I 758
H. Lutz, E. Breheret, and L. Lindqvist
been described does not exist. Although no scattering center was found, the conclusion must be reached that alkali metals do not perturb the solvent structure in a detectable manner in the concentration region studied.
Acknowledgment. We gratefully acknowledge the financial support of The Robert A. Welch Foundation. We are indebted to the University of Dallas for the loan of the Spex 1401. References and Notes (1) Metal-Ammonia Solutions, Physicochem. Prop., Coiioq. Weyl / I ,
1970, l(1971). (2) D. A. Copeland, N. R. Kestner. and J. Jortner, J. Chem. Phys., 53, 1189 (1970). (3) P. F. Rusch, Universite Cathoiique de Lilie. France, private cornmunication.
(4) G. C, Klick and J. H. Schulrnan, "Solid State Physics," Vol. 5, Academic Press, New York, N. Y., 195'7,p 97. (5) T. A. Beckman and K. S. Pitzer, J. Phys. Chem., 65, 1527 (1961). (6) D.F. Burowand J. J. Lagowski, J. Phys. Chem., 72,.169 (1968). (7) P. F. Rusch, Ph.D. Dissertation, The University of Texas at Austin, 1971. (8) P. Daure, Ann. Phys., 12,375 (1929). (9) S.Bhagavantam, lndian J. Phys., 5, 54 (1930). (IO) A.* Dadieu and K. W . Kohlrausch. Naturwissenschaften, 18, 154
(1930). (11) M. G.Costeanu, C. R. Acad. Sci., 207, 285 (1938). (12) S. Kinurnaki and K. Aida, Sci. Rep. Res. lnsf. Tokohu Univ., 6, 186 (1954). (13) C. A. Piint, R. M. B. Small, and H. L. Welsh, Can. J. Phys., 32, 653 (1954). (14) G. Seillier. M. Ceccaidi. and J. P. Leicknam. Method. Phvs. Anal. (GAM), 4, 388 (1968). (15) T. Birchall and I . Drummond, J. Chem. Sac. A, 1859 (1970). (16) 8. Bettignies and F. Wailart, C. R. Acad. Sci., 271, 640 (1970). (17) R . Quinn and J. J. Lagowski, J. Phys. Chem., 73, 2326 (1969). (18) D. F. Burow and J. J. Lagowski, Advan. Chem. Ser., No. 50, 1 11965), (19) G. Herzberg, "infrared and Raman Spectra," Van Nostrand, New York, N. Y.. 1966. (20) H. H. Claasen, H. Seiig, and J. Shanier, Appi. Spectrosc., 23, 8 (1969). (21) C. D. Ailernand, Appl. Spectrosc., 24, 348 (1970). (22) W. F. Murphy, M. V. Evans, and P. Bender, J. Chem. Phys., 47, 1836 (1967). (23) A. F. Slomba, C. D. Hinrnan, and E. H. Siegler. Proc. Conf. Anal. Chem. Appl. Spectrosc., (1965). (24) A. E. Douglas and D. H. Hank, J. Opt. SOC.Amer., 38, 281 (1948). (25) M. Gold and W. L. Joiiy, lnorg. Chem., 1, 818 (1962). (26) D. A. Kleinman, Phys. Rev. A , 134, 423 (1964). (27)J. Brandmuiler and H. Moser, "Einfuhrung in die Rarnan-spektroskopie," Dr. Dietrich Steinkopff Verlag, Darrnstadt, 1962 (28) J. M. Worlock and S. P. S. Porto, Phys. Rev. Lett., 15, 697 (1965). (29) S.Radhakrishna and H. K. Sehgai, Phys. Lett. A, 29,286 (1969). (30) R. Catterall, Metal-Ammonia Solutions; Physicochem. Prop., Coiioq. Weyl / I , 1970, 1 (1971).
