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Chemical Physics 52 (1980) 151-163

@ North-Holland Publishing Company

THEORETICAL

ANALYSIS

OF THE CYCLOADDITION

E. KASSAB, E.M. EVLETH,

J.J. DANNENBERG*

OF ETHYLENE

and J.C. RAYEZ**

Cenne de Micanique OndularoireAppliqu&, 75019 Paris, France,
and the Deparhnent of Chemistry, City Universityof New York, Hmrer College,
New York, N-Y. 10021, USA
Received 2 January 1980
Revised manuscript received 1 July 1980

The cycloaddition of ethylene is theoretically analyzed for portions of the excited singlet and triplet hypersurfaces
using a combination of semi-empirical and intermediate level ab initio techniques. The semi-empirical UHF calculations
on the addition of triplet ethylene and methyl radical to ethylene showed that these two reactions have comparable
theoretical parameters, including activation energies, spin transfer and spin polarization at the transition state. For the
?.S+ZS excitedsingletstate surfaces, the results of both the ab initio and semi-empirical calculations are qualitatively the
same and correspond to the classical ideas generated from orbital symmetry rules. At the ab initio level the results are
quantitatively poor, partially due to the use of an intermediate level configuration interaction treatment. In particular, it
was not possible to obtain other than a small fraction of the total estimated valence correlation energy in cyclobutane.
The configuration interaction problem for both ab initio and semi-empirical calculations is discussed in detail.

1. Introduction

The goals of this article are two-fold. First,
we will characterize the theoretical nature of the
photodimerization of ethylene for portions of
both the excited singlet and triplet hypersurfaces. Second, we will explore some of the
methodological problems encountered in using
semi-empirical and ab initio methods to elucidate photochemical reaction mechanisms. We
are especially interested in developing semiempirical methods in order to investigate larger
systems on which good quality ab initio calculations are presently financially impractical.
The dimerization of ethylene and other
related olefins to give substituted cyciobutanes
(or the retroaction) is well studied both
experimentally [l] and theoretically [2]. The
orbital symmetry rules for the concerted 2S+2S
process are a standard pedagogical exercise [3].

l

* City University of New York, Hunter College, USA.
* Present address: Univeaiti de Bordeaux I, Talence,
NATO Postodoctoral Fellow, 1975-76.

While existing theoretical work is in support of
these rules, there are several important nuances
with regard to the excited state surfaces. Firstly
the triplet surfaces have not been explored.
Secondly, recent work on the analogous Hq
surface [4] indicates that a conceivable route for
deactivation of the excited singlet state of the
ethylene dimer could occur by a crossed (Dzd)
approach of two ethylenes [4b]. Thirdly, the
theoretical nature of the so-called doubly
excited state at large ethylene-ethylene
separations is not anticipated by the orbital symmetry
rules [4]. In this article we will explore portions
of the triplet surface which yield the triplet
tetramethylene diradicd. For the singlet surface
we will only explore planar face-to-face
approaches having rectangular-trapezoidal
carbon atom configurations.
We will specifically treat the theoretical
nature of the doubly excited state at both small
and large ethyiene+thylene
separations. Finally,
we will discuss the problems encountered in
using an intermediate level configuration interaction treatment.

