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Theoretical Calculation of Bond Dissociation Energies and Heats of Formation for Nitromethane and Polynitromethanes With Density Functional

Theory
XINFANG SU, XINLU CHENG, YONGGANG LIU, QINGHUAN LI
Institute of Atomic and Molecular Physics, Sichuan University, Chengdu 610065, People’s Republic of China Received 15 January 2006; accepted 22 May 2006 Published online 28 September 2006 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/qua.21155

ABSTRACT: The CONO2 bond dissociation energies (BDEs) and the heats of formation (HOFs) of nitromethane and polynitromethanes (dinitromethane, trinitromethane, and tetranitromethane) system in gas phase at 298.15 K were calculated theoretically. Density functional theory (DFT) B3LYP, B3P86, B3PW91, and PBE0 methods in combination with different basis sets were employed. It was found that the CONO2 bond BDEs can be improved from B3LYP to B3PW91 to B3P86 or PBE0 functional. Levels of theory employing B3P86 and PBE0 functionals were found to be sufficiently reliable without the presence of diffusion functions. As the number of NO2 groups on the same C atom increases, the PBE0 functional performs better than the B3P86 functional. Regarding the calculated HOFs, all four functionals can yield satisfactory results with deviations of Ͻ2 kcal molϪ1 from experimental ones for CH2(NO2)2 and CH(NO2)3, when the diffusion functions are not augmented. For the C(NO2)4 molecule, the large basis sets augmented with polarization functions and diffusion functions are required to yield a good result. © 2006 Wiley
Periodicals, Inc. Int J Quantum Chem 107: 515–521, 2007

Key words: polynitromethanes; density functional theory; bond dissociation energies; heats of formation

Correspondence to: X. L. Cheng; e-mail: chengxl@scu.edu.cn Contract grant sponsor: National Natural Science Foundation of China. Contract grant number: NSAF10376021.

International Journal of Quantum Chemistry, Vol 107, 515–521 (2007) © 2006 Wiley Periodicals, Inc.

However. different computational methods are suitable for various kinds of molecular systems in calculating the BDEs. Nitromethane can also be used as rocket fuel. For example. Tetranitromethane (TNM) is a well-characterized oxidant that reacts with inorganic compounds such as superoxide to generate NO2 and the trinitromethane anion. So far as we know. However. while BHandH is demonstrated to be a better method than B3LYP for the BDEs of sulfur-containing molecules [15]. To the best of our knowledge. So. CBS. while not as good as the G2 predictions. The structures and vibrational frequencies have been studied for polynitromethanes theoretically by Tafipolsky et al. as elementary thermodynamic properties. are sufficiently accurate to be used to study many classes of molecules. in which numbers of electron pairs and chemical bond types are conserved. In the PBE0 functional. and chemical engineers need the values of bond dissociation energies (BDEs) of molecules. It can also serve as a much more powerful explosive when mixed with nitrobenzene. and the diffusion function is needed to scale down the results [16]. is one of the simplest aliphatic nitro compound and is a prototype for energetic materials that could widely serve as high pure solid explosives and propellant fuels. chemists. Thus. only one coefficient is theoretically adjusted to 0. the 516 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10. have been successfully employed for the calculation of HOFs [19. It was reported that the B3P86/ 6-31ϩG** procedure could compute the satisfactory BDEs of the studied small-size molecular system. a parameter free density functional model PBE0 [26]. the impractical problem is that the sophisticated methods require far too much computational time and disk space to treat electron correlation. Heats of formation (HOFs). 