Effects of Solvent and Substituents on the Absorption Spectra of Triplet Acetophenone and the Acetophenone Ketyl Radical Studied by Nanosecond Laser Photolysis Hanspeter Lutz,' Emilienne Breheret, and Lars Lindqvist* Laboratoire de Photophysique Moieculaire du C. N.R.S., Universite de Paris-Sud, 91405 Orsay, France (Received December 8, 1972) Publication costs assisted by the Centre National de la Recherche Scientifique
The triplet absorption spectra of p-trifluoromethylacetophenone, acetophenone, and p-methyl- and pmethoxyacetophenone in nonpolar solvents were measured by nanosecond laser photolysis using the third and fourth harmonics of a Nd glass laser. Acetophenone was also studied in acetonitrile and water. In the cases where the energy of the lowest 3(n,7r*) state is lower than that of the lowest 3(~,7r*)state, the triplet absorption spectra are characterized by two weak absorption bands a t about 410 and 450 nm and by a strong absorption appearing below 330 nm. When the 3(7r,7r*)'state is lowest, the triplet has a structureless, weak absorption in the visible and a strong maximum a t about 350 nm. The spectra of the ketyl radicals of p-trifluoromethylacetophenone, acetophenone, and p-methylacetophenone were determined in cyclohexane. The spectra are all very similar and resemble the triplet absorption spectra of the ketones which have lowest triplets of 3(n,r*) nature. The rate constants of hydrogen abstraction from 2-propanol by the triplet state of these latter ketones in benzene solutions containing 2 M 2-propanol are 6.2 X lo6, 1.2 x 106, and 1.3 x IO5 M-1 sec-1, respectively. The results indicate that measurements of triplet absorption spectra may be useful in determining the 3(n,n*)us. 3(n,7r*) nature of the lowest triplet state of alkyl phenyl ketones.
Introduction It is known that many alkyl phenyl ketones have almost isoenergetic lowest 3 ( n , ~ * and ) 3(7r,r*) states, a property leading to interesting spectroscopic and chemical consequences. Information about the nature of the lowest triplet state of these compounds has been obtained mainly The Journal of Physical Chemistry, Voi. 77,No. 14, 1973
from studies of phosphoresence,2-6 singlet-triplet absorption,7.8 and zero-field splitting.QJ0 Triplet absorption spectra are expected also to be of value in characterizing the triplet state; however, only few measurements of triplet absorption spectra of alkyl phenyl ketones have been reported previously.1l~l2
Absorption Spectra of Triplet Acetophenone and the Acetophenone Ketyl Radical In the present study the triplet absorption spectra of acetophenone and a number of acetophenone derivatives were determined using the nanosecond laser photolysis method. The lowest triplet state of acetophenone in nunpolar solvents is considered to be a 3(n,a*) ~ t a t e ; ~the ,~a second triplet, situated only a few hundred wave numbers above the lowest triplet state, is considered to be a 3 ( a , ~ * ) state.9 Vibronic coupling between these two states is efficient and produces a mixed character of the lowest triplet state.13 A consequence of the energetic proximity of the triplet levels is that even small perturbations, e.g., substituent5314 or solvents effects, may produce level inversion or changes in the extent of vibronic coupling between the two lowest lying triplet states. The effects of such perturbations on the triplet absorption spectrum were determined in the present study by comparing the absorption spectrum of triplet acetophenone in nonpolar solvents to those of para-substituted acetophenones containing electron-withdrawing (CFs-) or electron-donating groups (CH3-, CH30-). Solvent effects were determined from measurements of the acetophenone triplet absorption spectrum in solvents of varying polarity (cyclohexane, acetonitrile, and water). By the use of these solvents and substituents, it was possible to vary the nature of the triplet state progressively from a predominantly 3 ( n , ~ *to) a ) predominantly 3( a , ~ *configuration.
