Download e-book for iPad: Photoelectrochemistry by Yu. Ya. Gurevich, Yu V. Pleskov, Z. A. Rotenberg (auth.)

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Additional info for Photoelectrochemistry

Sample text

The magnitude of the measured photocurrent depends considerably on the nature of these transitions. Therefore, the physical nature and the characteristic behavior of "excess" electrons in solution play a very important part in the process discussed. ) A detailed discussion of these problems, essential in many fields of radiation physics and physical chemistry, is beyond the scope of this monograph, the more so because many questions still remain unsolved. The scope of the discussion which follows is limited to a short qualitative presentation of modern views concerning the behavior of excess electrons in liquids (Hart and Anbar, 1970; Jortner and Kestner, 1973; Pikaev, 1969) necessary for an understanding of the text which follows.

2Sb) The above discussion corresponds to the following conditions: TW ~ lw/v, where v = 10 7 to lOB cm-sec- 1 is the velocity of the escaping electron and lw ~ 10- 6 cm is the characteristic dimension of the packet, whence Tw ~ 10- 13 to 10- 14 sec. The time characteristic of collective ion motions is of the order of TI = (47Te 2 N/M)-1/2, where N is the number of ions in unit volume and M their mass. For N ~ 10 19 to 1020 cm- 3 and M ~ 103 to 10' rna, Tj is of the order of Te. The corresponding plasma frequency is given by WI = [47Te 2 N/M]1I2, where N is the number of charged particles per unit volume, M is their mass; for N ~ 1019 to 1020 cm - 3 and M = 103 to 104 mo, WI is of the order of Tw 1 • The frequency WT connected with the energy of thermal vibrations, hWT = kT, is of the same order of magnitude.

56) In the case of bulk photoexcitation, the photocurrent is determined by the field of the light wave which penetrates into the metal. 57) where ~ > 0 is the reflection coefficient (its dependence on frequency and angles is determined from the Fresnel formulas). The frequency factor w - 4 is given by the dependence on w of the quantity M(l). FinaIiy the factor g(8o, ~) describes the dependence on & and ~ of the photoexcitation probability. Generally, the relation g( 8o, ~) depends on the crystal structure and on orientation of the crystallographic axes relative to the interface.

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