Kassab et al.56 A. the rNiano9 searchbeing done over the next ‘8. 2. AIthougb the original calibration of the relative enthalpies of ethylene and cyclobutanewas done at the 60 x 60 CI level. respe&vely). at the 60x60 level. Important configurations were inch&d in the treatment as a result of a number of trial c2& culations in which the inadequzy of the Cl basis set was evident by disco&n&ties of the S** and Sf surfaces at the HOMN. it was found that the excited states were better treated at a larger CI level Thus.UiMO inversion geometry (ca. In add&n. no z!ltomatic confguration selection procedure was used in the semi-empirical CI treatment. the So and S** states shown here were treated at the 102 CI level of which 88 were doubly excited including 26 four open shel9 amfigurations whose importance will be d&cussed later.2.aes of 1.1 A separation between the two ethylenes).donly ORa portion of the &M arhitz\lswe decided to estimate the a%1 4%lencle currrelntiun energies of tiylobutane PI.one being the original sh@llconflgmkm.g. 2. an approximate enthalpy of -20 k&/mole [Zfj* (obs.. olg) for carbon and (5s/24 for hydromd with orbital exponents. @fesU%ZPcalculutionswere performed oh dk# @l@#B#hell ground and open shell singlet &nd @ipfftt ctlnflgurutians. respe-tively. have B1.the rlagtetand triplet states cal@&MrPj her@.87 ltndTI. The ST and T1 states were treated at the 75 md 84 CI level. the other being the nntigtration resulting from two promofcd from the HOMO to Is trentmentyields au after CI ground state. Thu Cl cxpansious for these open sr&ll etztes WQ~Q performed around only one %L”i”parent cznllgurutian. -18) [lc] for the reaction of two ethylenes to give cyclobutane as well as reasoaabk geometries for these two molecules (e.35 and 1. All CI calculations WVrl@the result of the threshold terms [?i] of 5 x n with tho number of configurations 1 4OfJin each af the three separate ‘i%lpcl salcululions were performed by EreezMI oh@~OWVM 1 MO’s (essentially Is on C). and the sonclted stnte..irrlly symmetricstates was expanded two parents. “Fhusthe highest 12 virtual orbitals %@~i-” not ttxaminad.. Semi-empirical The method used is the previowfy moderately reparameterized CM)0 te&niq~e [2fl applied at the medium CI tevei @O-120~ CPI at the UHF level. Since the Ci calculations @@IF perfarmr. We performed a partial point-by-point optimization for the S** state al t A misprinl in ref. This was done u&g & modification cf the Gaussian 70 m in which the size of the individual I d s-cl.1JI E. The semi-empirical CI treatment is to be contrasted with the ab initio one in that both the grauhd and excited singlet aud triplet Cl states were generated from the same set of CN00 SCF closed s!~ell molecular basis orbit&. 3G orbitals is related to the mrrelalion cw?gy Tlncmajor portionsof the ab initio cal~~~~t~~n~ were performedusing the gaussian dique of Whitten and co-workers [S]. By symmetry @QrMlUnn. CC distar. [SJ. these being r&&d to r&Hasgeneratedby cxcitoa interHi8dttbof the mr* (“%J. an over contractedvalence basis set. symmetries i&f the OJ~form of the dimsr. An identical paratneter&&on was used which yielded. / 77worelicnfnnnlysis of!hc cycloaddirion of erhpkne and ethylene. So. [2fl quotesthis value at 4 kczllmk .)stutes with the $$t%unrd 618IQ.Further studies using a ~~~~nt~r~d using the intermediate tevel CI W&Mrnffnt dl~ubeed below and lack of financial &a#b srrry oul a complete treatment. !P*. The CI treatment [6] 8%t9~ ir. At the time this study was done we had no available scheme for geometry optimization at the after-C1 level.

will still give be. For huge molecular systems. For reaction (3) we assume that.uface calculations. The main reason for their poor estimate of the relative ground state Available thermodynamic. This would make the value shown for (1) slightly more negative. (l! ‘I$. energies of different molecules [12] hes been established [13] and largely corrected at the MCSCF level [14].8 A. The disrepute of such methods lies mainly with their quantitative uncertainties and seemingly ever changing parameterization schemes.-I-‘I& = cyclobutaae.2.48 a [IS]) with ground state ethyfene (‘l$) to give the triplet tetra-methylene diradicai (“TMDR) is about 19 kcal/mole exothermic: ‘Eob+ 3Ego. AH = 64 kcal. part of what . theoretically ‘Ego0and ‘Ew are nearly isoenergetic and thus the energy of reaction (2) .18 kcal/moIe [ Ic]. = ‘TMDR. Thus.19 kcal/mole. large CI cnlculation can be trusted for a surface calculation involving some changes in relative correlstion energies along that surface [lo].2. exploratory calculations were aiso done using the unparameterized INDO as well as MINbO/S methods. 13) (1) This estimate (1) is obtained by combining reactions (2). AH = . For the UHF triplet surface a more complete optimization was performed [g] using the same repatameterized CNDO method [2f]. cyclobutane (:!‘. 3. Th. AH = . the activation energy for the thermal decomposition of cycfobutane is identical to the enthalpy change generating ‘TMDR even though it has been theoretically indicated [Zc] that there may be several ‘TMDR intermediates which are several kcal/mole lower in energy. Reaulls nnlddiscussion 3. In this case the advantages of the small basis set semiempirical CI method over its ab initio counterpart lies in its variable parameterization. b]. Llowevcr. however. *Eoo+ hv = ‘Euom. the CNDQ/S method [l 11. CC = 1. (3). It remains to be shown by comparative calculations.us. The same was done for the ST state at 2. Since both ab initio and semi-empirical calculntions using similar size basis sets will carry the same symmetry information. Only in reaction (2) do we have a true experimental value. Finaflv. and assuming that ‘TMDR and ‘TMDR are nearly isoenergetic. whether or not a CNDO CI method can generally mimic the excited state surface features generated by an ab initio calculation of similar basis size. Neither the CNDCI/S nor the original CNDQ/INDO methods were originally parameterized with the intention of doing s.-Jill be explored here is a comparison of such calculations and problems encountered.0 A ethylene-ethylene separation. AH =53 kcal/mofe [ICI. These latter methods were rejected for reasons discussed below. This afterCI optimization was done by varying only the CC distances and the CHI ffap angles.= 3TMDR. spectroscopic and theoretical data indicate that the reaction of twisted triplet ethylene (3E90-. Likewise. However. financial or technical limitations impose smeller basis sets such ih:lt a lorgc CI treatment may be difficult or presently impossible and the resulting surfaces poor [IO].. we have demonstrated that our reparameterized CNDQ CI method yields adequate appearing ground and excited state bond rupture surfaces [2f]. It 1s probably a general opinion that for small molecular systems with a large basis set. The ethylene-ethylene triplet dimerizatiotl 3.ter estimates of transition energies For a large system tharl will a small basis set ab initio method.‘mole. Gerteral methodological onsideratiorrs It is our general view that useful inexpensive information on excited state behavior can be obtained using semi-empirical methods [2f. the value shmvn for reaction (4) is theoretical [15a. semi-empi::ical CI methods still have the potential of giving useful information on large systems.1. 91.