Experimental Section Materials. Acetophenone (Eastman) and p-methylacetophenone (Fluka) were doubly vacuum distilled; p-trifluoromethyl- and p-methoxyacetophenone (Fluka) were purified by sublimation. Benzene, cyclohexane, 2-propanol, acetonitrile (Merck Uvasol), and perfluoromethylcyclohexane (Peninsular Chemresearch) were used without further purification. Water was doubly distilled. Solutions were degassed by three freeze-thaw cycles with intermittent saturation by argon. Laser Photolysis Equipment. The excitation light source was a Q-switched Nd glass laser (Compagnie G6n6rale d’Electricit6, Model VD 231, maximum energy 60 J) emitting a t 1058 nm; the pulse half-width was 35 nsec. The third (353 nm) and fourth (265 nm) harmonics, generated by means of KDP crystals, were used in the present study, at energies in the order of 1-20 mJ. Relative values of the laser energy were obtained by measuring the integrated photocurrent from a photomultiplier tube (EM1 9781 B) exposed to a small fraction of the ultraviolet laser beam. An optical system projected the laser beam, reduced to a height of 4 rnm and a width of 8 mm, on one side of a 10-mm square silica cell with polished sides, containing the sample. The monitoring light was obtained by discharging a 320-kF capacitor (1-1.8 kV) across a xenon flash tube (Verre et Quartz, VQX 65 N ) in series with an inductance of approximately 100 p H ; the flash half-width was 650 Msec. Triggering was made such that the laser pulse occurred during the period of maximum intensity of the analysis flash. The analyzing light passed in a crossed-beam arrangement through a 2 mm wide section of the sample cell, close to the laser entrance window. A narrow wavelength band ( 2 nm) of the transmitted light was selected by means of a monochromator (Jarrell-Ash, Model 82-410, f/3.5, f = 25 cm); the intensity in this band was measured using a photomultiplier tube (Radiotechnique, 150 UVP or 150 CVP). The output of the seventh dynode, terminated by 75 (2, was displayed on a n oscillo-
1759
scope (Fairchild, Model 777, 100 MHz). The overall. time resolution of the detector system was ca. 10 nsec. Transient absorption spectra were obtained from oscilloscope recordings over a range of wavelengths (every 3-10 nm). A linear correction of the transient optical densities was applied for variations in the laser energy.
( A ) Effect of Substituents on the Acetophenone Triplet Absorption. Laser excitation of acetophenone and some of its para-substituted derivatives in nonpolar solvents produced the end-of-pulse transient absorption spectra shown in Figure 1. The ultraviolet part of the spectra was obtained after excitation by the 265-nm harmonic. The SOlute concentration was chosen such that an OD of 1 to 2 was obtained across a 1-em path (0.002-0.006 M).The transient absorption in the visible is very weak and it was for this reason found necessary to use the higher output of the 353-nm harmonic and higher solute concentrations (0.1-0.2 M ) to obtain measurable absorptions in this spectral range. Aerated solutions gave the same end-of-pulse spectra as the degassed solutions. Measurements between 600 and 1000 nm did not reveal any perceptible absorption in this spectral range. Our previous study12 established that the transient spectrum observed immediately after laser irradiation of acetophenone is due to the triplet state. The spectra in Figure 1 are by analogy attributed to the lowest triplet state of the corresponding compounds. In the case of p-trifluoromethylacetophenone, measurements of the triplet spectrum in hydrogen-donating solvents was impracticable due to the high triplet reactivity of this compound. Perfluoromethylcyclohexane was chosen as solvent in the determination of the ultraviolet part (Figure l a , dotted line) and benzene, because of the higher solubility of the ketone in this solvent, in the determination of the visible part (Figure l a , full line) of the triplet spectrum of this ketone. Estimates of the extinction coefficients given in Figures 1 and 2 were obtained by comparison of the triplet absorption intensities of the acetophenone derivatives with the intensity of the benzophenone triplet absorption,12 measured at equal laser excitation energies. It was assumed that the extinction coefficient of triplet benzophenone in cyclohexane has the same value a t 533 nm as that determined in benzene solution15 (7630 M - I cm-I). It was also assumed that the triplet yield was unity for all the compounds studied. It is seen from Figure 1 that substitution in the benzene nucleus leads to pronounced changes in the triplet absorption of acetophenone. Substitution by the electron-withdrawing trifluoromethyl group produces a shift of the strong ultraviolet absorption to shorter wavelengths. The electron-donating methyl and methoxy groups instead lead to complete disappearance of the structure of the absorption in the visible while a high-intensity absorption band shows up in the near ultraviolet around 350 nm. These spectral changes may be discussed by considering the effect of substituents on the electronic nature of the lowest triplet state. Low-temperature studies of the lifetime, structure, and polarization of the phosphorescence of acetophenone in hydrocarbons indicate that the lowest triplet state of the ketone is of 3 ( n , ~ * nature ) under these conditions.l3~2J This state is expected to be strongly perturbed by a near) The closeness of the two states is demonby 3 ( ~ , a *state. The Journai of Physical Chemistry, Voi. 77, No. 14, 1973
51. Lutz, E. Breheret. and L. Lindqvist
WAVELENGTH (nm)
Figure 1. Triplet absorption spectra of para-substituted acetophenones in aerated solutions determined by nanosecond laser photolysis (end-of-pulse spectra): (a) p-trifiuoromethylacetophenone in perfluoromefhylcyclohexane (- - - -) and in benzene (-); ( b ) acetophenone in cyclohexane; (c) p-methylacetophenonein cyclohexane; and (d) p-methoxyacetophenone in cyclohexane.
