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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, Peoples 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 sufciently 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 2 kcal mol1 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: 515521, 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, 515521 (2007) 2006 Wiley Periodicals, Inc.

SU ET AL.

Introduction
itromethane, CH3NO2, 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. Nitromethane can also be used as rocket fuel, and its detonation velocity is near that of RDX (cyclotrimethylene) with the same density. Dinitromethane is known to be distinguished with extremely low thermal stability, and a series of 4-nitropyrazoles can be synthesized from it [1]. Trinitromethane is a less explosive detonator. It will be decomposed at a temperature of 298 K and will be detonated by friction or impact. A severe explosion was reported [2] during the preparation of a sodium trinitromethanide salt. Tetranitromethane (TNM) is a well-characterized oxidant that reacts with inorganic compounds such as superoxide to generate NO2 and the trinitromethane anion. It can also serve as a much more powerful explosive when mixed with nitrobenzene. It is well known that the breaking and making of chemical bonds is involved in most chemical reactions. Thus, chemists, biochemists, and chemical engineers need the values of bond dissociation energies (BDEs) of molecules. Moreover, the stabilities and impact/shock sensitivities of explosives are closely correlated to the strength of CONO2 bond [35]. The structures and vibrational frequencies have been studied for polynitromethanes theoretically by Tapolsky et al. [6] and Vladimiroff [7]. To the best of our knowledge, no attempt has been made to compute the CONO2 BDEs. Heats of formation (HOFs), as elementary thermodynamic properties, are required to evaluate the explosive performances of energetic materials. For stable compounds, there are experimental data of HOFs. However, for unstable compounds, determination of the HOFs experimentally is impractical and dangerous. Therefore, it is necessary to determine the CONO2 BDEs and HOFs theoretically for polynitromethanes. As for the computational method, it has been demonstrated that high-quality levels of theory, such as G2, G2(MP2), G2(MP2, SVP), CBS, and CCSD(T), have been developed to give accurate results [8 12]. However, the impractical problem is that the sophisticated methods require far too much computational time and disk space to treat electron correlation. This limits their applicability to rather small molecules, consisting of up to seven or eight non-hydrogen atoms where computational re-

sources are limited. The density functional theory (DFT) predictions, while not as good as the G2 predictions, are sufciently accurate to be used to study many classes of molecules. They empower us both to obtain results close to experimental results at moderate computational cost and to extend calculations to much larger systems. Therefore, we employed DFT in our study. Generally, different computational methods are suitable for various kinds of molecular systems in calculating the BDEs. For example, 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, while BHandH is demonstrated to be a better method than B3LYP for the BDEs of sulfur-containing molecules [15]. It was reported that the B3P86/ 6-31G** procedure could compute the satisfactory BDEs of the studied small-size molecular system, and the diffusion function is needed to scale down the results [16]. And for nitroaromatic molecules, the B3P86/6-311G** method was reported to be able to give satisfactory CONO2 BDEs [17]. Thus, it would be useful to test which method is reliable for the calculation of the BDEs for the polynitromethane molecular system. Isodemic reactions [18], in which numbers of electron pairs and chemical bond types are conserved, have been successfully employed for the calculation of HOFs [19, 20]. They allow for a cancellation of errors inherent in the approximate treatment of electron correlation on both sides of the reaction. So, to increase the accuracy, we applied isodemic reactions to the prediction of HOFs for the polynitromethane molecular system.

Methods and Computational Details


All calculations were carried out with the Gaussian 03 program package [21]. The hybrid density functionals used in this study are semi-empirical exchange-correlation functionals B3LYP [22, 23], B3P86 [22, 24], and B3PW91 [22, 25]; a parameter free density functional model PBE0 [26]; 6-31G*, 6-31G*, 6-31G**, 6-31G**, and 6-311G** basis sets were used. In the PBE0 functional, only one coefcient is theoretically adjusted to 0.25, reecting the mix of HartreeFock or exact exchange and the DFT exchange, which is represented by the PBE density functional [27]. The correlation part is also represented by the PBE correlation functional [27] with coefcient equal to one. So far as we know, the

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BDEs AND HOFs FOR NITROMETHANE AND POLYNITROMETHANES WITH DFT prediction of BDEs using PBE0 has not been reported. In this work, we will assess and compare the reliability of this functional in combination with different basis sets. The bond dissociation energy for a species, RX, at room temperature is the enthalpy change of thermochemistry, DH(R X):
0 0 DH R X H 0 f R H f X H f RX .