however. would only be important if for some reason the regeneration of starting material from ‘DR was highly favored only in the case of acyclic olefins. Since the same CNDO reparameterization is used in our CI calculations discussed in the next section we decided to retain the same overall parameterization for both the UHF triplet and RHF-CI singlet surface in spite of the fact.. . and 3TMDR. versus -19 estimated) as well as intuitively false geometries for 3TMDR and intermediate structures. Likewise. for the -CHz-CHz distance.J. will give rise to a relative corf See also ref. in ethylene is strongly dependent on the 3AS(l. It was initially determined that an unreparameterized INDO-UHF method gave a hopelessly false enthalpy for reaction (1) (ca. as will be shown. If so. The near degeneracy of the tripIet and ground state surfaces in olefins occurs onIy near the twisted 90” configuration of the p-orbitals comprising the z-bond. It should be stressed. There is an additional nuance to the arguments posed above. the MIND0/3 optimized geometry for trans3TMDR gave 1.44 8. a result similar to the known experimental and theoretical energy gap dependence for triplet-ground state intersystem crossing in aromatics [17]. that the final computed activation energy for reaction (1) was not satisfactory. at a dissociation limit. a closed and open shell species. [k]. somewhat far from what one would expect from a C-C sp3-sp2 hybrid (1.1A90.49 and 1. one can anticipate radical-like kinetic parameters. then: d(3A)/dt = -!c~(~A) . and 1.52 for the C-C distances in 3Egc. Kassab et al. While the triplet states of small ring olefins will undergo some relaxation. We will only report in detail on the computed optimized triplet reaction path for reaction (1) generated using our reparameterized CNDOUHF method [2f]. This observation WI be conveniently rationalized [lg] by examining the kinetic expression for the disappearance of triplet olefin (3A) by competitive unimolecular intersystem crossing 3A%1A.energy gap.52) [IS]+. Our goal will be to estimate activation energy and enthalpy for reaction (1) as well as to attempt to characterize the radical-like nature of the reaction pathway using geometry and spin transferspin polarization criteria_ We will also investigate the possibie differences in triplet sensitized photodimerization cyclic and acyclic olefins. indicate that ki. It is commonly assumed that triplet addition reactions are radical-like in character.. it can be argued that it is the variation of kk with olefin structure which controls the partitioning of reactions (5) and (6). Our own CNDO-UHF reparameterization yielded -27 kcal/mole for the enthalpy of reaction (l). ‘DR+ ‘DR. 1 theoretical analysis of the cycloadditiin of ethylene 154 will approach the known activation energy for thermal cis-trans isomerization of ethylene [lc]. Even though triplet sensitized photodimerizations of small ring oIefins have been commonly observed [le-j] reaction (1) has never been fully demonstrated to occur with ethylene . While the MINDOi3 half-electron method gave a reasonable estimate of this enthalpy (-31 kcal/moIe). it is axiomatic that the T-S energy gaps in relaxed cyclic olefin triplets will be larger than for acyclic triplets. if we assume that only reactions (5) and (6) dominate in both types of olefins. that from a general methodological point of view the use of a UHF single determinate method to compute a surface of a bimolecular reaction between what are.E. -100 kcal/moIe. the optimized C-C geometry for 3E90n(1.kX3A)(‘A. 2 3DR_ (6) The fates of the generated diradical.of simple acyclic olefins. If the values for kd are less than diffusion controlled ones! this implies enthalpyas well as entropy of activation effects in reactions of the same type as (1).48) [15]. (5) and bimoIecular dimerization 3A c ‘A.36 A) was very far from the best ab initio value (1. Thus. (7) The trajectory calculations of Warshel and Karplus 1161.