~
~ (nm)
V
~
Figure 2. Triplet absorption spectra of acetophenone in aerated polar solvents determined by nanosecond laser photolysis (endof-pulse spectra): (a) acetophenone in acetonitrile and (b) ace-
tophenone in water.
strated by the ease of inversion of the states with change of solvent; in the more polar EPA glass the lowest triplet is a 3(n,7r*)state according to a study of the polarization of the phosphore~cence.~3 The appearance of vibrations assigned to nonplanar modes in the 3 ( n , 7 r * ) phosphorescence of acetophenone in 1EPBal3 and some substituted acetophenonesle reveals a strong vibronic coupling between the 3(n,n*) and 3 ( ~ r , n *configurations. ) p-Trifluoromethylacetophenone has been studied using phosphorescence excitation techniques.14 It was found that the energy of the 3(n,s*) state of acetophenone is decreased by the substituent; no evidence was obtained as to the location of the upper ~ ( T , T * )state. From the fact that trifluoromethyl substitution produces a blue shift of the absorption maximum of the IL, IA transition,17 one may expect a similar increase in energy of the corresponding 3(n-,~*)state 3L,. It follows that the energy spacing between the low-lying 3(n,n*) and ~ ( A , A * ) levels should increase when a trifluoromethyi group is introduced in the acetophenone molecule, thus bringing about a reduction in the vibronic coupling between the two states. The enhancement of the 3(n,n*) character of the lowest triplet state is further supported by the very short phosphores*I4 cence lifetime of p-tr~~uoromethy~acetopheno~e Q -
The Journal of Physical Chemistry, Voi. 97, No. 74, 7973
Triplet state assignments have been made for p-methylacetophenone in 3-methylpentane glass a t 77OM.13 It is concluded from the results that the lowest triplet state in this case is a 3(7r,n*)state, coupled vibronically to a closelying 3(n,7r*) state. The S ( X , K * ) assignment of the lowest triplet state of p-methylacetophenone is also supported by its phosphorescence excitation spectrum14 The lowest triplet of p-methoxyacetophenone in a moderately polar solvent is considered to be a 3(n,n*)state.5.16 The 3(n,7r*) state was located 2100 cm-1 above this state.5 Due to the large energy gap between the two states, vibronic interactions are expected to be small, and variations in the solvent polarity thus should not have a great influence on the orbital character of the triplet state. Indeed, it has been shown that the phosphorescence lifetime of this ketone i s almost the same in 3-methylpentane glass as in EPA, demonstrating the lack of influence E ~ ~ ~ ~ of~the solvent on the triplet state character in this case.13 Making use of the assignments cited above in discussing the absorption spectra given in Figure 1, we note that the absorption spectra of the ketones with lowest triplet states of 3(n,7r*) nature (p-trifluorornethylacetophenone and acetophenone) show two absorption bands in the visible. The presence of these bands seems to be directly connected ) of the triplet state since no such with the 3 ( n , ~ * nature * ) is bands are observed in the cases where the 3 ( ~ 7 n state lowest. It may also be noted that the visible band system is most pronounced in the triplet absorption spectrum of p-tri~uoromethyiacetophenon~in which vibronic perturbation of the lowest 3(n,n*) state is expected to be weak. The ketones with lowest triplet state of 3(n,n*) nature (p-methyl- and p-methoxyacetophenone) have triplet absorption spectra showing a strong maximum a t about 350 nm and weak structureless absorption in the visible. The triplet absorption spectra in the present study were obtained