For the above reactions, the heats of reaction H298.15 K at 298.15 K can be calculated through the following expression: H 298.15 K

product

H0 f

reactant

H0 f,

(4)

(1)

By denition, it can be calculated as follows: DH R X H R H X H RX (2)

where H0 f (R) and H(R) are the heats of formation and enthalpy for R, respectively. Molecular and fragmental geometries were optimized for each computational method. The optimized structures were characterized to be the relative energy minimum of the potential surface by frequency calculation (no imaginary frequencies was found). The zero-point energies (ZPEs) and the corresponding thermal corrections (HT) to the enthalpy (H) at 298.15 K were also obtained from frequency calculations and were subsequently added to the electronic energies. The enthalpies H were then determined and the CONO2 bond dissociation energies were obtained from equation (2). With respect to HOFs at 298.15 K, two different approaches were used. For nitromethane, the HOF was computed based on HOFs of isolated atoms and the total atomization energies D0, which was described in detail elsewhere [10]. The experimental HOFs of C(g), H(g), N(g), and O(g) were taken from JANAF [28]. 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, we employed B3LYP, B3PW91, and PBE0 functionals with 6-31g**, 6-31G**, and 6-311G** basis sets. For polynitromethanes, the HOFs were derived by designing isodesmic reactions. Choosing suitable references is the key point to ensure that the conjugated bonds of NO2 are not destroyed during the reaction. We selected CH3NO2 (g) as the reference compound and designed the reaction: CH 4nNO2n n 1CH4 nCH3NO2 n 0, 1, 2. (3)

0 where product H0 f and reactant Hf are the sums of the heats of formation for products and reactants in gas at 298.15 K, respectively. Since the HOFs of reference compounds CH3NO2(g) [H0 f (CH3NO2) 19.3 0.3 kcal mol1] [30] and CH4(g) (H0 f (CH4) 17.89 kcal mol1) [30] are available from experiment, the HOFs of polynitromethanes can be obtained if the heats of reaction H298.15 K are known. And the H298.15 K can be calculated from the following equations:

H 298.15K E298.15 K PV E0 ZPE HT nRT, (5)

where E0 and ZPE are the total energy difference and the ZPE difference between products and reactants at 0 K, respectively; HT is the changes in thermal correction to enthalpies between products and reactants; (PV) equals nRT for reaction in gas phase. For isodemic reactions, n 0.

Results and Discussion


CONO2 BOND LENGTHS First, we examine the CONO2 bond length of nitromethane and polynitromethanes by various DFT methods (Table I). Compared with the corresponding experimental values available, the bond lengths predicted by B3LYP functional are the worst. B3PW91 functional produces a better result than B3LYP with a slight overestimation of the CONO2 bond length. An even better agreement with experimental values is obtained by the B3P86 and PBE0 functionals. As for different basis sets, it should be noted that the use of diffusion functions cannot improve the results. BOND DISSOCIATION ENERGIES FOR THE CONO2 BOND The BDEs computed from Eq. (2) for the CONO2 bond of nitromethane and polynitromethanes are shown in Table II, also included are the experimental values. It is found that B3LYP functional with a

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SU ET AL. TABLE I ______________________________________________________________________________________________


CONO2 bond lengths () of nitromethane and polynitromethanes calculated with different DFT methods. B3P86 CH3NO2 6-31G* 6-31G* 6-31G** 6-31G** CH2(NO2)2 6-31G* 6-31G* 6-31G** 6-31G** CH(NO2)3 6-31G* 6-31G* 6-31G** 6-31G** C(NO2)4 6-31G* 6-31G* 6-31G** 6-31G**
a

B3PW91

B3LYP

PBE0

Expt. 1.489a

1.488 1.490 1.488 1.489 1.490/1.503 1.490/1.505 1.490/1.505 1.493/1.506 1.507 1.511 1.508 1.511 1.526 1.531 1.526 1.531

1.491 1.492 1.491 1.492 1.490/1.503 1.490/1.500 1.494/1.500 1.496/1.500 1.511 1.515 1.511 1.514 1.531 1.536 1.531 1.536

1.498 1.499 1.498 1.499 1.499/1.515 1.500/1.516 1.499/1.515 1.503/1.517 1.517 1.521 1.517 1.521 1.538 1.544 1.538 1.544

1.487 1.488 1.487 1.488 1.489/1.900 1.491/1.500 1.489/1.900 1.490/1.503 1.505b 1.505 1.508 1.505 1.508 1.526c 1.523 1.528 1.523 1.528

Ref. [31]. Ref. [6]. c Ref. [7].