AH = -28 kcal/mole. The optimized geometry of the tfansition state for reaction (l). In any case. in a certain sense. giving theoretical support to the idea [22] that some triplet state reactions are radicallike in character. respectively. In any case. small ring cyclic olefin triplets contain about 16 kcal/mole excess energy as compared to relaxed acyclic olefin triplets. The possibly more critical measure of progress along the reaction coordinate is the spin density.. 2. As discussed below. about a factor of two. Reaction (1) has a computed activation energy of 28 kcaljmole while that of a simulated cyclopentene triplet-cyclopentene is 21 kcal/mole. the theoretical profiles for both radical and triplet addition to ethylene are similar. a polarization which occurs well before the transition state. In both reactions there is virtually no spin transfer at the transition state. too large (ohs. this being sufficiently large at the transition state (ca. (8) (9) Reactions (8) and (9) have previously been estimated by Baird and co-workers 1201 at -32 and -16 kcal/mole. for the methyl radical-ethylene reaction which is. 19 kcal/mole. 2. 8 kcal/mole) [23]. Kassab et al. what is observed demonstrates the principle that a negative spin density at the receiving carbon atom in radical reactions is a required precondition for bond formation [22]. with the ethylene ground state is shown in fig. 1.54) = 3E90. shown in fig. it is predicted that the low quantum yields of acyclic triplet sensitized photodimerizations are due to a combined high value for kec and lower than diffusion controlled rate for kd.(CC= 1.5 A) that little activation energy difference was found for rotational variants about the forming CC bond. shows little geometry change in the reacting moieties as compared with their isolated structures. the main negative feature of the CNDO-UHF calculations presented is that they give unreasonably high activation energies. Therefore. in turn.49). This latter value is comparable with our own computed value. the accepting carbon atom in both reactions exhibits a large negative spin density. we performed geometry optimizations on ethylene in which only two cis-hydrogens and the CC distance were allowed to vary and found an essentialIy planar structure with the same CC distance and energy as shown for reaction (8).54).E. the following energetic analysis is given using the reparameterized CNDO-UHF approximation. What we had not anticipated is that such spin polarization would occur at distances very much larger than that occurring for the threshold for spin transfer. while little spin transfer has occurred. On the other hand. For comparison purposes. Thus. However. M = -16 kcal/mole. First. in cyclic olefins ka should . it can be argued that the olefin tripiet-olefin reaction should have an activation energy comparable to normal radical addition reactions.35) = 3Erp(CC = 1. The geometry optimized CNDO-UHF minimum energy pathway for the reaction of 3Eg0. the reaction of the methyl radical with ethylene is shown in the same figure. we decided to use our CNDO-UHF calcuiation of the methyl radicalethylene reaction to estimate the probable activation energy of reaction (1). Acyclic olefin triplets may have activation energies several kcaljmole higher than this value. in order to determine the energetics of the reaction of nearly rigid smali ring triplets we computed the following UHF geometry optimized reactions using our modified CNDO parameterization: 3Eoa(CC= 1. 3Eoe(CC= 1. Even though an unprojected UHF calculation will overemphasize such spin polarization. As a model calculation for the cyclopentene triplet. The critical coordinate is the CC bond distance between reacting carbon centers. Thus. Both the geometry and spin density transfer criteria are consistent with the inter- 155 pretation that the transition state is more reactant-like than product-like. with virtually the same optimized CC distance. However. based on this comparative method we predict that the reaction of cyclic olefin triplets with olefins should have activation energies in a region of 8 kcal/mole. / Theoreticalanalysisof the cycloodditionof ethylene relation energy error [19]. Thus.

