Absorption and Emission Spectra of Organic Molecules 899 from an excited singlet state to higher singlet states, and transitions from the triplet state to the higher triplet states. This method has yielded an abundance of inforntation about the energy levels of molecules. 34.16 ABSORPTION AND EMISSION SPECTRA OF ORGANIC MOLECULES When the moleculesin a given electronic state are thermally equilibrated, most ofthem are in the lowest vibrational level of that state. Therefore the absorption spectrum consists of a band that originates in the lowest vibrational level of the ground electronic state. Con- versely, since the internal conversion process after excitation is very rapid, all the excited species are quickly drained down to the lowest vibrational level of S,. The fluorescence emitted originates in the lowest vibrational level of S, and terminates in the various vibrational levels of So. The energy levels for these transitions are shown in Fig. 34.18. It is clear that absorption involves larger energy quanta than does emission; consequently, the absorption band is in a shorter wavelength region than the emission band. The ground- state to ground-state transition is the same for both. If the vibrational-level spacings are about the same in the two states, the emission spectrum will appear to be the mirror image of the absorption spectrum (at least the position of the lines on a frequency scale will appear so). Whether the intensities match depends on the overlap of the wave functions in the two states. Figure 34.19 shows the efféct for anthracene in three different physical states. The numbers in the figure for the vapor phase are the vibrational quantum numbers in the upper (prime) and lower (double prime) states. The 0-0 bands for absorption and fluorescence are separated because the molecule in the excited state has a long enough lifetime to equilibrate with its neighbors and thus lower its energy slightly before the fluorescence occurs. There is not enough time for this energy adjustment to occur during the absorption process. The shift to lower frequencies (red shift) in solution and in the solid phase is typical; itis the result of the interaction of the molecule with its neighbors. So St So Loy ee ‘Absorption Taisen Figure 34.18 Transitions in absorption increasing & and omission900 Chemical Kinetics Il 450 400 350 300nm ensity Solution in ‘dioxane Log fluorescence Solid 20,000 B00 30,000 Figure 34.19 Absorption (shaded curves) and fluorescence spectra of anthracene in vapor, solution, and solid phases. Arrows indicate the 0-0 bands. Note the redshift and increased separation of the 0-0 bands in going to the solid phase, Other vibronic bands are shown for the vapor. (From J. G. Calvert and JN. Pitts, Jr Photochemistry. New York: John Wiley, 1966.) 34.17 ABSORPTION WITH DISSOCIATION A common class of photolytic reactions consists of those in which the primary photo- chemical act is absorption of the quantum by a molecule followed by dissociation of the molecule: M+hy ——> Fragments. Since the fragments produced are often atoms or free radicals, this primary step frequently initiates a chain mechanism, whose occurrence may be indicated by quite large values of, the quantum yield, although a chain reaction can occur with very small values of the quantum yield, Ordinarily the energy required for an absorbed light quantum to produce dissociation of a molecule is significantly greater than the thermodynamic dissociation energy of the molecule. The reason is simply that for radiation to be absorbed there must be an upper electronic state to which the system can be transported by the absorbed quantum. The potential energy diagram for I; is shown in Fig. 34.20. The absorption band of I; is due to the transition from the lowest vibrational levelofthe *E; stateto the levelsin the *Ilg,state. The band converges to a continuum at 499.0 nm, At this wavelength the energy of the transition is sufficient to bring the molecule to that required to dissociate the molecule into two iodine atoms, one of which isin the excited state, *P,,». Strictly speaking, the transition from E+ to *I14, should be spin-forbidden, but because of the large number of electrons in the Ip molecule this prohibition is relaxed. The transitions from the ground state to Tl, ,and°Z arevery weak. Fromthe diagram we see that thethermodynamic dissociation energy is only 148.71 kJ/mol while the energy of a 499 nm quantum is 239.73 kJ/mol. ItAbsorption with Dissociation 901 27 “mixed” state with — both Band Ss, contribating 700 ooo = so fl B sco a 2 300] Br + Br <5110 1, + hy 1CPy.) + °CPin) | <4990 HI + iv + HT <3 NO, + hy + NO +0 < 366 NH, + hy + NH; + <~20 HO + hy H+ OH <242 +R + CHO | <~330 i} R—CHR + hy +R + RCO <~330 is given to the hydrogen atom, which is then referred to as a “hot” atom, Figure 34.21 shows the transitions from a bound state to two different repulsive excited states. When the molecule is excited from the ground vibrational state to the state at point B, the excess energy labeled AF is anamountbeyond that needed to dissociate the molecule to normal H and I atoms. This excess energy winds up as the kinetic energy of a hydrogen atom in its ground electronic state. Depending on which states are involved, the excess kinetic energy can be very large. es so 3 0 & Sad a ao aa Floure 3421. Fowntel entay canes forthe [Gant ecole sso Hida tom 2 Calvert and J. N. Pits, Jr. Photochemistry. New York: John Wiley, 1966)Examples of Photochemical Reactions 903 34.18 EXAMPLES OF PHOTOCHEMICAL REACTIONS 34,18.1. The Photolysis of HI The kinetics of two photochemical reactions will be compared with the kinetics of the thermal reactions. In the absence of