a t room temperature whereas the triplet state assignments discussed above were obtained from low-temperature studies. It has been shown,3bJs that the overall orbital character may vary with the temperature when the triplet states are closely spaced. In the absence of quantitative estimates of such effects, their possible influence on the triplet nature was neglected in the interpretation of the results. A verification of the above assignments arid of their validity a t room temperature conditions may be obtained by determining the hydrogen-abstracting power of the triplet state, since it is known that hydrogen abstrac-
Absorption Spectra of Triple?Acetophenone and the Acetophenone Ketyl Radical 6
6
5 4
4
1761
h P
P
I
v
7 9 x
2
2
w
350
450
550
350
450
550
WAVELENGTH ( n m )
Figure 3. Ketyl radical absorption spectra of para-substituted acetophenones in degassed cyclohexane; (a) p-trifluoromethylacetophenone (measured 1 psec after laser excitation); ( b ) acetophenone (measured 1.4 psec after laser excitation); and (c) p-methylacetophenone (measured 10 gsec after laser excitation).
vents are similar to those found in acetophenone containing an electron-donating substituent in the benzene ring. The band structure in the visible observed in cyclohexane (Figure Ib) does not appear in the more polar solvents, but instead, a strong absorption maximum is found at about 330 nm. This change may be interpreted as being due to the ) of the lowest triplet change from 3(n,n*) to ~ ( T , x * nature with increasing solvent polarity. Lamolag predicted the 3(n,n*) and 3(n,n*)states of acetophenone to have nearly the same energy in ethanol. This prediction is supported by the observation of dual phosphorescence from acetophenone in ethanol and solvents of similar polarity, such Compound k,, M-lsec-I as EPA.21 It appears from recent phosphorescence studies that the ~ ( T , T * )state of acetophenone is located even p-Trifluoromethylacetophenone 6.2 X 1Q6 below the 3(n,n*) state in ethanol-containing glass.13 Acetophenone 1.2 X lo6 In a previous study we have presented evidence for a p-Methylacetophenone 1.3 x 105 strong solvent dependence of the acetophenone triplet Information regarding the effect of ring substituents on state reactivity and explained this in terms of the extent the triplet state reactivity of acetophenone was obtained of mixing of the lowest 3(n,n*) and 3(n,n*)states.lg The by Yang and Dusenbery14 from quantum yield studies. dependence of the acetophenone triplet absorption on the These authors reported somewhat lower values of k , than solvent polarity observed in the present study lends furthose obtained in the present work; the relative importher support to this conclusion. tance of k , is about the same, however. (C) Effects of Substituents on the Acetophenone Ketyl The strong decrease of k , in going from p-trifluoromethRadical Absorption. In the preceding discussion, the variylacetophenone to p-methylacetophenone is consistent ations in triplet absorption due to substitution were interwith the proposed change of the orbital character of the preted as being due to changes in the relative positions of lowest triplet state from 3(n,n*) to 3(a,n*).The high reacthe 3(n,7r*) and 3 ( n , ~ *levels. ) If other specific substituent tivity of triplet p-trifluoromethylacetophenone compared effects produce the observed variations one would expect to that of acetophenone may be attributed to the reduced to find similar effects on the acetophenone ketyl radicals. perturbation of the lowest 3(n,n*) by the upper 3(n,n*) To examine this possibility the ketyl radical spectra of acstate. The lowest triplet