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# Definitive heat of formation of methylenimine, CH2=NH, and of methylenimmonium ion, CH2NH⁺₂, by means of W2 theoryDedicated to Prof. Paul von Ragué Schleyer on the occasion of his 70th birthday

## I Introduction

Methylene imine (methanimine, formaldimine, CH2=NH) is a pyrolysis product of amines as well as a photolysis product of methylazide and diazomethane. It has obvious chemical importance as the simplest imine, and with its carbon-nitrogen double bond, methylenimine is a bonding paradigm for numerous nitrogen-containing heterocycles. The molecule is also of astrophysical interest, having been detected in dark interstellar dust clouds.

The heat of formation of methylenimine (methanimine, formaldimine, CH2=NH), is the subject of a long-standing controversy in the literature. Experimental values for the heat of formation ($`\mathrm{\Delta }H_f^{}`$) of this molecule span a range of 10 kcal/mol, and have fairly large experimental uncertainties (about 2 to 3 kcal/mol). The first experiment, by DeFrees and Hehre in 1978, used the bracketing method to evaluate the hydride affinity of HCNH+, and hence derived $`\mathrm{\Delta }H_{f,298}^{}`$\[CH2=NH\]=26.4$`\pm `$3.2 kcal/mol. Ten years later, Grela and Colussi obtained a value of 25$`\pm `$3 kcal/mol from the deprotonation reaction of CH3NH. A Moscow group had meanwhile obtained 21$`\pm `$4 kcal/mol by photoionization mass spectrometry of pyrolysis products of azetidine. In 1990, Peerboom, Ingemann, Nibbering, and Liebman (PINL)  bracketed the proton affinity (PA) of CH2NH as 204$`\pm `$2 kcal/mol by means of ion cyclotron resonance: in combination with an earlier determination of the heat of formation of CH2NH$`{}_{}{}^{+}{}_{2}{}^{}`$ (177–178 kcal/mol) by Lossing et al. from appearance energy measurements, they obtained $`\mathrm{\Delta }H_{f,298}^{}`$\[CH2=NH\]=16.5$`\pm `$2 kcal/mol. Then in 1992, Holmes et al. determined the ionization potential of the CH2NH radical by means of energy-resolved electron impact, and derived an upper limit of 22$`\pm `$3 kcal/mol for $`\mathrm{\Delta }H_{f,298}^{}`$\[CH2=NH\]: they propose an ‘evaluated’ $`\mathrm{\Delta }H_{f,298}^{}`$\[CH2=NH\]=21$`\pm `$4 kcal/mol, which happens to be identical to the Moscow group value. Around the same time, Smith, Pople, Curtiss, and Radom (SPCR) carried out a computational study in which reaction energies for ten reactions involving CH2NH were computed by means of G2 theory: in combination with experimental data for the auxiliary species, they obtained $`\mathrm{\Delta }H_{f,298}^{}`$=20.6$`\pm `$2.4 kcal/mol averaged over the ten reactions. Although this is in good agreement with the Holmes et al. experiment, the error bars are still a far cry from ‘chemical accuracy’ (1 kcal/mol).

Very recently, two of us proposed two new computational thermochemistry methods known as W1 and W2 (Weizmann-1 and Weizmann-2) theory which, for molecules dominated by dynamical correlation, yield heats of formation to within 0.25 kcal/mol (1 kJ/mol) accuracy, on average. A subsequent validation study for a much larger data set came to similar conclusions. Since CH2NH is still small enough for a W2 calculation to be carried out on fast workstation computers, this would appear to be the tool of choice for resolving the controversy on its heat of formation for once and for all. This is the primary purpose of the present paper.

As a by-product, we shall obtain an accurate ab initio anharmonic force field for CH2NH. (For the highest possible accuracy, it is in principle advisable to obtain the molecular zero-point vibrational energy ZPVE from an anharmonic force field rather than from scaled harmonic frequencies.) Aside from matrix isolation work, a respectable amount of high-resolution IR data is available for this molecule. Following early high-resolution work by Johnson and Lovas, Allegrini et al. obtained a high-resolution $`\nu _4`$ by CO laser Stark spectroscopy. Duxbury and Le Lerre studied the $`\nu _5`$ and $`\nu _6`$ bands by Fourier transform IR (FTIR) spectroscopy, including an analysis of the Coriolis interaction (along the $`c`$ axis) between those modes. The $`\nu _7`$, $`\nu _8`$, and $`\nu _9`$ modes, as well as the strong Coriolis interactions between them, were studied by Halonen and Duxbury, while these same authors studied $`\nu _2`$ and the ($`\nu _3`$,$`2\nu _5`$) Fermi resonant band pair in a companion paper and reported $`\nu _1`$ elsewhere.

