SELECTIVE IR LASER INDUCED ISOMERIZATION AND DISSOCIATION OF BIS ( TRIFLUOROMETHYL ) KETENE MOLECULES

Multiphoton IR laser induced isomerization and dissociation of (CF3)2C=C=O (FMK) molecules have been studied. The antisymmetric stretch v1 = 2192 cm-1 of C=C=O—and antisymmetric v16 = 991 cm-1 of C—C— bonds were excited by the second- and first harmonics of a pulsed TEA CO2 laser. The dependence of isomerization conversion on laser radiation frequency, fluence, and number of shots was measured. The isomerization channel was predominant compared with dissociation for the conditions of IR multiphoton excitation under study.The isomerization of FMK by the second–harmonic radiation of a CO2 laser was proved to be selective with respect to oxygen isotopes. The isomerization product (FMA molecules) was enriched with 18O with maximum value of selectivity α(18/16) = 3.9 when FMK molecules were excited at 2ωlas = 2143.8 cm-1.


INTRODUCTION
The effect of vibrational multiphoton excitation and dissociation (MPD) of poly- atomic molecules by powerful IR laser radiation has been under intense studies in many laboratories of the world since the early seventies and remains under investi- gation now as regards photochemical processes and its potential applications-laser chemical synthesis, isotope separation, etc. 1'2 Less attention has been given to isomeric transformations resulting from MP excitation.At the same time, it has been pointed out that in practical applications molecular isomerization has a numb- er of advantages over MPD, such as the formation of a stable molecule as a product rather than reactive radicals and, secondly, a lower reaction barrier. 1 '2 In our opinion, MP isomerization is of much interest since it gives an opportunity of directed production of the only reaction product, an isomer, as the laser radiation fluence and (or) frequency vary, as well as an opportunity to change the isotopic composition of the products.'2 In, 3 for example, as cyclopropane molecules were excited by an optical parametric oscillator with a wavelength 3.22 tm, only isomeriz- ation was observed and the only reaction product was propylene.On the other hand, the final products consisted of equal quantities of the isomer and various dissociation products, when 9.50 lam radiation of TEA CO 2 laser was used.The isomerization of hexafluorocyclobutene selective with respect to carbon isotopes was reported by the authors of. 4The opportunity for isotopically (14N/15N) selective isomerization of methyl-and ethylisocyanide molecules was demonstrated in.To the best of our knowledge these works were the first attempts to realize isotopically selective isomerization of molecules under MP excitation.The above advantages of MP isomerization over MPD in practical applications, we believe, give a reason for further research in this direction.
This work is concerned with investigation of isomerization and dissociation processes of bis (trifluoromethyl) ketene molecules (FMK) (CF3)2C--C---O during their MP excitation by the first-and second harmonics of pulsed radiation from a TEA CO2 laser.Besides, the problem of realization of oxygen isotope selectivity was put as the molecules are excited via the vibration of the C---O bond, where a large isotopic shift was expected. 2

EXPERIMENTAL
The initial FMK was kindly provided by Scientific Industrial Association P&M.
The analysis of the IR absorption spectrum of FMK (Fig. 1) shows a good agree- ment with the reference spectrum in 6 as well as the absence of any impurities level < 1%.In the range from 5 to 10 pm FMK has rather intense IR absorption bands (v =2192 cm-and vx6--988 cm-) assigned to antisymmetric stretching vibrations of bonds C--C--O and CC. 6 The FMK molecules were excited in two ways.In the first case the CO 2 laser frequency C%s=983.25 cm -(10R32 line) was nearly at resonance with the band v x6--988 cm-x.In the second case FMK was excited by the second harmonic of a TEA CO laser with the frequency 2C%s= 2175.5+ 2143.8 cm-(2.9R32+ 2.9R10) that fell on the long-wave wing of the band v =2192 cm -.The nonlinear single crystal AgGaSez 7 was used for efficient frequency doubling.
The TEA CO 2 laser operated on the mixture CO2:N2:He= 1:0.2:4.The temporal shape of radiation pulse was standard-a front peak with FWHM of 80 ns con- taining 70% of the total pulse energy and a "tail" with its full width of about 1.5 las.The TEA CO2 laser radiation was focused by lenses with f= 80 / 200 cm and directed into stainless steel cells with NaC1 windows, 100 and 112 mm long and 24 and 14 mm in diameter, respectively.The second-harmonic radiation was focused by lenses with f= 8 and 20 cm, the ratio of the fluence in the focus of the lens to that at the inlet of the cell being 10 and 1.5, respectively.The radiation fluence in the short-focus lens caustic was usually 2 + 3 J/cm z and in the caustic of the lens with f= 20cm 0.5 +0.7 J/cm2.The IR absorption spectra of FMK and photochemical reaction products were recorded with an IR spectrophotometer (SPECORD-M82).