state of p-methylacetophenone is etophenone and p-trifluoromethyl- and p-methylacetopheexpected to be a 3(n,n*)state, yet p-methylacetophenone none were determined and compared. The ketyl radicals shows significant photoreactivity. This behavior has been were obtained by laser excitation of the ketones in deattributed to the vibronic coupling of the lowest 3 ( ~ , a * ) gassed cyclohexane. Figure 3 shows the transient spectra with the closely spaced 3(n,n*) state.14 due to this radical, measured after disappearance of the (B) Effect of Solvent Polarity on the Acetophenone triplet absorption. The extinction coefficients of the radiTriplet Absorption. Figure 2 shows the triplet absorption cals were estimated roughly assuming that the correspectra of acetophenone in the polar solvents acetonitrile sponding triplet disappears exclusively to produce the (a) and water (b). The triplet absorption spectrum of aceradical. tophenone in ethanol has been given elsewhere.12 The The similarity of the spectra indicates that substitution spectra were measured under the same experimental condoes not specifically change the electronic configuration of ditions as the spectra shown in Figure 1. The wavelength the acetophenone ketyl radical. This observation strengthof the triplet absorption peak in water is in agreement ens the hypothesis that the spectral changes in the triplet with recent flash photolysis results.20 It is seen that the absorption arising by substitution are indeed due to absorption spectra of triplet acetophenone in polar sol3(n,n*)-3(7r,n*)level inversion.
tion from the solvent by an aromatic ketone in the triplet state will be efficient only if the state has 3(n,a*) orbital character. The hydrogen-abstracting efficiency is obtained conveniently by the nanosecond laser technique from measurements of the triplet decay rate. We determined in this manner the rate constants of photoreduction, k , , of p-trifluoromethylacetophenone, acetophenone, and p methylacetophienone. Details of the procedure have been described elsewhere.19 The measurements were made in degassed solutions of these compounds (0.1 M ) in benzene solutions that were 2 M in 2-propanol. The following values were obtained
The Journal of Physical Chemistry, Vol. 77, No. 14, 1973
1762
Howard D. Mettee
It is seen that the ketyl radicals have spectra very similar to those of the triplet state of 3 ( n , ~ *nature. ) Such a relation was already found for benzophenone and was attributed to the similarity in the a electron configuration of the 3 ( n , ~ *state ) and the ketyl radical.22 Conclusions The present study provides evidence of strong solvent and substituent effects on the absorption spectrum of triplet acetophenone. These effects are shown to be relat) ed to variations in the extent of 3 ( n , ~ *us. ) ~ ( P , T * orbital nature of the lowest triplet state. One may conclude from these results that triplet absorption spectra are useful criteria in determining the lowest triplet configurations of alkyl phenyl ketones. Measurements of the decay of the triplet in hydrogendonating solvents show that the changes in the triplet absorption spectra due to solvent and substituent effects are associated with significant changes in the reactivity of the triplet state. These findings are direct evidence that the variations in the acetophenone photoreactivity are due to variations of the electronic con'figuration of the lowest triplet state. References and Notes (1) Present address, Laboratory for Research on the Structure of Matter, The University of Pennsylvania, Philadelphia, Pa. 19174. (2) V . G. Krishna, J. Mol. Spectrosc., 13, 296 (1964).