General harmonic force fields were derived by Jacox and Milligan, by Hamada et al. and by Halonen, Deeley, and Mills: the latter authors also remeasured and reanalyzed the $`(\nu _7,\nu _8,\nu _9)`$ triad. (A microwave substitution structure was obtained by Pearson and Lovas.) To the authors’ knowledge, the only anharmonic force field available is a comparatively low-level (MP2/6-311G\**) ab initio calculation by Pouchan and Zaki. Extensive experience has shown (e.g.  and references therein) that the CCSD(T) (coupled cluster with all single and double substitutions and a quasiperturbative correction for connected triple excitations) electron correlation method in conjunction with a basis set of $`spdf`$ quality generally yields computed fundamentals within better than 10 cm-1 of the observed gas-phase values. Thus, obtaining a force field of such quality is the secondary purpose of the present note.

## II Computational methods

Geometry optimizations and vibrational frequency calculations using the B3LYP (Becke 3-parameter-Lee-Yang-Parr) density functional method have been carried out using Gaussian 98 revision A7. All other calculations were carried out using MOLPRO 98.1, and a driver for the W1/W2 calculations written in MOLPRO’s scripting language, running on Compaq XP1000 and Compaq ES40 computers in our research group.

W1 and W2 theory are described in detail elsewhere. Briefly, both methods involve separate extrapolations to the infinite-basis limit, using a sequence of Dunning correlation consistent (cc-pV$`n`$Z) and augmented correlation consistent (aug-cc-pV$`n`$Z) basis sets, of the SCF, CCSD valence correlation, and (T) valence correlation energies. In addition, contributions of inner-shell correlation and (Darwin and mass-velocity) scalar relativistic effects are obtained at the CCSD(T) and ACPF (averaged coupled pair functional) levels with the MTsmall basis set. While the more economical W1 theory uses a B3LYP/cc-pVTZ reference geometry and extrapolates from aug-cc-pV$`n`$Z (n=D,T,Q) basis sets, the more expensive (and rigorous) W2 theory employs a CCSD(T)/cc-pVQZ reference geometry and aug-cc-pV$`n`$Z ($`n`$=T,Q,5) basis sets. (Regular cc-pV$`n`$Z basis sets are used throughout on hydrogen.) In addition, we considered W1h and W2h results, where the ‘h’ (for ’hetero-atom’) indicates that augmented basis sets are only used on group V, VI, and VII elements and not on group III and IV elements.

The largest basis set CCSD calculations in W2 and W2h theory were carried out using the direct CCSD implementation of Lindh, Schütz, and Werner as present in MOLPRO 98.1. All energies for the open-shell separated atoms were obtained using the restricted open-shell CCSD(T) energy as defined in Ref..

For comparison, we shall also present data for the isoelectronic C2H4 and N2H2 molecules.

A complete CCSD(T)/cc-pVTZ quartic force field for CH2NH was generated in internal coordinates (four stretches, three bends, two torsions). Internal coordinate geometries were generated by recursive application of the central difference formula to the coordinates being differentiated, with step sizes of 0.01 Å or radian around the minimum energy geometry being used. Cartesian coordinates for this ‘grande list’ of points were generated using INTDER: this list of geometries was reduced to a ‘petite list’ of unique points by means of comparison of sorted distance matrices. Thus, 2241 points in $`C_s`$ symmetry and 460 additional points in $`C_1`$ symmetry are obtained. Since this type of application is a textbook example of an ‘embarrassingly parallel’ computational problem, the energy calculations were carried out on a 26-node experimental PC-farm at the Department of Particle Physics, Weizmann Institute of Science. In order to minimize roundoff error in the finite differentiation, integral evaluation cutoffs as well as SCF and CCSD convergence criteria were tightened such that the energies are obtained to essentially machine precision. Quartic contamination was removed from the quadratic force constants. The final internal coordinate force field was transformed to Cartesian coordinates using INTDER, and transformed to normal coordinates as well as subjected to a standard second-order rovibrational perturbation theory (VIB-PT2) analysis using SPECTRO and POLYAD.