20]. have been developed to give accurate results [8 –12].1002/qua VOL. [6] and Vladimiroff [7]. It will be decomposed at a temperature of Ͼ298 K and will be detonated by friction or impact. As for the computational method. Moreover. the B3LYP method is considered by Jursic to be a reliable method for the computation of the BDEs of polar molecules [13] and the NOH bond BDEs [14] for small amines and hydrazines. For stable compounds. 6-31G**. which is represented by the PBE density functional [27]. CH3NO2. 107. and CCSD(T). we employed DFT in our study. are required to evaluate the explosive performances of energetic materials. SVP). 3 . They allow for a cancellation of errors inherent in the approximate treatment of electron correlation on both sides of the reaction. reflecting the mix of Hartree–Fock or exact exchange and the DFT exchange. 24]. Methods and Computational Details All calculations were carried out with the Gaussian 03 program package [21]. determination of the HOFs experimentally is impractical and dangerous. G2(MP2. A severe explosion was reported [2] during the preparation of a sodium trinitromethanide salt. and B3PW91 [22. B3P86 [22. the stabilities and impact/shock sensitivities of explosives are closely correlated to the strength of CONO2 bond [3–5].SU ET AL. there are experimental data of HOFs. no attempt has been made to compute the CONO2 BDEs. Isodemic reactions [18]. to increase the accuracy. The density functional theory (DFT) predictions. G2(MP2). And for nitroaromatic molecules. Therefore. and a series of 4-nitropyrazoles can be synthesized from it [1]. 6-31G*. it is necessary to determine the CONO2 BDEs and HOFs theoretically for polynitromethanes. Introduction itromethane. biochemists. 23]. the B3P86/6-311G** method was reported to be able to give satisfactory CONO2 BDEs [17]. NO. It is well known that the breaking and making of chemical bonds is involved in most chemical reactions. The correlation part is also represented by the PBE correlation functional [27] with coefficient equal to one. such as G2. Therefore. Trinitromethane is a less explosive detonator. it has been demonstrated that high-quality levels of theory. we applied isodemic reactions to the prediction of HOFs for the polynitromethane molecular system. consisting of up to seven or eight non-hydrogen atoms where computational re- N sources are limited. They empower us both to obtain results close to experimental results at moderate computational cost and to extend calculations to much larger systems. 25]. Generally. 6-31ϩG*. it would be useful to test which method is reliable for the calculation of the BDEs for the polynitromethane molecular system.25. and its detonation velocity is near that of RDX (cyclotrimethylene) with the same density. for unstable compounds. 6-31ϩG**. Thus. and 6-311ϩG** basis sets were used. Dinitromethane is known to be distinguished with extremely low thermal stability. The hybrid density functionals used in this study are semi-empirical exchange-correlation functionals B3LYP [22. This limits their applicability to rather small molecules.