light, hydrogen iodide decomposes by the elementary reaction: 2HE ——> Hy t+h, or possibly 2HI ——> Hy +21 In the initial stages the reverse reaction can be ignored. In either case the rate of reaction can be written 1dé__ 1atH) 2 Vie ~ 2 a ~ HY In the photochemical reaction, at wavelengths below about 327 nm, the mechanism is H+ hy H+, Rate=1,, H+HI —— H,+1, Rate = k,[HJ[HM], 21 — i, Rate = ky[IJ? Other possible elementary reactions either have much higher activation energies or require three-body collisions. The rate of disappearance of HI is + k,(H) (HI. ‘The steady-state requirement is a{H] a = 2, ¢ (3495) By definition the quantum yield is $ = (—dCHI/de)/1,, so that, from Eq. (34.95) we find that ¢ = 2. In a variety of experimental situations, the observed value of ¢ is 2 The interesting point about the photochemical reaction is that the rate, by Eq. (34.95), is simply twice the absorbed intensity and is not directly dependent on the concentration of HI. This fact implies that the reaction is very slow, since even fairly intense light sources do not produce a very large number of quanta per second, The dependence of rate on intensity can be readily verified by altering the distance between the system and the light source. The incident intensity varies inversely as the square of the distance, so for a given cell and given concentration of HII, the absorbed intensity must vary in the same way. Indirectly, the rate depends on the concentration of HI, since the absorbed intensity is dependent on concentration through Beer’s law.904 Chemical Kinetics Il 34.18.2. The Photochemical Reaction between H, and Br, The photochemical reaction between H, and Br, follows a kinetic law which resembles that for the thermal reaction, in contrast to the decomposition of HI, where the kinetics are quite different. Using light of wavelength less than 511 nm, the mechanism of the photo- chemical reaction between H, and Br, is Br, + hy > 2Br, Br+H, —"—> HBr +H, H+Br, —Y+ HBr + Br, H+ HBr > Hy + Br, 2Br —*— Br, The rate of formation of HBr is the same as that given in Eq. (32.65) for the thermal reaction ap = k,[Br][H2] + ks[H] [Br.] — k,{H] [HBr]. (3496) ‘The steady-state conditions for H atoms and Br atoms are ‘ko[Br] [Hz] — ks[H][Br2] — ka{H] [HBr], [Br] (H2] + ks[H][Br2] + k,[H] [HBr] ~ 2ks[Br]}. Addition of these two equations yields 2ks[Br]? = 21,, so that I,\'? n= (t) Tis result in ether of the steady-state equations yields ultimately (&) 2 an) [Br] + [HBr] These values in Eq, (34.96) bring it to the form (H] = 2k \ paray . dt 14 SLABr] * Bn] ‘The expression in Eq, (34.97) is very similar to that for the thermal reaction where the factor 13? is replaced by k}/(Br,)"2, This means that the bromine atom concentration is main- tained by the photochemical dissociation of bromine rather than the thermal dissociation, ‘The dependence on the square root of the intensity is notable, since it has the consequencePhotosensitized Reactions 905, that the quantum yield is inversely proportional to the square root of the intensity: (HBr) 2k.) at In Asthe intensity increases, a greater proportion of the bromine atoms formed are converted to Br, instead of entering the chain; most of the additional quanta therefore are wasted, and the process is lessefficient. Because k, is very small, the quantum yieldis less than unity at room temperature in spite of the fact that the HBr is formed in a chain reaction. As the temperature increases, the increase in k increases the quantum yield (ks is nearly inde- pendent of temperature) 34.19 PHOTOSENSITIZED REACTIONS Photosensitized reactions make up an important class of photochemical reactions. In these reactions the reactants are mixed with a foreign gas; mercury or cadmium vapor are often used, The primary photochemical act is the absorption of the quantum by the foreign atom or molecule. Ifamixture ofhydrogen, oxygen, and mercury vapor is exposed to ultraviolet ight, the mercury vapor absorbs strongly at 253.7 nm with the formation of an excited mercury atom, He* Hg + hv + Het. ‘The energy corresponding to this wavelength is 471.5 kJ/mol. The energy required to dissociate a molecule of hydrogen in its ground state to two hydrogen atoms in their ground state is 432.0 kJ/mol. The dissociation of oxygen requires 490.2 kJ/mol. The energy possessed by the excited mercury atom is more than enough to dissociate H, but not enough to dissociate O,. The quenching reaction He +H+H introduces H atoms into the mixture, which can initiate chains to form HO’ by the usual mechanism, A reaction that is initiated by light in this way is a photosensitized reaction; the mercury is called a sensitizer. ‘The importance of photosensitization derives from thefact that reaction is produced in the presence of the sensitizer in circumstances where the direct photochemical dissociation is not possible. The example just cited is a case in point. Radiation of wavelength 253.7 nm was absorbed by a mercury atom. The excited mercury atom dissociated a molecule of hydrogen by transferring the excitation energy in a collision. The mercury atom had 471.5 kJ; of this 432.0 kJ were needed for the dissociation; 39.5 kJ are left over and go into additional translational energy of the two hydrogen atoms and the mercury atom. If the attempt is made to dissociate H, directly by the process Hg* + Hy H,+hyv ——> H+H, we find that light of 4 = 253.7 nm willnot produce any dissociation even though it still has the 471.5 kJ, which is more than enough if we consider only the thermodynamics of the process. For the direct absorption to produce dissociation, the wavelength must lie in the absorption continuum; for H, the continuum begins at 849 nm. The absorption of light