## III Results and Discussion

### A Anharmonic force field

A plethora of resonances exists involving the three XH stretching modes $`\nu _1,\nu _2,\nu _3`$ on the one hand and two-quantum states within the $`\nu _4,\nu _5,\nu _6`$ block on the other hand (the modes involved are the CN stretch, the HNC bend, and the HCH scissoring mode, respectively). For this reason, we deperturbed the anharmonic constants for all resonances of the type $`\nu _x\nu _y+\nu _z`$ (where x={1,2,3} and y,z={4,5,6}, e.g. $`\nu _2\nu _4+\nu _6`$ or $`\nu _32\nu _5`$), and set up and diagonalized a $`9\times 9`$ resonance matrix involving all these states. (Formulas for the various higher-order resonance matrix elements were taken from Ref..) The resonance matrix and its eigensolution are given in Table I, while the computed harmonic frequencies and fundamentals (as well as any bands in resonance with them) are given in Table II, compared with experiment and with results from the previous lower-level (MP2/6-311G\**) calculation by Pouchan and Zaki. A complete force field and sets of spectroscopic constants are available as supplementary material to the present paper.

First of all, as readily seen from the solution of the $`9\times 9`$ resonance matrix, the $`\nu _32\nu _5`$ resonance is so severe that the two perturbed states are basically 50:50 mixtures of the respective deperturbed states, and that an assignment of an observed band to either $`\nu _3`$ or $`2\nu _5`$ is somewhat academic. Similar remarks apply to the $`\nu _2\nu _4+\nu _6`$ resonance: in both cases, the assignments in the table were made based on the ordering of the deperturbed states. The $`\nu _12\nu _4`$ resonance is also quite severe but an unambiguous assignment is still possible there. (For a system like this, a full nine-dimensional solution by variational methods or high-order canonical Van Vleck perturbation theory would certainly be helpful: this is however beyond the scope of the present study since we are primarily interested in the thermochemistry.)

This being said, agreement between computed and observed vibrational band origins is basically as good as we can reasonably expect at this level of theory, with all computed-observed discrepancies lying below 10 cm-1. The very good agreement between the present band origins and the earlier lower-level results is somewhat fortuitous, given the discrepancies of up to 50 cm-1 between the two sets of harmonic frequencies. It has been our experience that MP2 computed anharmonicities for XH stretching modes tend to be seriously overestimated, and the present system forms no exception.

The only experimental equilibrium geometry available from the literature is a microwave ($`r_s`$) substitution structure. Agreement between our calculations and the $`r_s`$ geometry is as good as we can reasonably expect (Table III). The effect of correlating the (1s)-like inner-shell electrons on the geometry follows expected trends (Table III). (The MTsmall core correlation basis set as used in W1 and W2 theory was employed for this purpose.) No experimental $`r_e`$ or $`r_z`$ geometry is available, but an indirect measure of the quality of our computed CCSD(T)/MTsmall geometry can be obtained by substituting it in the VIB-PT2 analysis and comparing the ground-state rotational constants thus obtained with their precisely known experimental counterparts. Our computed $`A_0`$=6.54242, $`B_0`$=1.15615, $`C_0`$=0.97936 cm-1 agree to better than 0.1% with the observed values 6.544896(1), 1.1555459(1), and 0.9790851(1) cm-1: given the quadratic dependence of the rotational constants on the geometry, this in fact suggests an even better agreement between the underlying computed $`r_e`$ geometry and Nature. In order to assist future experimental work on the protonated species CH2NH$`{}_{}{}^{+}{}_{2}{}^{}`$, we have computed its geometry at the same level (Table III).

For the mode pairs in Coriolis resonance, the computed interaction constants $`\xi _{79}^a`$=4.701, $`\xi _{79}^b`$=-0.315, $`\xi _{78}^a`$=3.630, and $`\xi _{78}^b`$=1.918 cm-1 are in fair agreement with the experimental values 4.529(1), -0.3305(1), 4.212(1), and 1.8125(1) cm-1, respectively. The computed $`\xi _{56}^c`$=0.552 cm-1 is likewise in reasonable agreement with the observed value of 0.6911(1) cm-1.