The conversion of FMK molecules was determined from the consumption which, in its turn, was calculated from the IR spectra before and after irradiation.After irradiation, when necessary, the remaining FMK was separated from the resultant isomer (pentafluoromethacrylyl fluoride, FC---C(CF3)COF-FMA) through low- temperature distillation.The purity of the separated compounds was controlled by IR spectra.The IR spectrum of FMA (Fig. 1.) was compared with those known from references.8'9 Due to a large difference in boiling temperature between FMK and FMA (5 and 52C, accordingly8) the content of residual FMK in FMA and vice versa did not usually exceed 5%.It should be noted, that FMK and the products of its isomerization and dissociation are stable in a gas phase.After keeping the irra- diated FMK and its products in the cell for 24 hours we have not found any appreciable changes in the IR spectra.Isotopic analysis of irradiated FMK and its isomer as well as the detection of the dissociation product CO were performed with a mass spectrometer (MI 1309).The content of oxygen isotopes in FMK and FMA was calculated from the inten- sities of the mass-peaks with m/e= 159 and 161 which corresponded to the ions C4F5160 + and C4F580+, respectively.The enrichment factor with respect to 60 or 80 isotopes in FMK and FMA and isotopic selectivity were es- timated using the formulas taken from.The selectivity was defined as a ratio of isomerization yields of molecules with 60 and 180o(18/16)=fl8/fl6 or z(16/18)=fl6/fl 8.The dissociation product CO was detected using a mass spec- trometer via the peaks with m/e=28,29,30.Before analysis CO was separated from FMK and the rest of the products by freezing them at -196C.All the experiments were carried out at a constant pressure of FMK (0.85 Torr).This pressure ensures near-collisionless conditions of FMK MP excitation by a laser pulse with duration of about 80 ns.

RESULTS AND DISCUSSION
The first experiments revealed a considerable difference in the products of photochemical reactions as a result of irradiation of FMK at the frequencies 2o91as=2171.5+ 2143.8 cm -1 and Olas=983.25 cm -1.In the first case we could only observe isomerization of FMK to FMA.At the same time, small amounts of CO were detected by a mass spectrometer.The latter is an indication of some dissocia- tion of FMK molecules.According to our estimations, however, the contribution of dissociation to the whole conversion of FMK was insignificant (< 1%), despite rather a high fluence of the second-harmonic radiation (2 + 3 J/cm2).In the second case a set of products was essentially different.The characteristic bands in the IR absorption spectrum allowed us to conclude that, besides the isomer, C3F6, C2F4, COF 2 as well as an unidentified product, with its band at the frequency 0f 2052 cm-1, were formed.Also, CO was recorded by mass spectrometry.Figure 2 shows the kinetics of accumulation of some of the listed products with an increase in the number of laser pulses (o91,=983.25cm-1).It may be seen that the formation of C3F6 and the product with band 2052 cm-1 increase with irradiation.At the same time, the amount of FMA increases only at the starting of irradiation and then begins to drop.Such behaviour can be attributed to the dissociation of the ac- cumulating isomer.This is possible, since the frequency of exciting radiation oa=983.25 cm-1 is at resonance with the IR band of the isomer at 986 cm-1 (see Fig. 1).Indeed, as the pure isomer was irradiated at 091,=983.25 cm-1, its dissocia- tion was observed and the qualitative and quantitative composition of the products was the same as in the case of FMK.
To understand what products are formed as a result of dissociation of FMK itself we recorded them after irradiation of the sample by a single laser pulse.The basic products of FMK dissociation were C3F6 and CO, which agrees with the results of the experiments on UV photolysis of unfluorinated dimethylketene, (CHs)zCzC--O. 1The quantitative and qualitative composition of the products, resulting from MP excitation of FMK, depends on the excitation level which is determined, in turn, by laser radiation fluence.With OOla=983.25cm - and tI) < 1 J/cm2, for example, the only product of reaction observed is the isomer FMA.The absence of other products was confirmed by both IR and mass spectra.As the fluence exceeds 1 J/cm2, CF6 and CO-dissociation products of FMK begin to appear.