. It is known that the qunntum yields for sensitized photodimerization OFcyclohexadiene (ca.Ol) [22]. Also shown are the spin transfer from the radical or triplet species to e~I~@oe and the mzgz~~ spz~ dcnuily n1 the occepling carbon atom along the reaction coordinate. We will dli ia detail s~mr:d the complications invoived in treatig a very much larger system. I. oost amsi&rat&ms preventing us from doing a surface sear& fcr the 9* minimum. \ve have found virtually no reported experimcntul values for activation energies for triplet nddition reaction aside from a recent value for tht! reaction of triplet trimethylenemethane with a substituted olefir~ (6 kcal/mole) [24]. Rep~rnmcterizizd [2f] CNDO4JHF calculations of the addition of triplet ethylene to ethyk~ and m&. especially in wbzt mzmncr OUTcalcul2tions are diEerentia@d &om mrE+ calculations on the same system.!cuLat&~. in a renl sense.08 A.2 A regk~~ Qualitatively.. I. 3. 1) are much higher than for butadiene (O. surface wea Michl and co-workers 13 possible photochemical faces has already been these workers. 2) were bzsed cm S&ese1?3empirical results. respectively. Sin&r effects should occur in cyclic and acyclic polyenes.4 r&k%! BD cthylct~c.CARBQN-CARBON BOND DISTANCE. the ab initio ay. On the other nand.0-2. I%e geometry choices for the ab in&o ~~~~~ at the intermediate geometries (ca. In both the semi-empfal a& & initio czlculatians the minimum d timeS” 51ifface is in the 2. nlso be lower than diffusion controlled rate. l’hus. Qttalitative aspects The essential details of the calculations presented here are shown in figs.3. ANGSTROMS Flfl. 3 and 4 for the semi-empirical and ab initio calculations. The detailed energeti of the latter calculations are shown in tablie P.xdse&e calculations show the same be portions af the H.3 LVe cthyltme-eth ylene excited singlet surfaces 3. B-5 table 1 and fig. Shown is the minimum geometry optimized pathway for an in-plane carbon amm co&go&o% wi~-irhCfM &T%B~ kept constnnl al 1. . ir is the variation in the kilir values which differentiate the triplet sensitized phatodimerization kinetics of acycIic and cyclic olcfins.

the configurational compasitinns of the SOand s”” states are as expected from orbitel symmetry rules. Both the semi-empirical and ao initio ca!culatiors give essentially the same qualitative infarmation. ethylene-ethylene separatian the S** state becomes lower in energy. ar large ethylene-ethylene separations. at short ethjrkne-ethylene distances. They both consist mainly of plus and minus combinations of two major configurations. S**. 1. Initially.E. S’. Kmab er al. tbe ST surface is lower or nearly isoenergetic to the S** state. A5 seen in table 2. but dt the HOMQ-LUMP avoided state crossing region near 2. namely that there are two excited states Sf and S** of the ethylene dimer which oftlthz cyclnaddirion ofethylene 157 are involved in the photodimerizadon process.0-i-2 8. f Th@orelfcal at&is Fig 2. The relative weights of these two configurations change radically for the SOand S** states over a Iairly narrow geometry region of significence singlet excited stare. and dauhty excited state. A&J shown are the individual atomic spin deMies as well I the total amount of spin density tidefred of retained on each ethylene udit. . The geomeby of the uptiMid transition state of the calculation shown in fig. one the closed shell SCF solution (HOMO doubly occupied) and the other the doubly excited configuration (LUMO doubly occupied).

