HENCSEI, P.

NAGY, J.

English

Periodica Polytechnica (Budapest University of Technology and Economics)

CALCULATION OF THE MOLECULAR STRUCTURE OF ANILINE DERIVATIVES By J. NAGY and P. HENCSEI Department of Inorganic Chemistry. Technical University. Budapest (Received December 23. 1970) Introdnction Seyeral authors haye already dealt with the calculation of the molecular structure of aniline and aniline deriYatiYes. Calculation of the bond structure of aniline deriyatives served to investigate the molecular structure of N-tri-methyl-silyl-aniline derivatiyes. In our "work the =r bond systems were cal-culated by the Pariser-Parr-Pople method taking the a polarization into consideration, thus, by combining the Del Re and PPP methods. Our results were compared with data from ultraviolet spectra and experimental dipole moment values. Molecular structures of the following compounds were investi-gated: aniline (I), N-methyl-aniline (H), N,N-dimethyl-aniline (HI). Quantum-chemical calculations In calculating the a bond system of molecules the approximate method of DEL RE was used [1]. The parameters, partly original and partly modified by us, necessary for the calculations, have been published in [2]. The a charge distribution of the molecules is given in Fig. 1. The direction of bond dipole moment vectors are shown by arrows in the figure. The =r system has been .calculated by the PARISER-PARR-POPLE method [3, 4]. In each compound, the valence state ionization potential of atoms 'was calculated as a function of effective nuclear charge defined by BURl'is [5]. Our calculations haye shown that the BURNS method determines the shielding factors more exactly as if calculating with the effectiye nuclear charges fixed according to Slater. In the course of determining the shielding parameters, promotion and hybridization states haye been taken into account, too. Go partial charges obtained hy the DEL RE method and q:r electron popu-lations ohtained from the calculation of the :iT system have heen considered for the calculation of the effective nuclear charge of an atom in a molecule. So the real effectiye nuclear charges have been calculated in the following ,,-av: z= zo 114 H H H H J. NA.GY and P. HEI'!CSEI +0.2799 H~CD/H .l\ -0.6746 +0.0660 CD °0° CD CV o -0.0450 H +0,0409 +0,0424 H -0.0203 -0.0389 I H +0,0410 -:-0.0259 H +OJ~ /~~ N -0.4838 +0.0486 o -0.0405 H 0.0409 +0.0423 H 0.0220 -0,0392 II H +0,0410 H H CALCULATION OF MOLECULAR STRUCTURE +0,0357 o -0,0405 H +0.0409 +0,0422 H . -0,0236 -0,0393 H +0,0410 ILL 115 Fig. 1. u-partial charges of aniline (1), N-methyl-aniline (II) and N,N-dimethyl-aniline (Ill) +0,1514 NHz -0,0290 o -0.0238 -0,0441 -0,0052 T +0,1241 NHCH J -0,0191 o -0,0200 -0,0383 -0.0042 Il +0,1047 N(CH J )2 a-.... ~ ; -0,0]25 o -0.0174 -0,0339 -0,0035 III Fig. 2. :x-partial charges and :it bond orders of aniline (1), N-methyl-aniline (11) and N,N-dimethyl-aniline (Ill) Instead of parabolic functions found in the literature, exponential func-tions determined by transformation were used or experimental data were started from for the calculation of ionization energies. The equations of car-2 116 J. SAGY and P. HENCSEI bon and nitrogen atoms are the following: Uc = -0.6133 exp (1.036 Z) U N+ = -3.6528 exp (0.5468 Z) Values for ('if were taken from [6]: ('cc = 11.13 eV, YNN = 17.44 eV. The values of Yij were calculated according to NiATAGA and NISHHIOTO [7] from the bond distances. The resonance integrals (f3ij) were determined by the approximate for-mula of \VOLFSBERG and HELl\IHOLTZ [8] in the following way: where