Since Charles [29] reported that the B3LYP hybrid functional in conjunction with large basis sets performs better at the computation of atomization energy compared with the B3P86 hybrid functional.15 K ϭ product ͸ ⌬H0 f Ϫ reactant ͸ ⌬H0 f. N(g). 3 DOI 10. Compared with the corresponding experimental values available. which was described in detail elsewhere [10]. BOND DISSOCIATION ENERGIES FOR THE CONO2 BOND The BDEs computed from Eq. For isodemic reactions. the HOFs were derived by designing isodesmic reactions.15 K ϩ ⌬͑PV͒ ϭ ⌬E0 ϩ ⌬ZPE ϩ ⌬HT ϩ ⌬nRT. B3PW91 functional produces a better result than B3LYP with a slight overestimation of the CONO2 bond length. (5) where ⌬E0 and ⌬ZPE are the total energy difference and the ZPE difference between products and reactants at 0 K. it can be calculated as follows: DH ͑ R Ϫ X ͒ ϭ H ͑ R ͒ ϩ H ͑ X ͒ Ϫ H ͑ RX ͒ (2) where ⌬H0 f (R) and H(R) are the heats of formation and enthalpy for R. ⌬HT is the changes in thermal correction to enthalpies between products and reactants. The optimized structures were characterized to be the relative energy minimum of the potential surface by frequency calculation (no imaginary frequencies was found).3 kcal molϪ1] [30] and CH4(g) (⌬H0 f (CH4) ϭ Ϫ17. As for different basis sets. respectively.15K ϭ ⌬E298. For the above reactions. An even better agreement with experimental values is obtained by the B3P86 and PBE0 functionals. and PBE0 functionals with 6-31g**. (4) (1) By definition.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 517 . Molecular and fragmental geometries were optimized for each computational method.15 K. DH(R Ϫ X): 0 0 DH ͑ R Ϫ X ͒ ϭ ⌬ H 0 f ͑ R ͒ ϩ ⌬ H f ͑ X ͒ Ϫ ⌬ H f ͑ RX ͒ . respectively. With respect to HOFs at 298. two different approaches were used. And the ⌬H298.15 K.15 K can be calculated from the following equations: ⌬ H 298. (3) 0 where ¥product ⌬H0 f and ¥reactant ⌬Hf are the sums of the heats of formation for products and reactants in gas at 298. H(g). RX. In this work. The zero-point energies (ZPEs) and the corresponding thermal corrections (HT) to the enthalpy (H) at 298. (2) for the CONO2 bond of nitromethane and polynitromethanes are shown in Table II. It is found that B3LYP functional with a VOL. we examine the CONO2 bond length of nitromethane and polynitromethanes by various DFT methods (Table I). 2͒. and O(g) were taken from JANAF [28]. the bond lengths predicted by B3LYP functional are the worst.15 K can be calculated through the following expression: ⌬ H 298. at room temperature is the enthalpy change of thermochemistry. ⌬ (PV) equals ⌬nRT for reaction in gas phase. We selected CH3NO2 (g) as the reference compound and designed the reaction: CH 4Ϫn͑NO2͒n ϩ ͑n Ϫ 1͒CH4 ϭ nCH3NO2 ͑n ϭ 0. the HOF was computed based on HOFs of isolated atoms and the total atomization energies ⌺D0. 107. we will assess and compare the reliability of this functional in combination with different basis sets. Results and Discussion CONO2 BOND LENGTHS First. The bond dissociation energy for a species. 1. The experimental HOFs of C(g).89 kcal molϪ1) [30] are available from experiment.15 K at 298. the heats of reaction ⌬H298.15 K were also obtained from frequency calculations and were subsequently added to the electronic energies. it should be noted that the use of diffusion functions cannot improve the results. For nitromethane. B3PW91.15 K are known. and 6-311ϩG** basis sets. we employed B3LYP. The enthalpies H were then determined and the CONO2 bond dissociation energies were obtained from equation (2).3 Ϯ 0. also included are the experimental values.BDEs AND HOFs FOR NITROMETHANE AND POLYNITROMETHANES WITH DFT prediction of BDEs using PBE0 has not been reported. For polynitromethanes. the HOFs of polynitromethanes can be obtained if the heats of reaction ⌬H298. ⌬n ϭ 0. Choosing suitable references is the key point to ensure that the conjugated bonds of NO2 are not destroyed during the reaction. respectively. NO. Since the HOFs of reference compounds CH3NO2(g) [⌬H0 f (CH3NO2) ϭ Ϫ19. 6-31ϩG**.