41 13 1. Other geometries were taken from semi-empirical calculations. The configurational behavior of the S** state is much more complicated. Table 1 AS initio SCF-CI calculations on ethylene-ethylene Cal.745 -155.809 -155.079 -156.644 . RL R. A detailed discussion is necessary concerning the correlation of the S** state at large ethylene-ethylene separations [26].931 -155.747 -156.155. R2 and RO_ . See fig.477 -155. 1 for definitions of S.889 -155.700 -155.40 11 1. R.955 -155. HCH bond angle at 112’. This is shown in table 2 where the S** state is shown to be neither principally a closed shell doubly excited state nor a two open shell monoexcited state but a four open shell doubly excited state at 3.425 I.767 -155.415 1. 4.562 -155.945 -155. It does not evolve towards a S** state of monomeric ethylene as might be indicated by a 2 ~2 CI [2b] or a state correlation diagram. CH kept constant at 1. Kasab eta!.723 -77. The configurational behavior (table 2) of the So state is ? Note that this point is overlooked in the correlation diagrams proposed in related types of photocycloaddition reactions: see for instance ref.672 CI SCF CI -155.952 -155.00 2. .766 -155.8 134 ethylene” cyclobutaneb’ 1.38 3.639 -155. Likewise.. it becomes largely monoconfigurational at the cyclobutane or two ethylene limit.09.852 a)Experimental geometry.10 2. Unfortunately.936 -155. / ?heoreticaI analysis of the cycloaddition of ethylene 158 I I simple.029 -155.20 335 S** S” T* SCF CI CI SCF -155. than it is usually. If the dimer is calctdated under DZh symmetry.90 2. State SO 1 2 3 4 5 6 7 IS 1.838 -155.771 -155.surfaces [257.792 -155.435 1.39 9 1.645 -155. Ab initio CI calculation of the cycloaddition of ethy!ene to give cylobutane. this surface instability will permit the formulation of diabatic functions interconnecting the SOand S**. a set of delocalized MO’s is obtained which have a correspondance with those anticipated from orbital symmetry rules. Energies for the e:hylene (e) dimer limit (00) are twice the energies shown in table 1.500 1.078 -78. Caicularion used an after contraction 40 orbital basis set for cyclobutane plus CI at about the 400x400 level using a configuration selection threshold of 5x IOm1hartree.961 -155.E.562 -155.908 -77.736 -155. the configurational composition of the S”* state at large ethylene-ethylene separations depends on whether one is working with localized or delocalized MO’s In the case of Fig.733 -77.757 -155.26]f.866 -155.808 -155.875 -17. ‘) Planar geometry as found in 6-31G* calcuiation of Cremer [32].893 -155.789 -155. geometrical parameters not shown were not changed.526 -77. [27].886 -155.825 -155. As in the case of I& the S** state correlates with two ethylene triplets [4.9 R. The calculation shown in table 2 is done under conditions where the ethylene dimer is in a trapezoidal geometry where the MO’s are Iocalized on either one ethylene or the other at large ethylene-ethylene separations. More simply stated.5 A. See table 1 for geometry detaiIs.440 1.787 nonconvergent -77. this geometry region is sutliciently theoretically special to warrant the speculation that it is where the internal conversion from S** and So occurs [4d].640 -155.

Kassab eta!.420 0. The energy of this configuration at large ethyleneethylene distances tends to become bitriplet in character because only the central two determinates contribute to the orbital-orbital exchange term K. Similarly a srpall CI treatment [2b] at the STO-3G level shows a much greater energy lowering for ethylene than for cyclobutane [2c].1)2-+ (LUMO -I-1)’ together with the four-bpen-shell determinate shown above. the ground state thermodynamics are greatly in error using a small ST0 [2b] or STOJG [2c] basis set (talc.59 correlation energy problem With regard to the computed ground state energetics of the cycloaddition of ethylene.665 0.5-0.846 0. ca.900 0.639 0. This behavior is also found in the semi-empirical calculations performed using localized orbitals. With respect to the ab initio calculations the configurational behavior of the SF and T1 states is simple.) has Z-U* not Z-T* character at large ethylene-ethylene separations but undergoes change in configurational character at small separations and becomes JXT*. 50 kcal/mole) for two ethylenes. the major configuration (0. HOMO’+ (LUMO + 1)‘. HOlMO’+ LUM02.1 2. Ri’ coeKb’ = (HOMO)’ 1.9.S** So !Y* SO .9 So s** So . 2~1 as well as ihe semi-empirical level [2a. With regard to the semiempirical calculations the lowest energy S* state (‘Bz in C. / Theoreticalanalysis of the cycloaddition of ethylene Table 2 Leading configurational terms in the ab initio calculations Config. i. -18) [lc]. ” For this distance the major configuration is a four open shell having a value of 0. they are both largely purely HOMO+ LUMO open shell states (over 90% monoconfigurational).379 0.359 0.397 0.842 0.048 2.e. ‘) Either double occupation of HOMO or LUMO. between these five configurations and two triplet ethylenes at large ethylene-ethylene separations is difficult to see.5 (LUMO)’ + -I+ c - 0. Quantitative aspects-the localized orbitals (table 2) the double triplet character of the proper (S2 = 0) four open shell configuration is hidden within the polydeterminatal structure shown below: where the indices 1 and 2 refer to orbitals largely localized on either ethylene 1 or 2.662 0. 2c] SCF-small CI [2b. -80 kcal/mole.215 0. this configuration is related IO two ethylene triplets.. (HOMO l)‘+ LUM02. At the SCF level.771. see text. obs.0 2. The conceptual relationship 1.. Likewise these central determinates are triplet in character because one has either both (Yor fl spins in the same molecule. there are a number of previous calculations at the ab initio SCF [2b.S** So S** = = = = = = = = = 0.2 3. This implies that the total valence correlation energy of two ethylenes is much different than . 2f2i].08 au (ca.919 0. (HOMO .E.807 0. 2d.151 0. However.539 0.213=j ” AngtrBm units. 3. This is an artifact of the CNDO method even under our parameterization. Our general conclusion is that in this and similar types of calculations it is best to impose a slight symmetry breaking on the system is order to obtain localized orbitals at large separations.2.860 0. With regard to the STO-calculations [2b] a simple 2 ~2 CI showed essentially no energy lowering for cyclobutane but about 0.929 -0.200 0. d’ For both the S* and T states at each distance.3.96) has a single occupation for the HOMO and LUMO. These small C&mall basis set treatments essentially improve the apparent agreement between the calculated (after CI) and observed enthalpies of the reaction by lowering the energy of ethylene more than cyclobutane. Essentially experimental values are obtained from 4-31G and 6-31G* calculations [28]. using del6calized orbitals the S**state becomes polyconfigurational at large distances.