k is a proportionality factor the value of which was determined from the experimental and calculated resonance and overlapping integrals of ben-zene: k = 0.6426. Sij is an overlapping integral the value of which 'was calculated from an integral tabulation [9] as a function of the bond distance and effective nuclear charges. Table I compiles the initial data necessary for the calculation of the ;r systems. In our calculations the nitrogen atom "was considered to be in Sp2 hybrid state in the three molecules. Accordingly, the bond angles of nitrogen were chosen as 1200 and a planar arrangement was supposed. Bond distances were assumed [10] as: RNH = 1.014 A, RNC .. ~r = 1.426 A, R NCAlk = 1.474 A, Rcc = 1.397 A, RCAcH = 1.084 A, RC .. ~IkH = 1.093 A. The calculations were carried out on a computer RAZDAN-3. The Zi' U i and (Xi values were changed using the results obtained in the oth approx-imation, but the {Jij values were considered to be constant. The approxima-tions were continued to self-consistence. The eigenvalues, linear coefficients, partial charges, electron densities and bond orders for the examined compounds were determined. Configuration interactions "were taken into consideration, too, and by the aid of these interactions the values of singlet and triplet CALCGLATIOS OF JIOLECVLAR STRGCTURE IF Table I Initial data for calculation of n-bond system of aniline-derivatives with PPP method I. lI. Ill. Zl 4.264 4.331 4.385 Z2 3.173 3.167 3.163 Za 3.143 3.142 3.142 Z4 3.136 3.136 3.136-Zo 3.136 3.136 3.136 Ul (eV) -25.637 26:591 -27 .. 396 U2 -11.430 -11.358 -11.306 U a -11.078 n,071 -11.064 U 4 11.004 -11.003 -11.002 Uo -10.997 10.997 -10.997 fJ12 (eV) 2.1845 2.1899 2.1855 fJ23 2.4109 2.4147 2.4084 fJa4 2.4015 2.4006 2.3997 fJ40 2.3927 2.3926 2.3924 transItIOn energies as well as oscillator strengths were determined. The cal-culation results are presented in Fig. 2, Tables 2 and 3. Discussion The bond polarities, bond moments, PG and p" dipole moment and resuit-ant dipole moment of the compound were calculated from the (j and :T charge Table 2 Eigenvalues of aniline-derivatives (cV) I. H. Ill. El -13.5225 -13.6502 -13.7816 E2 11.3935 11.6465 11.8860 E a 9.9615 -10.00:H -10.0303 E4 8.6564 8.9614 9.1817 Eo 0.4003 0.4462 0.4782 EG 0.2552 0.3102 0.3564 E; 2.6342 2.5932 2.5574 2* 118 J. NAGY and P. HENCSEI Table 3 Values of singlet (lEcl) and triplet (3ECI) transition-energies and oscillator strengths for aniline derivatives 'Ecr(eV) f 'Em (eV) 4.4334 0.044 2.8222 5.3496 0.393 3.4939 I. 6.2965 0.420 3.7664 6.6909 0.805 4.8337 7.5866 0.665 5.8202 7.8297 0.189 6.4295 I 4.5716 0.033 2.9357 5.5392 0.324 3.6354 6.4807 Il. 0.598 3.8314 6.7218 0.894 4.8424 7.7247 0.506 6.1545 7.9329 0.140 6.6249 4.6556 0.024 2.9906 5.6808 0.261 3.7253 6.6194 0.766 3.8745 Ill. 6.7552 0.980 4.8469 7.8826 0.349 6.4346 8.0379 0.097 6.7720 I distribution of molecules. The calculated dipole moments are compared with experimental values in Table 4. The experimental ultraviolet absorption data of the aniline derivatives are compared "With the calculated values of singlet and triplet transitions and oscillator strengths. For sake of comparison, the figure shows a few results by other authors. Tables 4 and 5 sho'w a good agreement between experimental and cal-Table 4 Calculated and experimental dipole moments of aniline-derivatives f1.q 1-'" rent I-'exp [11] Ll (D) (D) (D) (D) (D) 1. 