536 1.499/1.490 1.538 1.489 1. So we attribute the reason partly to the optimized CONO2 bond lengths.3 kcal molϪ1 to C(NO2)4. B3PW91.491 1.508 1.490/1. For CH2(NO2)2 and CH(NO2)3 molecules.492 1.499 1. the accuracy of PBE0 functional becomes better than B3P86 functional.487 1.528 1. we find that as the number of NO2 groups increases on the same C atom.5 kcal molϪ1.521 1. 32].488 — 1.544 1.517 1.511 1.490/1.500 1.1002/qua VOL. in accordance with the conclusions drawn by Politzer and colleagues [16. are presented in Table III.528 Ref. [6].492 1.503 1. What is more.505b 1.531 1.490/1.503 1. The agreement between the value calculated by B3LYP/6-31G** and the experimental value is the best.523 1. which is the desirable precision of order for quantum thermochemical methods. 107.500 1. b wide range of basis sets underestimates the BDEs for all four molecules.511 1.2 kcal molϪ1 to B3PW91. the DFT predictions become less accurate with the average absolution deviations increasing by 1.493/1. TABLE I ______________________________________________________________________________________________ CONO2 bond lengths (Å) of nitromethane and polynitromethanes calculated with different DFT methods.SU ET AL. HOF OF NITROMETHANE AND POLYNITROMETHANES Detailed results for calculated HOFs of nitromethane and polynitromethanes in the gas phase at 298.900 1. In addition.536 1. B3PW91/6-31G**.505 1.489/1. The values increase in average increment of 1.490/1. 3 . c Ref.531 1.499/1.516 1.496/1.515 1. NO. the use of polarization functions is more computationally effective than diffusion functions in the BDEs calculation for polynitromethanes system.499 1.8 kcal molϪ1 from CH3NO2 to CH2(NO2)2.503 1.505 1.503/1.526 1. levels of theory employing all four functionals (B3LYP. B3P86 CH3NO2 6-31G* 6-31ϩG* 6-31G** 6-31ϩG** CH2(NO2)2 6-31G* 6-31ϩG* 6-31G** 6-31ϩG** CH(NO2)3 6-31G* 6-31ϩG* 6-31G** 6-31ϩG** C(NO2)4 6-31G* 6-31ϩG* 6-31G** 6-31ϩG** a B3PW91 B3LYP PBE0 Expt.489/1.511 1. And as the number of nitros attached to carbon atom increases.15 K. which was also reported for CO dissociation enthalpy of hexacarbonyl molybdenum [34] and NH2OH dissociation energy calculated by the B3LYP method [14].526 1. Comparing the deviations further. [7].544 1.498 1.506 1.900 1. B3P86.490/1.498 1.488 1.517 1. Ref. The absolute deviations are within 2 kcal molϪ1.515 1.500/1. and PBE0) with 6-31G* and 518 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.531 1. we find the same trend much stronger from B3PW91 to B3P86 or PBE0 functional.488 1. The basis sets including a diffusion function (6-31ϩG*.526c 1.523 1.505 1. then 0.505 1.490/1.521 1. Both trends fit the results to experiments. together with experimental values.507 1. and PBE0/631G** are all in good agreement with experiment. 1. 6-31ϩG**) increase the error by ϳ1.514 1.494/1. which is consistent with the conclusion of CONO2 bond lengths.7 kcal molϪ1 to CH(NO2)3.508 1.491/1.517 1.511 1.489a 1.500 1.488 1. For CH3NO2. the HOFs based on atomization energies calculated by B3LYP/6-31g**.500 1.531 1.515 1.508 1. [31].487 1.491 1. and 2.538 1.