R) which while better than the STO-3G-ST0 cefculationa quoted above is worse than a 41 I G or 6-31G” estimate. imposition af Cf at about the 400x400 level makes this value in even worse*(ca. Does this mean that we can regard that portion of fig..207 vnlctke shell * 0. “.516 0.. [7].1040 1. As one proceeds afong the surface some of the orbit& will fncrease in energy and states witi approach one another. 4 and table 1 ..bfe sohnxon of imptovbrg rho SCF treatment using a larger basis set will not improve the above agreement except at the SCb Icvel.06593 IIIR. 4 (and table 1) as more “believable” if one rejects the consideration of the two ethylene limit? Two things argue against this ahernate pofie. rmd the CH and CC valence orbitals for koth ethylene and cyclobutane as obtained from a correlative equation [7] relating the SKI-3Ci localized orbital size to the correlation energy. since only 10% of the valence correlation energy is estimated in the case of the grouno state of cyclobutane there remains a large margin of error.068 for cyclabutane. An analysis of this problem requires some estimate of the correlation energies of both ethylene and cyclobutane in order to find cut how much of this energy is not being cnlculntcd.. if we were onfy interested in the enthafpy of this reaction. First. the computed total corrclntion energy.re faultsd because of an imbalance in the estimated relative correlation energies of ~~ctobutane and two ethylenes. the valence correlation energy actmlly obtained has evolved over the years from intermedir?e values of about 0. core * 0.522) 17.0560 1._ _ 0iiylrnc cyclulullrrllc Donrl or orbital type lacnlircd In Cti CT Is C. -!.7 shown in table I and fig... Our computed valence correlation energies of ethylene (0. Correlation energya’ (au) (1. +bO kcal/mole) ngrcrmcnt with the experimental value than at the SCF level! The possi. Since the CI space of ethy.333) and cyclobutane (8. ” ‘V’h). h~<Illxulo . However.515 0. is not the case. is sufficiently close 10 the estimated vult~c (0. Thus. 4 are comparable. The problem resides in the CI technique used. Especially in the case of cyclobutane the Cl treatment has only obtained about 10% of the total valence correlation energy. as we wid show.1033 I.544 0.317 0. Our own calculation at the SCF level yielded a computed enthalpy for this ethylene cyeloaddition reaction of -44 kcaf/mole (exptl. see textnnd ref.*.. Thus.316 0.for cyclobutane which..rputed value of about 0. only calculations l-5.“_” . _-_ AimatCs ___ fat ethylene and cyclobutane ((rllr’l$))“* “R. We know from the above discussion that the calculations shown in fig. OS4 au. we would not wish to go beyond a large basis set SCF estimate.6X 0.36 estimated] l30].0560 1.2 au to the most recently co. core = 0. With regard to a very large basis set-nearly complete CI treatment of the ground state of etiyfene. Shown in tnble 3 are the estimated correkition cncrgies for each localized carbon 1s ?orc.671 j are such that there is essentizify no great carrelation energy difference for the reactioraof two ethylenes to give cyclobutane.333 total * 0.671 total = 1.. fi is likely that the same configuration selection threshold energy wit1 produce a much higher percentage of the vafence correlation energy . The reason for this imbalance is that the CI ~afcufation estimates between cyclobutane and ethylene are not size consistent [31]. x confidence can be placed in ~dd~t~o~~ par& tioning of this energy into core and valence terms.13 au for ethylene and 0..~~f CC __. In the RISCof ethylene.413 velencr shell = 0.291 that some l’ilhk I ~‘~~~IcIIII~B~ energy __Ix_ -.084 ” I’idculuted from the equation. Our own middle level CZ treatment yielded only 0.540 0.0546 correlation energy.0567 corrclntion cnurgy. from a size consistent stand point.-_.ne is smaller than cyclobutane the same configurational selection criteria (5 X lO-4 au) will yield more correlation energy in the case of ethyfene thhn for cyclobutane.33 au (0. Emrr = -0.