0.176 1.757 1.933 1.56 -0.37 Il. 0.163 1.460 1.615 1.67 +0.05 Ill. 0.125 1.249 1.374 1.57 +0.20 Table 5 Experimental and ealculatcd singlet transitions (in eV) and oscillator strengths of aniline-derivatives 'Ear (f) lEar(f) Diffl!rtmcc Dutu enkulntcd hy other nllthorH (~XpCriUlcntnl cnlculutcd ("V) I I hy UH [14J [15 J [16] [17] [18J [6) ~ ~ 4.40 (0.023) [12] 4.43 (0.044,) -0.03 4,.37 (0.05) 4,.39 (0.043) '1 .. 33 (0.0,1.3) 4.31 (0.033) 4 .. 39 (0.05) 4,.39 (0.075) 5.39 (0.144) 5.35 (0.393) -1-0.04 5.35 (0.34,) 5.50 (0.264,) 5.50 (0.265) 5.30 (0.435) 5.23 (0.33) 5.43 (0.316) <"'l :>. I 6.40 (0.510) 6.35 (0.55) 6.40 (0.732) I. 6.30 (0.'1.20) -1- 0.10 6.40 (0.729) 6.6B (0.737) 6.33 (0.54) 6.36 (0.606) t-< <"'l 6.33 (0.570) 6.69 (0.305) -1-0.19 6.55 (0.37) 6.60 (1.035) 6.59 (1.06t\.) 6.74 (1.023) 6.50 (0.32) 6.63 (1.034.) (::l :>. 7.37 (0.630) 7.59 (0.665) +0.23 7.66 (0.295) 7.65 (0.295) ..., Cl 7.33 (0.139) 7.70 (0.003) ~ c ":! 4,.20 [13] 4.57 (0.033) -0.37 4.09 (0.07) '"" .... c t-< 5.54 (0.324) 5.03 (0.4.6) 5.10 -0.404 t>l <"'l II. I 6.43 (0.593) 6.07 (0.27) (::l :>. 6.72 (0.394) 6.49 (0.76) ~ '" 7.72 (0.506) ;;J 7.93 (0.140) R ..., ~ 4,.30 (0.M4) [12] 4.66 (0.024) -0.36 3.93 (0.03) 4.23 (0.065) t>l 5.15 (0.256) 5.63 (0.261) -0.53 5.01 (0.50) 5.33 (0.343) Ill. I 6.25 (0.350) 6.62 (0.766) -0.37 6.01 (0.22) 6.27 (0.540) 6.33 (0.575) 6.76 (0.930) -1-0.12 6.403 (0.74) 6.59 (1.044.) 7.63 (0.310) 7.33 (0.34,9) -0.20 7.403 (0.4053) 3.04 (0.097) 7.'1.9 (0.016) --<0 120 J. ,''-AGY and P. HESCSEI culated values for both dipole moment and ultraviolet data. This fact proves that the applied Del Re and PPP methods supply proper values for the molec-ular structure of aniline derivatives. Summary Quantum·chemical calculations were made for various aniline derivatives. For calcu-lating the u- and :r-bond systems the Del Re method and the Pariser-Parr-Pople method, respectively, were used, taking the u-polatization into account. The results show a good agree-ment for the experimental dipole moments and the data of ultraviolet spectra. References 1. DEL RE, G.: J. Chem. Soc. 4031 (1958) 2. NAGY, J., HENCSEI, P., REFFY, J.: Acta Chim. Acad. Sci. Hung. 65, 51 (1970) 3. PARISER, R., PARR, R. G.: J. Chem. Phys. 21, 767 (1953) 4. POPLE, J. A.: Trans. Faraday Soc. 49, 1375 (1953) 5. BURNs, G.: J. Chem. Phys. 41, 1521 (1964) 6. NISHThIOTO, K., FORsTER, L. S.: Theoret. Chim. Acta, 4, 155 (1966) 7. l\lATAGA, K., NISHDIOTO, K: Z. Phys. Chem. (Frankfurt) 13, 40 (1957) 8. WOLFSBERG, M., HEL:ilIHOLTZ, L.: J. Chem. Phys. 20, 837 (1952) 9. KRUGLJAK, A., W'HIT)[AN, D. R.: Tab!. integro kvantovoy khimii, Tom I, Vychislitelniy Centr. Akad. Nauk USSR. Moscow. 1965. 10. Tables of Interatomic Distan~es and Configuration in Molecules and Ions. The Chemical Society, London, 1958 11. MCCELLAN, A. L.: Tables of experimental dipole moments. Freeman and Co. London, 1963 12. KIlIWRA, K, NAGAKURA, S.: Molecular Physics 9, 117 (1965) 13. KmvRA, K, TsuBo:\wRA, H., NAGAKVRA, S.: Bull. Chem. Soc. Japan 3i, 1336 (1964) 14. BILLINGSLEY, F. P., BLooR, J. E.: Theoret. Chim. Acta, 11, 325 (1968) 15. NISHDIOTO, K.: Theoret. Chim. Acta i, 207 (1967) 16. NISHIMOTO, K.: Theoret. Chim. Acta, 10, 65 (1968) 17. FORSHEY, D. R., PUKANIC, G. W., WEGENER, BR. J. D., GREENSHIELDS, J. B.: Theoret. Chim. Acta 9, 288 (1968) 18. KLESSINGER, M.: Theoret. Chim. Acta 5, 236 (1966) Dr. J6zsef NAGY Dr. Pal HENCSEI } Budapest XL, Gellert ter 4, Hungary 

CALCULATION OF THE MOLECULAR STRUCTURE OF ANILINE DERIVATIVES

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CALCULATION OF THE MOLECULAR STRUCTURE OF ANILINE DERIVATIVES

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Periodica Polytechnica (Budapest University of Technology and Economics)