(3) (a) R. Shimada and L. Goodman, J. Chem. Phys., 43, 2027 (1965); (b) M. Koyanagi, R . J. Zwarich, and L. Goodman, ibid., 56, 3044 (1972), (4) T. F. Hunter, Trans. FaradaySoc.. 66, 300 (1970). (5) D. R. Kearns and W. A. Case, J. Amer. Chem. SOC., 88, 5087 (1966). (6) W. A. Case and D. R. Kearns, J. Chem. Phys., 52,2175 ('1970). (7) S. Dym and R. M. Hochstrasser, J. Chem. Phys., 51, 2458 (1969). (8) Y. Tanimoto, H. Kobayashi, S. Nagakura, and T. Azurni, Chem. Phys. Lett., 16, 10 (1972). (9) A. A. Lamoia, J. Chem. Phys., 47, 4810 (1967). (10) (a) N. Hirota, Chem. Phys. Lett., 4, 305 (1969); (b) J. B. Gallivan and J. S. Brinen, ibid., 10, 455 (1971); (c) T. H. Cheng and N. Hirota, ibid., 13, 194 (1972); (d) S. W. Mao, T. C. Wong, and N. Hirota, ibid., 13, 199 (1972); (e) T. H. Cheng and N. Hirota, J , Chem. Phys., 56, 5019 (1972). (11) D. S. McClure and P. L. Hanst, J. Chem. Phys., 23, 1772 (1955). (12) H. Lutz and L. Lindqvist, Chem. Commun., 493 (1971). (13) Y. H. Li and E. C. Lim, Chem. Phys. Lett., 7, 15 (1970). (14) N. C. Yang and R. L. Dusenbery, J. Amer. Chem. SOC.. 90, 5899 (1968), (15) R. Bensasson and E. J. Land, Trans. Faraday SOC., 67, 1904 (1971). (16) E. C. Lim, Y. H. Li, and R. Li, J. Chem. Phys., 53, 2443 (1970). (17) N. C. Yangand R. L. Dusenbery, Mol. Photochem., 1,159 (1969). (18) E. Migirdicyan, Chem. Phys. Lett., 12, 473 (1972). (19) H. Lutz, M. C. Duval, E. Breheret, and L. Lindqvist, J. Phys. Chem., 76, 821 (1972). (20) M. B. Ledger and G. Porter, J. Chem. SOC., faraday Trans. 7, 68, 539 (1972). (21) (a) N. C. Yang and S. Murov, J. Chem. Phys., 45, 4358 (1966); (b) P. Gacoin and Y. Meyer, C. R. Acad. Sci., 267, 149 (1968); (c) R. N. Griffin, Photochem. Photobiol., 7, 159, 175 (1968); (d) P. J. Wagner, M. J. May, A. Haug, and D. R. Graber, J. Amer. Chem. Soc., 92, 5269 (1970); (e) M. E. Long, Y. H. Li, and E. C. Lim, Mol. Photochem., 3, 221 (1971). (22) H. Tsubomura, N. Yamamoto, and S. Tanaka, Chem. Phys. Lett., 1, 309 (1967).
Vapor-Phase Dissociation Energy of (HCN);! Howard D. Mettee Departmenf of Chemistry, Youngstown State University, Youngstown. Ohio 44503 (Recieved April 2. 7973) Publication costs assisted by The Graduate School, Youngsto wn State University
The temperature dependence of fundamental infrared absorbance intensities of vl in monomeric and dimeric forms of HCN vapor is used to calculate a AED = -3.80 f 0.16 kcal/mol. This value is somewhat greater than the earlier experimental value of -2.6 kcal/mol, determined by classical vapor density measurements, and compares more favorably with a recently theoretically computed value of AED" = -3.7 kcal/mol, based on apriori methods.
With the exceptions of the work of Inskeep,l Bernstein,2 and Dunken and Winde,3 very few measurements of the thermodynamic properties of small, hydrogen-bonded complexes in the vapor phase are currently being reported. Since recent theoretical methods have advanced to the point where a priori calculations may now be performed on such system^,^ there exists a need to have reliable experimental data a t hand for comparison. The recent calculations of Kollman, et aL,5 on the HCN dimer illustrates the problem rather nicely. For the reaction
2HCN
(HCN)Z
The Journalof Physical Chemistry, Vol. 77. No. 14, 1973
the calculated energy of reaction (AEDo = -3.7 kcal/mol of bonds) could only be compared with an experimental value (AED = -2.6 kcal/mol of bonds) determined 34 years ago by Giauque and Ruehrweine using vapor density data which were still 10 years older. In view of the acknowledged occurence of higher polymers in HCN vapor such data are somewhat suspect. In fact, the above autho& caution against taking equilibrium constants based on such measurements too seriously. In the case of HCN the infrared measurements of Hyde and Hornig7 provide an independent means of checking the earlier vapor density value and the more recent calculated one. The v1 mode of monomeric HCN is an example