the latter containing all totally symmetric mono. Originally the overall thermodynamics of the cyclobutane-two-ethylene reaction was calibrated at the 60x60 CI level by individual calculations on cyslobutane and a sblgle ethylene to give the experiniental value of about 20 kcal/mole [2f].g. This results from the fact that as with the ab initio CI calculation it is easier to compute a greater percentage of the correlation energy when the system is smaller (e.5 h. 3 and 4j shows that there is a VISUJresemblance in the two computations ~II the region of avoided crossing at 2.0 to 4. the semiempirical Cf treatment can be kept wlthin the level 100 x 100. a completc CI is not necessary as long as the major correlatively important configurations are included.uble+xcitations. In the surface actually generated in fig. Likewise. it must be pointed out that the amount of semi-empirical “carrel&ion” energy will also depend on the size of the Cl treatment. The theoretical profi!t. Ir this mtmner. In principle. $1 comparison of the semi-empirical and ab initio stirfeces (figs. 3 the same configurational composit. Both sets of calculations.rt the transition state as well as the general :!ppearance of the reaction diagtan?. a ‘2x 2 CI). This is less than the observed activation energy (+63 kcal/mole) [lc] for a process which is probably biradical-like in character [2c]. Karsnb et al.ined by a few preliminary calculations at various points along ?he reaction surface. Likewise.045 au for the So stntc of ethylene.2 A ill: well as along the surface between 2. In the case of the S** surface at large ethylene-ethylene sepatations the semi-empirical CI treatment must include doubly excited four-open-shell configurations. 3. The latter energy obviously has no relationship to lhc above discussed estimated valeilce correlation energy (table 2) of 0.:: problem treated here. For the triplet diradical surface reparameter&ted CNbO-UHF calculations indicate that the reaction of olefin triplets with olefins should involve activation energies similar to I-adical-olefin reactions. as measured by spin transfer and spin polarizotiotl . The So surface in fig. a semi-empirical technique can be recalibrated under size consistent conditions (i.e. A comparison of ab initio sod semi-empilic“l! I :I calculations for the 2S+ 2S cyctoaddition .ltion under another set.and dr.087 au ai the 1lllx 110 level. The semi-empirical calculation gives the same correlative information as does the ab initio one.33 au. With regard to the CNDO-CI calculations it must be pointed out that a similar size consistency problem exists with regard to the CI This can be demonstrated by examining fig. the computed barrier for the concerted 2S+2S transition state for the ground State surface decomposition of cyclobutane to two ethylenes is less than 60 kcal/mole. / Theoreiicqt analpis along certain portions of the surface than along others in addition to that obtained from a mere HOMO-LUMO indwcd avoided crossing behveen SOand S*” (i. however. 3 does not asympotitically approach the 20 kcal/mole calibrated value at large separations.G. cyclobutane and ethylene dimer at large separations).e. However. Jo Ilot give us an accurate idea as to the height of the So and S*‘kstates in the region of thy HOMOLUMQ crossing. increasing to 0. since the semiempirical-after-Cl results are parameter dependent. ethylene) than larger (ethylene dimet) using the same number of configurations. Our conclusion is that an intermediate level CI treatment cannot give adequate results on this surface regardlessof the irrikd ab initib basis set.. unlike the ab initio calculations. With regard to I~. However. In the case treated here. At the 60 x 60 level this energy was found to be 0.0-2. the important configuratiuns can be detelm.an was maintained along a soxface which begins with cyclobutane and terminates at 4. a semiempirical potential eaergy curve calibrated with one set of configurations Will be out of calibr. the inclusion of of the cycloaddition ofethykne 161 such configurations would involve a large CX treatment requiring a Parge search ta obtain rhe important ones* In fact.s of both types of reaction are similar.5 A with an ethyb.e dimer.

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