b

wide range of basis sets underestimates the BDEs for all four molecules. The values increase in average increment of 1.2 kcal mol1 to B3PW91, in accordance with the conclusions drawn by Politzer and colleagues [16, 32]. What is more, we nd the same trend much stronger from B3PW91 to B3P86 or PBE0 functional. Both trends t the results to experiments, which is consistent with the conclusion of CONO2 bond lengths. So we attribute the reason partly to the optimized CONO2 bond lengths. And as the number of nitros attached to carbon atom increases, the accuracy of PBE0 functional becomes better than B3P86 functional. In addition, the use of polarization functions is more computationally effective than diffusion functions in the BDEs calculation for polynitromethanes system. The basis sets including a diffusion function (6-31G*, 6-31G**) increase the error by 1.5 kcal mol1, which was also reported for CO dissociation enthalpy of hexacarbonyl molybdenum [34] and NH2OH dissociation energy calculated by the B3LYP method [14]. Comparing the deviations further, we nd that as the number of NO2 groups increases on the same

C atom, the DFT predictions become less accurate with the average absolution deviations increasing by 1.8 kcal mol1 from CH3NO2 to CH2(NO2)2, then 0.7 kcal mol1 to CH(NO2)3, and 2.3 kcal mol1 to C(NO2)4. HOF OF NITROMETHANE AND POLYNITROMETHANES Detailed results for calculated HOFs of nitromethane and polynitromethanes in the gas phase at 298.15 K, together with experimental values, are presented in Table III. For CH3NO2, the HOFs based on atomization energies calculated by B3LYP/6-31g**, B3PW91/6-31G**, and PBE0/631G** are all in good agreement with experiment. The absolute deviations are within 2 kcal mol1, which is the desirable precision of order for quantum thermochemical methods. The agreement between the value calculated by B3LYP/6-31G** and the experimental value is the best. For CH2(NO2)2 and CH(NO2)3 molecules, levels of theory employing all four functionals (B3LYP, B3P86, B3PW91, and PBE0) with 6-31G* and

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BDEs AND HOFs FOR NITROMETHANE AND POLYNITROMETHANES WITH DFT TABLE II ______________________________________________________________________________________________ BDEs (kcal mol1) for CONO2 of polynitromethanes.
B3P86 CH3ONO2 3 CH3 NO2 6-31G* 6-31G* 6-31G** 6-31G** CH2NO2ONO2 3 CH2NO2 NO2 6-31G* 6-31G* 6-31G** 6-31G** CH(NO2)2ONO2 3 CH(NO2)2 NO2 6-31G* 6-31G* 6-31G** 6-31G** C(NO2)3ONO2 3 C(NO2)3 NO2 6-31G* 6-31G* 6-31G** 6-31G**
a b

B3PW91

B3LYP

PBE0

Expt.a 60.8

60.2 (0.6) 60.2 (0.6) 60.0 (0.8) 59.8 (1.0) 47.0 (1.8) 45.8 (3.0) 46.7 (2.1) 45.5 (3.3) 41.2 (2.5) 39.7 (4.0) 41.0 (2.7) 39.5 (4.2) 36.1 (4.4) 33.8 (6.7) 36.1 (4.4) 33.8 (6.7)

57.3 57.2 57.0 56.8 44.1 42.9 43.9 42.6 38.3 36.7 38.1 36.5

(3.5) (3.6) (3.8) (4.0) (4.7) (5.9) (4.9) (6.2) (5.4) (7.0) (5.6) (7.2)

56.4 56.2 56.2 55.8 43.0 41.3 42.8 41.1 37.2 35.1 37.1 34.9

(4.4) (4.6) (4.6) (5.0) (5.8) (7.5) (6.0) (7.7) (6.5) (8.6) (6.6) (8.8)

59.6 (1.2) 59.5 (1.3) 59.3 (1.5) 59.1 (1.7) 48.8 46.9 (1.9) 45.6 (3.2) 46.6 (2.2) 45.3 (3.5) 41.6 (2.1) 40.0 (3.7) 41.4 (2.6) 39.8 (3.9) 36.9 (3.6) 34.4 (6.1) 36.9 (3.6) 34.4 (6.1)

43.7 2.5

40.5 32.9 (7.6) 30.5 (10.0) 32.9 (7.6) 30.5 (10.0) 31.9 (8.6) 28.6 (11.9) 31.9 (8.6) 28.6 (11.9)

Ref. [33]. Values in parenthesis are deviations between computational results and experimental ones.