Table 1 presents the fractions of the isomer and the dissociation product C3F6 for two fluence values.It can be seen that with a small excess (@= 1.3 J/cm2) over the Table 1 The ratio of isomerization and dissociation yields for different levels of MP excitation of FMK molecules, O91as 983.25 cm-1.
@, J/cm number ot pulses Figure2 Dependence of amount of product on the number of ltser pulses; Oglas=983.25cm-1,@= 2.6 J/cm2; UP-unidentified product with IR absorption band at 2052 cm-1, the amount of UP is expressed through absorption factor K.
threshold fluence (@ 1 J/cm2), the main reaction product is FMA and the percen- tage of dissociation products is insignificant (about 5%).As the fluence increases up to 3.4 J/cm2, the share of dissociation products increases but isomerization domi- nates (58%) over dissociation as before.The presence of such a phototransformation channel as isomerization, which is the main one under the conditions of our experiments, makes the pulsed IR photolysis of FMK quite different compared with UV photolysis of dimethylketene (CH3)2C--C----O.To relate the fluence of exciting radiation to the average excitation level of FMK molecules we measured the energy absorbed per molecule (Eabs) as a function of fluence (see Fig. 3).Since with > 1 J/cm 2 the conversion of initial FMK to its products is close to 100%, it is possible to consider, that all the molecules in the volume under irradiation interact with the field.Therefore, the average excitation level measured really corresponds to the average energy of the ensemble of excited molecules.
We shall note two important items.First, with @> 1 J/cm 2 (C01as=983.25 cm -1) the average excitation level of FMK molecules exceeds, and sometimes considerably, the energy of cleavage of the weakest bond C--C ( 80 kcal/mol). 11MP absorption of excess energy, sometimes exceeding the dissociation energy by several times, quite often takes place for MP excitation of polyatomic molecules with the number of atoms n> 10 (see 12 and13'l').Using the semiclassical approximation of RRKM theory, similarly to, 12 we estimated the level of excitation of the l 1-atom FMK molecule for typical values of excitation rate in a quasi-continuum ( 10 9 S-1) and frequency factor ( 1013 s-1).The vibrational energy absorbed by FMK from the IR field was found to be 260 kcal/mol which is in qualitative agreement with Figure 3.The second important point is also related to the features of excitation of polyatomic molecules with n > 10.For example, with the average absorbed energy E 90 kcal/mol exceeding the cleavage energy of the CC bond, the contribution of dissociation to the entire conversion of FMK is not high ( 5%) and the iso- merization channel dominates over the dissociation channel.This is conditioned by the small value of the unimolecular dissociation rate compared with the rate of isomerization at a given excitation level because of a higher activation energy barrier for dissociation.As the internal vibrational energy of the molecules increases up to 200 kcal/mol, the unimolecular decay rate rises rapidly and the contribu- tions of the dissociation and isomerization channels become almost the same.
The data in Table 1 allows us to estimate the minimal difference AE between the energies of FMK dissociation and isomerization.This can be done with the use of the semiclassical approximation of RRKM theory.Under the corresponding as- sumption, as in, 12 the expression for the rate constant (kuni) of the unimolecular reaction is: where is the frequency factor; D 80 kcal/mol is the dissociation energy; E is the vibrational energy accumulated in a molecule; E o is the zero-point vibrational en- ergy of the molecule; s 27 is the number of vibrational degrees of freedom of an 11-atom molecule.Now we shall make the following assumptions.Let the isomeriz- ation and dissociation yields fliso and fldiss be proportional to the corresponding rate constants of unimolecular reaction and, hence, the ratio of the isomerization yield to the dissociation yield be equal to the ratio of the rate constants.Then, assume that the frequency factors for the isomerization and dissociation reactors are equal, i.e. (_Diso-"(Ddiss.In this case we get the following expression: AE [(fliso/fldiss) 1/(s-1)_ 1](E + E o D) The value of E o estimated from the data obtained iri 6 is 26 kcal/mol.The substitution of the values of/iso,/diss and E from Table 1 and E o and D into the formula gives AE= 2 +6 kcal/mol.The first assumption is valid and semiclassical approximation of RRKM theory can be used when the isomerization is irrevers- ible.The latter is supported by experimental observation of 100% isomeric conversion.At the same time, it should be kept in mind that barrier reactions, isomerization being one of them, are usually characterized by lower frequency factors as compared to dissociation reactions, 15 co-'is < (D'-'diss.Thus, AE= 2 +6 kcal/ mol is a minimal value of the difference in energies between isomerization and dissociation channels. As noted above, only one product of photochemical reaction (FMA) was detected in the IR absorption spectrum as FMK was excited by second-harmonic radiation at 2C%s=2171.5+2143.8cm-. The a average absorbed energy measured with (I).,o-0.7 J/cm 2 was 40 kcal/mol.Therefore, with o=2+3 J/cm 2 FMK mole- cules are expected to be excited to higher vibrational states.Nevertheless, there is no marked dissociation of FMK observed.The dependence of the average excitation level on the first-harmonic radiation fluence E(@)(see Fig. 3) makes it possible to evaluate the level of energy when the contribution of dissociation to the total conversion of FMK becomes appreciable (> 1%).This value comes to about 80 kcal/mol.The absence of pronounced dissociation in case of FMK excitation by the second harmonic shows that the average excitation level of molecules is less than 80 kcal/mol.This fact indicates that the dependence E(@) is less steep for the second harmonic which is not surprising because the excitation conditions for the first and second harmonics differ greatly.