Let us finally turn to the zero-point vibrational energy (ZPVE). Our computed value from the CCSD(T)/cc-pVTZ quartic force field, and including the $`E_0`$ correction, is 24.69 kcal/mol. As seen in Table IV, this differs by no more than 0.10 kcal/mol from the zero-point correction used in W1 theory, i.e. B3LYP/cc-pVTZ harmonic frequencies scaled by 0.985. The same remark holds true (Table IV) for the isoelectronic molecules C2H4 (difference +0.04 kcal/mol) and trans-HNNH (difference +0.03 kcal/mol), for which large basis set CCSD(T) quartic force fields are available from previous work. There are certainly situations (e.g. nonrigid molecules — i.e. those exhibiting low-barrier internal rotations and/or inversions, or very low frequency modes — or very anharmonic systems such as $`H_3^+`$) where anything less than an anharmonic force field is fundamentally inappropriate for the zero-point energy. Yet it would appear to be that the immensely less expensive scaled harmonic B3LYP ZPVE is appropriate even for benchmark work: any situation where accuracy of $`\pm `$0.1 kcal/mol on the computed atomization energy is essential is presently beyond direct treatment even by W2 theory.

### B Heat of formation

Total atomization energies (TAEe if zero-point exclusive, TAE0 at 0 K) at the W1, W1h, W2, and W2h levels for CH2NH, CH2NH$`{}_{}{}^{+}{}_{2}{}^{}`$, trans-HNNH, and C2H4 are given in Table IV, together with a breakdown by components of the results at the highest level of theory (W2).

In the light of our observation above, and in order to achieve consistency among the species considered (including CH2NH$`{}_{}{}^{+}{}_{2}{}^{}`$, for which no anharmonic force field is available), all heats of formation reported in Table IV use the scaled B3LYP ZPVEs rather than their anharmonic counterparts.

At the highest level of theory, we obtain $`\mathrm{\Delta }H_{f,298}^{}`$(CH2NH)=21.1 kcal/mol. The W2h result is essentially identical; the W1 and W1h results are slightly different, but still by less than 0.2 kcal/mol. In the original W2 paper, the mean absolute error for a sample of some 30 very accurately known total atomization energies was 0.23 kcal/mol; we shall conservatively take our error bar to be twice that amount, or (after roundoff) $`\pm `$0.5 kcal/mol.

Our calculation stays below the Holmes et al. upper limit and is in excellent agreement with both the Holmes et al. evaluated $`\mathrm{\Delta }H_{f,298}^{}`$and the G2-thermodynamic cycle derived value of SPCR: of course, our error bar is an order of magnitude smaller than the former and several times smaller than the latter.

What is the source of the 5 kcal/mol disagreement between these values and the earlier PINL measurement? In order to shed light upon this question, we calculated the heat of formation of protonated methylenimine, and hence also the PA of the latter compound. At the W1 and W2 levels, we find PA(CH2NH)=207.8 and 207.5 kcal/mol, respectively: this is a minor exception to the rule that W1 and W2 theory yield essentially identical proton affinities. Our W2 PA is 3.5 kcal/mol higher than the bracketed value of 204$`\pm `$2 kcal/mol, but lies within the error bar of the very recent Bouchoux and Salpin value, 206.2$`\pm `$1.5 kcal/mol, obtained by the thermokinetic method. We note that the accuracy of the bracketing is, by its very nature, in turn dependent on the accuracy of the PAs of the bases involved in the bracketing experiments. For the five bases used, namely pyrrole, diisopropyl ether, ammonia, styrene, and diethyl ether, the PA values from the 1988 Lias et al. compilation employed by PINL differ by up to 2.5 kcal/mol from the more recent 1998 compilation of Hunter and Lias.