6-31G** basis sets can yield good agreement with the well-established tabulated data. The absolute deviations are within 1.2 kcal mol1, which is lower than 1.58 kcal mol1, the mean absolute deviation of G2 theory for G2 neutral test set [10]. Of all four functionals, the PBE0 functional is the best method to predict the HOFs. In addition, the calculation of HOFs is sensitive to basis sets and the largest difference amounts to 6.3 kcal mol, which is also pointed out in previous study [34, 39, 40]. For the two molecules, the calculated result of HOFs shows a dependence on the diffusion functions in the basis sets. 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, as much as 6.6 kcal mol1. However, for our molecule system, basis sets not augmented with diffuse function enhance the calculation accuracy of HOFs. For C(NO2)4, PBE0/6-311G** yields the best result with a deviation of 2.28 kcal mol1. Unlike the case of CH2(NO2)2 and CH(NO2)3, the diffusion function can improve the result for B3P86, B3PW91, and PBE0 functionals. It is found that large basis sets (6-311G**) with diffusion functions and polarization functions can improve the HOFs for C(NO2)4 molecule.

Table III also lists the PM3 predictions [37] of HOFs for the four molecules and the BAC/MP4 (bond-additivity-corrected MllerPlesset fourthorder perturbation theory) result of CH3NO2 and CH2(NO2)2 from Meliuss [38] results.

Conclusions
Our results indicate the following: 1. Of all the four DFT approaches (B3LYP, B3P86, B3PW91, and PBE0), B3P86 and PBE0 functionals are found to be reliable in the calculation of CONO2 BDEs of nitromethane and polynitromethanes molecules, surpassing the most commonly used B3PW91 and B3LYP functional. This appears to be related to the optimized CONO2 bond length. And the accuracy for CONO2 BDEs degrades in the presence of diffusion functions. As the number of NO2 group increases on the same C atom, the PBE0 functional can produce the best BDEs of all the four DFT approaches. 2. As for HOFs, satisfactory results were obtained

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SU ET AL. TABLE III _____________________________________________________________________________________________


Calculated HOFs and experimental ones at 298.15 K for nitromethane and polynitromethanes (kcal mol1). CH3NO2d B3LYP/6-31G* B3LYP/6-31G* B3LYP/6-31G** B3LYP/6-31G** B3LYP/6-311G** B3P86/6-31G* B3P86/6-31G* B3P86/6-31G** B3P86/6-31G** B3P86/6-311G** B3PW91/6-31G* B3PW91/6-31G* B3PW91/6-31G** B3PW91/6-31G** B3PW91/6-311G** PBE0/6-31G* PBE0/6-31G* PBE0/6-31G** PBE0/6-31G** PBE0/6-311G** Expt. PM3f Meliusg
a

CH2(NO2)2e 13.5 (1.2) 11.4 (3.4) 13.5 (1.2) 11.5 (3.2) 11.6 (3.1) 13.5 (1.2) 11.7 (3.0) 13.6 (1.1) 11.9 (2.9) 12.0 (2.7) 13.5 (1.2) 11.7 (3.0) 13.5 (1.2) 11.8 (2.9) 11.9 (2.8) 13.6 (1.1) 11.8 (2.9) 13.7 (1.0) 11.9 (2.8) 12.0 (2.7) 14.7 0.3a 11.9 11.87 4.2

CH(NO2)3e 2.6 (0.6) 3.1 (6.3) 2.7 (0.5) 2.8 (6.0) 2.4 (5.6) 2.8 (0.4) 2.0 (5.2) 3.0 (0.3) 1.6 (4.8) 1.3 (4.5) 2.6 (0.6) 2.2 (5.4) 2.7 (0.5) 1.9 (5.1) 1.5 (4.7) 3.1 (0.1) 1.7 (4.9) 3.2 (0.0) 1.4 (4.6) 1.1 (4.3) 3.2b 4.7

C(NO2)4e 15.3 (4.39) 25.84 (6.15) 15.00 (4.69) 25.42 (5.73) 24.59 (4.90) 14.69 (5.00) 23.20 (3.51) 14.32 (5.37) 22.71 (3.02) 22.21 (2.52) 15.28 (4.41) 23.86 (4.17) 14.94 (4.75) 23.38 (3.69) 22.71 (3.02) 14.23 (5.45) 22.87 (3.17) 13.96 (5.73) 22.45 (2.76) 21.97 (2.28) 19.69c 6.4

18.7 (0.6) 14.5 (4.8) 10.7 (8.6) 20.3 (1.0) 16.9 (2.4) 13.5 (5.8) 20.8 (1.5) 17.4 (1.9) 13.8 (5.5) 19.3 0.3a 15.9 18.76 1.02

Ref. [30]. Ref. [35]. c Ref. [36]. d Based on atomization energies. e Based on isodesmic reactions. f Ref. [37]. g Ref. [38]. h Values in parentheses are deviations between computational results and experimental ones.
b

with the deviation of 2 kcal mol1 from experimental ones for CH3NO2, CH2(NO2)2, and CH(NO2)3 molecules, when the diffusion functions are not included. For C(NO2)4 molecule, the large basis sets augmented with polarization functions and diffusion functions are required to yield a good result.

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