2) 56.1 (Ϫ1. B3P86 CH3ONO2 3 CH3 ϩ NO2 6-31G* 6-31ϩG* 6-31G** 6-31ϩG** CH2NO2ONO2 3 CH2NO2 ϩ NO2 6-31G* 6-31ϩG* 6-31G** 6-31ϩG** CH(NO2)2ONO2 3 CH(NO2)2 ϩ NO2 6-31G* 6-31ϩG* 6-31G** 6-31ϩG** C(NO2)3ONO2 3 C(NO2)3 ϩ NO2 6-31G* 6-31ϩG* 6-31G** 6-31ϩG** a b B3PW91 B3LYP PBE0 Expt.0 (Ϫ3. Values in parenthesis are deviations between computational results and experimental ones.9) Ref.6) (Ϫ7.6 (Ϫ2.5) (Ϫ3. For the two molecules.0) (Ϫ5.9 (Ϫ8.8 (Ϫ1.1 36.6) (Ϫ5.4 56.8 (Ϫ6.2) (Ϫ5.9 (Ϫ4. B3PW91.6 (Ϫ11.8 (Ϫ6.1 (Ϫ4. 3 DOI 10.6) 28. and PBE0 functionals.5 (Ϫ3.3) 41.6) 39.1 (Ϫ4. 40].6) 30.4 (Ϫ6.1) 40. and PBE0). The absolute deviations are within 1. which is also pointed out in previous study [34.8 46.0) 46.5) 41.6 (Ϫ11.6) 28.7) 36. surpassing the most commonly used B3PW91 and B3LYP functional.2) 36.6) (Ϫ6.6) (Ϫ4.8) 59. PBE0/6-311ϩG** yields the best result with a deviation of 2.8 41.9) 36. The study by Sniatynsky and Ceden ˜ o [34] showed that the introduction of a diffuse function into the basis set decreases the error of HOFs. the PBE0 functional can produce the best BDEs of all the four DFT approaches.4) 33.3 42.8) 45.7 (Ϫ2.1 37.9) 31.1) 43.0) (Ϫ5.6) (Ϫ8.28 kcal molϪ1.1 37.5) 39.1) 36.8) 59.0 56. B3PW91.2) 46.9 (Ϫ3.5 (Ϫ10.0) (Ϫ7. NO.2 56.9 43.3 57.9 (Ϫ3.7 (Ϫ4.8 44. It is found that large basis sets (6-311ϩG**) with diffusion functions and polarization functions can improve the HOFs for C(NO2)4 molecule.a 60.2 55. This appears to be related to the optimized CONO2 bond length.2 35.7 Ϯ 2.6 (Ϫ1.6) 60.0 (Ϫ1.3 (Ϫ3.BDEs AND HOFs FOR NITROMETHANE AND POLYNITROMETHANES WITH DFT TABLE II ______________________________________________________________________________________________ BDEs (kcal mol؊1) for CONO2 of polynitromethanes.1) 45.4 (Ϫ6. 107.9) (Ϫ6.2) 45. As for HOFs. basis sets not augmented with diffuse function enhance the calculation accuracy of HOFs.9 (Ϫ7.4 (Ϫ2. the PBE0 functional is the best method to predict the HOFs.9 (Ϫ7. Unlike the case of CH2(NO2)2 and CH(NO2)3.6 (Ϫ3.7) 39.7) 41.6 kcal molϪ1. And the accuracy for CONO2 BDEs degrades in the presence of diffusion functions.8 (Ϫ3.1002/qua INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY 519 .0) 47.5 40.7) (Ϫ6. 2.6 38.4) 33.7) (Ϫ5.2 (Ϫ0. Conclusions Our results indicate the following: 1.7) 48. the calculation of HOFs is sensitive to basis sets and the largest difference amounts to 6.7 38. the diffusion function can improve the result for B3P86.0 41.8) (Ϫ4.8 60.0) (Ϫ4.5 (Ϫ10. In addition.5 (Ϫ1. B3P86 and PBE0 functionals are found to be reliable in the calculation of CONO2 BDEs of nitromethane and polynitromethanes molecules. 6-31G** basis sets can yield good agreement with the well-established tabulated data.2 kcal molϪ1. which is lower than 1.4) (Ϫ4.58 kcal molϪ1.1 42.7) 57. as much as 6.0) 41. Table III also lists the PM3 predictions [37] of HOFs for the four molecules and the BAC/MP4 (bond-additivity-corrected Møller–Plesset fourthorder perturbation theory) result of CH3NO2 and CH2(NO2)2 from Melius’s [38] results. satisfactory results were obtained VOL.4) (Ϫ7.6 (Ϫ2. for our molecule system. Of all four functionals.8) (Ϫ7.0 (Ϫ0.6) 34. Of all the four DFT approaches (B3LYP.3) 59.1 34.9 (Ϫ1.8 (Ϫ3.6) 34.5 32.6) 60. B3P86.8 43. the calculated result of HOFs shows a dependence on the diffusion functions in the basis sets.0) 32.2 (Ϫ0.3 36.9 42. [33].9 (Ϫ8.6) (Ϫ3.2) 59. the mean absolute deviation of G2 theory for G2 neutral test set [10].5 (Ϫ3. 39.2 57.5 (Ϫ4.5) (Ϫ8.3 kcal mol.0) 31.5) (Ϫ6. As the number of NO2 group increases on the same C atom.6) 30.9) (Ϫ4. For C(NO2)4.0 (Ϫ2.3 (Ϫ1. However.2 (Ϫ2.5) 59.9) 45.