As for the heat of formation of CH2NH$`{}_{}{}^{+}{}_{2}{}^{}`$, our computed W1 and W2 values are 1.0 and 1.4 kcal/mol higher, respectively, than the value of Lossing et al. used by PINL. Hammerum and Sølling (HS) recently re-evaluated the experimental data of Lossing et al., using the 298 K enthalpy contributions of Traeger and McLoughlin to convert the reported threshold energy measurements into heats of formation at 298 K. In this manner, the value found for methylenimine is 179.7 kcal/mol, in excellent agreement with our W2 calculated result of 179.4$`\pm `$0.5 kcal/mol. HS also calculated the heat of formation of CH2NH$`{}_{}{}^{+}{}_{2}{}^{}`$ at the G2(MP2) and CBS-Q levels, and found 179.0 and 180.2 kcal/mol, respectively. For CH2NH, the corresponding values are 20.8 and 22.0 kcal/mol; agreement with our W1 and W2 values is as good as can reasonably be expected for the G2(MP2) and CBS-Q methods.

W2 is most reliable for molecules that are dominated by dynamical correlation energy. One index which we found to be very reliable for this purpose is the percentage of the binding energy that is recovered at the SCF level. For CH2NH this is found to be 70%, which is closer to C2H4 (77%) and to molecules essentially devoid of nondynamical correlation at their equilibrium geometry (e.g. water, H2) than to trans-HNNH (52%, comparable to N2) which is in a regime of moderate nondynamical correlation. For CH2NH$`{}_{}{}^{+}{}_{2}{}^{}`$, SCF accounts for about 63% of the binding energy.

Interestingly, the reaction

$$\frac{1}{2}\mathrm{H}_2\mathrm{C}=\mathrm{CH}_2+\frac{1}{2}\mathrm{𝑡𝑟𝑎𝑛𝑠}\mathrm{HN}=\mathrm{NH}\mathrm{H}_2\mathrm{C}=\mathrm{NH}$$
(1)
is computed to be exergonic by about 9 kcal/mol. At the SCF level, this is even slightly larger: electron correlation reduces the difference by about 1.1 kcal/mol. For comparison, the reaction

$$\frac{1}{2}\mathrm{H}_3\mathrm{C}\mathrm{CH}_3+\frac{1}{2}\mathrm{H}_2\mathrm{N}=\mathrm{NH}_2\mathrm{H}_2\mathrm{C}=\mathrm{NH}$$
(2)
is exergonic by 6.7 kcal/mol, while

$$\frac{1}{2}\mathrm{HC}\mathrm{CH}+\frac{1}{2}\mathrm{N}\mathrm{N}\mathrm{HC}\mathrm{N}$$
(3)
is endergonic by 6.9 kcal/mol.

## IV Conclusions

We have calculated benchmark heats of formation of methylenimine and protonated methylenimine by means of W2 theory. Our best calculated values, $`\mathrm{\Delta }H_{f,298}^{}`$(CH2NH)=21.1$`\pm `$0.5 kcal/mol and $`\mathrm{\Delta }H_{f,298}^{}`$(CH2NH$`{}_{}{}^{+}{}_{2}{}^{}`$)=179.4$`\pm `$0.5 kcal/mol, are in good agreement with the most recent measurements but carry a much smaller uncertainty. As such, they resolve a long-standing experimental controversy.

As for many other systems, the difference between a fully anharmonic ZPVE (zero-point vibrational energy) and a simple B3LYP/cc-pVTZ calculation scaled by 0.985 is negligible for our purposes.

A first-ever high-quality quartic force field for CH2NH has been made available. Agreement with experimental high-resolution IR data is better than 10 cm-1. Reliable band origins for the stretching modes require diagonalization of a $`9\times 9`$ resonance polyad involving $`\nu _x+\nu _y`$ ($`x,y`$=4,5,6).

###### Acknowledgements.

GdO was a Postdoctoral Fellow of the Feinberg Graduate School (Weizmann Institute) when this work was initiated. JM is the incumbent of the Helen and Milton A. Kimmelman Career Development Chair. The Weizmann Institute Pilot PC Farm was used courtesy of the Department of Particle Physics and the Weizmann Institute Computing Center. JL thanks the US National Institute of Standards and Technology for partial support of his thermochemical studies.

### Supplementary material

The CCSD(T)/cc-pVTZ quartic force field of methylenimine in internal and in normal coordinates is available on the World Wide Web at the Uniform Resource Locator (URL) http://theochem.weizmann.ac.il/web/papers/ch2nh.html