As pointed out above, MP excitation of 0.85 Torr FMK by a pulse with its duration of 80 ns occurs practically in collisionless conditions.However, all subse- quent chemical reactions of isomerization and dissociation proceed in the presence of collisions.This is because of the long lifetime of vibrationally highly-excited FMK molecules.The reaction rate constant of unimolecular reaction estimated in a semic- lassical approximation of RRKM theory for molecules with their vibrational energy of 130 kcal/mol comes to 160 s-1, i.e. the lifetime of excited molecules is about 6 ms.
Since the fraction of excited molecules approaches 100% in the volume under irradiation, they are not be able to be deactivated and therewith stabilized in a certain isomeric form due to vibrational exchange.The role of V-T relaxation is insignificant because of high vibrational heat capacity of 11-atom molecules.There- fore, deactivation of excited molecules and their isomeric stabilization may only occur due to diffusion from the exposed volume into the cold part of the cell where they relax when colliding with unexcited molecules.The diffusion time estimated in our experiments was several milliseconds.
The isomerization of FMK in case of MP excitation at the frequency 2091as=2171.5+2143.8cm -1 was found to be selective with respect to the oxygen isotopes 16 0 and 180.The isotopic selectivity of isomerization was calculated from the variation of the isotopic ratio in FMK and the isomer separated from each other.Figure 4 shows the selectivity as a function of laser radiation frequency.It can be seen that as the frequency decreases, the isomerization selectivity of FMK mol- ecules with 160 drops and, starting with 2091as2153 cm -1, the molecules with 018 are mainly isomerized.The maximum selectivity values with respect to 16 0 or 180 measured in our experiments come to 4.2 and 3.9, respectively.
In spite of a considerable detuning of the laser radiation (up to 48 cm-1) from the center of the linear IR absorption band (v =2192 cm -1) of molecules with the basic isotope 160, the values obtained for selectivity with respect to 180 are comparatively low -(18/16)= 3.9.In our opinion, it may be caused by the follow- ing factors.First, with detuning below 2150 cm -1 the laser radiation frequency is at resonance with the IR combination mode of the molecules with the isotope 16 0 v2+Vls=2136cm-1. 6This band, when excited, can contribute to the isomeriz- ation yield and therby reduce the selectivity.Second, primary (spectral) selectivity of MP excitation can be reduced by interisotopic vibrational exchange since under the conditions of our experiment, as it was shown above, the FMK mol- ecules are in highly-excited states for a long time and are deactivated due to the diffusion from the exposed volume into the cold area in times of around several milliseconds.2. The contribution of dissociation becomes comparable to isomerization only at high levels of vibrational excitation of FMK molecules (more than 200 kcal/ mol).3. The isomerization of FMK by the second-harmonic radiation of a pulsed TEA CO2 laser was found to be selective with respect to oxygen isotopes.The maximum value of selectivity with respect to 160 or 180 come to 4.2 or 3.9, respectively.

2 Figure 3
Figure 3 The energy absorbed per FMK molecule (Eab) as a function of laser radiation fluence; oo=a 983.25 cm-1.

CONCLUSION 1 .
The main channel of phototransformation of bis (trifluoromethyl) ketene mole- cules following IR MP excitation is isomerization into pentafluoromethacrylyl fluoride.