9) Ϫ3. W.6 (4. Laikhter.4 (3. 7. b with the deviation of Ͻ2 kcal molϪ1 from experimental ones for CH3NO2.3) Ϫ2. Curtiss.90) 14.2) Ϫ3. Curtiss..3 (Ϫ4. Redfern..7) Ϫ13. 106.4) 2. Redfern. V.6 (0.9 Ϫ18.15) 15. 233. 370.7 — C(NO2)4e 15.4) Ϫ13. 149. TABLE III _____________________________________________________________________________________________ Calculated HOFs and experimental ones at 298. A. Kluwer Academic: Dordrecht.5 (4.17) 14.6) Ϫ14.21 (2..1 (6..4 — — — Ϫ18. Trucks.1) Ϫ13.17) 13.... A. A. 94.4 (5.5) Ϫ19.15 K for nitromethane and polynitromethanes (kcal mol؊1). References 1. A. Glukhovtsev. Ref.8 (2. L.73) 24.7 (4.9 (5.2 CH(NO2)3e Ϫ2.73) 22. h Values in parentheses are deviations between computational results and experimental ones.0 (5. 1990.69c 6. f Ref.8 (6.0 (2.8) 1. 5.7) Ϫ3.0 (2. A. 1995.9) Ϫ13.7 (3. J.28) 19.9) Ϫ12. 40. A. B. [36]. 2463.9 Ϫ11. Raghavachari. [30]. N.1) Ϫ11.59 (4.00 (Ϫ4.5 (1. the Netherlands.39) 25. 13. 3 . J Mol Struct (Theochem) 2002.69 (Ϫ5.8 (0..3) 1. p 139.75) 23.0) Ϫ16. S. B.5 (5. L.76) 21.71 (3.45) 22.8) Ϫ13. Raghavachari. Pople.SU ET AL. 12.5 (1.4) Ϫ2. Shlyapochnikov.. I. L.. 4. J. 9. T. J Chem Phys 1991. P.3) Ϫ3.4 (4.1) 1. CH3NO2d B3LYP/6-31G* B3LYP/6-31ϩG* B3LYP/6-31G** B3LYP/6-31ϩG** B3LYP/6-311ϩG** B3P86/6-31G* B3P86/6-31ϩG* B3P86/6-31G** B3P86/6-31ϩG** B3P86/6-311ϩG** B3PW91/6-31G* B3PW91/6-31ϩG* B3PW91/6-31G** B3PW91/6-31ϩG** B3PW91/6-311ϩG** PBE0/6-31G* PBE0/6-31ϩG* PBE0/6-31G** PBE0/6-31ϩG** PBE0/6-311ϩG** Expt.6 (1. Vladimiroff. 46. PM3f Meliusg a CH2(NO2)2e Ϫ13. Rice. I. V. [35].3 Ϯ 0. J Mol Struct (Theochem) 1996.4 (1.84 (6.7 (0.97 (2. J Chem Phys 1998.42 (5.6 (3.0) Ϫ13.5) Ϫ2.38 (3.02) 14. J Chem Phys 1997. e Based on isodesmic reactions. F. 692. c Ref. CH2(NO2)2. when the diffusion functions are not included.8 (Ϫ1. Ed. F.1) 1.2) Ϫ11. C.8 (5.6 (1. the large basis sets augmented with polarization functions and diffusion functions are required to yield a good result.6) 1.6) 3. Bull Acad Sci USSR Div Chem Sci 1991. P. C. L. A.2) Ϫ11.1002/qua VOL. d Based on atomization energies.00) 23. Langhoff. 6. Curtiss.5) 2. Owens.6 (0. G. L.6) 2. 11. S. 2537.. 17460. Macbeth. S.3a Ϫ15.51) 14. 8.69) 22.69) 25. NO.3a Ϫ11. A.2) Ϫ11. K. 510.7 (3.76 Ϯ 1. F.1) Ϫ11.45 (2. Chemistry and Physics of Energetic Materials.8) Ϫ12. A. 7221.5) Ϫ17.32 (Ϫ5.5) 1.0) 2..5 (3. C. K. Nicolaides. J. and CH(NO2)3 molecules.5 (1. Raghavachari. 69. Semenov.3 (Ϫ1. J. Radom. B. 520 INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY DOI 10.9 (2.23 (Ϫ5. Mol Struct (Theochem) 1998.20 (3..02) 22. Sahu. A. B.9 (2. 452. Cherkasova. 108. L. M.5 (4. V.86 (4. M.9) Ϫ11. Ber Dtsch Chem Ges 1913. Tokmakov.. Jursic. K.96 (Ϫ5. Melius. J Mol Struct (Theochem) 1996.0 (0. 10.7 (0. A.4) Ϫ13. Quantum Mechanical Electronic Structure Calculations with Chemical Accuracy.8) Ϫ10.7 (0. [38].6) — — — — — — — Ϫ20.0) Ϫ11.5 (1. Raghavachari..9 (2.9 (2. Stefanov. J Mol Struct 1999.7 (1.37) 22.87 (3.28 (Ϫ4. Rauk. g Ref. Owens.8) — — Ϫ20.87 Ϯ 4. For C(NO2)4 molecule. Pople. the Netherlands. V.6) Ϫ2.2) Ϫ11. [37]. Curtiss. K. 65.3 (4. 2... J. 100. 370.94 (Ϫ4.. L. A.0) 1. 1063.02 Ref. Kluwer Academic: Dordrecht.7 Ϯ 0.5 (1.8 (2..1 (4. T.2 (0. 583. 3. 107.2 (5. J Phys Chem 1996.9) Ϫ13.41) 23.2) Ϫ11.7 (8. Tafipolsky.1 (0.2b Ϫ4. 11..71 (3.2) Ϫ11.0) Ϫ13..52) 15.7) Ϫ14. M. R.

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