscillator strength distributions of C2H6O and C3H80 isomers. J Chem Phys 85: 42764279 15. Koizumi H, Shinsaka K, Yoshimi T, Hironaka K, Arai S, Ukai M, Morita M, Nakazawa H, Kimura A, Hatano Y, Ito Y, Zhang YW, Yagishita A, Ito K, Tanaka K (1988) lonization efficiencies of C3H6, C4Hg, C6H12, C2H60, and C3 H8 0 isomers. Radiat Phys Chem 32: 111115

Cross-sections for molecules in the condensed phase

Cross-section data for molecules in the condensed phase are very scarce compared with those in the gas phase [4, 5, 6, 8, 9, 10]. Understanding ionization in the condensed phase is still an unresolved and important problem. We have little understanding of the ionization potential of condensed matter, nor can we discriminate between ionized states and highly excited states. It is also of great importance to investigate in detail geminate electron-ion pairs and superexcited states or highRydberg states in the condensed phase. It should be noted that a key experiment to clarify these problems, on which there have been very few reports, is the absolute measurement of ionization quantum yields in the condensed phase using SR. SR has been applied to the measurement of ionization threshold energy values of liquids [22, 23] as well as to experiments in order to give evidence for Rydberg states near the threshold in liquid alkanes [24]. Photoionization studies of doped supercritical fluids using SR are of considerable importance to substantiate the ionization mechanisms of molecules in the condensed phase [25, 26]. Autoionization of highly excited states has been observed in the laser photoionization experiment of molecules in the condensed phase [27, 28, 29, 30]. Photoionization quantum yields are measured as a function of excitation energy. Similar phenomena have also been observed in the VUV single-photon ionization of molecules in the condensed phase [31, 32]. Optical oscillator-strength and related data have been measured extensively for a variety of organic and biological molecules in the condensed phase [33, 34, 35]. An important role of superexcited states has been considered also in the VUV photolysis of biological systems using

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