# studying of the phenomenon of internal rotation in n-mononitroalkilnyh radicals

Electronic structure n-mononitroalkilnyh radicals C^{e}H_{2} (CH_{2}) _{n}NO_{2}интересно that in electronic density ρ (r) their endgroups two diffuse clouds - not coupled electron е* in C^{e}H_{2}и not divided pairs oxygen in NO_{2} are located.

^{e}H

_{2}(CH

_{2})

_{n}NO

_{2}, including, and on internal rotation characteristics (factors of potential functions V (φ) and barriers conformational peyorehodov V). Earlier it has been shown, that radical centre C

^{e}H

_{2}(Chapter 3 and [4, 3, 24]) okazyyovaet essential influence on parametres V (φ) and barriers of two communications C-C going successively in n-alkilnyh radicals (Chapters 2 see, 3 and [10]). Is of interest to track podobyonye changes in molecules C

^{e}H2 (CH2) nNO2, containing heteroatoms, to position zakoyonomernosti, connected directly and with rotation of the radical centre and it vzaiyomodejstviem with not hydrocarbonaceous group, and also to compare the received results with inductive effects of nuclear groupings in molecules of alkanes and mononitroalkayonov [10, 2].

Potential functions V (φ) n-trans-mononitroalkilnyh radicals (only 44 functions, Table 4.116 ÷ 4.120) have been calculated for all internal rotations in C^{e}H_{2} (CH_{2}) _{n}NO_{2} where n = 0 ÷ 7, method B3LYP∕6-311 ++ (3df, 3pd), and also in initial goyomologah by means of MP2∕6-311 ++ (3df, 3pd) by means of program GAUSSIAN [226] in the Cartesian basis 6d 10f the Step of co-ordinate of reaction - two-sided angle φ - made 10 °. For each rotation positions and values full energy perehodyonyh conditions and local minima - extremums of a surface potential eneryogii (SHHE) have been specified. Transient states are found by means of procedure QST3 [492, 493]. poyogreshnost numerical calculation of full energy E_{tota}lне exceeded 1? 10^{-10}а.е. (Less than 1 Dzh/MOLE), and elements of a matrix of density 3? 10^{-6}. Proceeding from it, factors razloyozhenija V (φ) abreast Fouriers of Table 4.116 ÷ 4.120 are resulted to within 1 Dzh/MOLE. Functions V (φ) at rotation about communication C-N are approximated by a number (4.142) with n = 2, and round communications C-C, as in the form of decomposition (4.142) with n = 1, and (4.167)

Molecule C^{e}H2NO2 - initial homologue of a number - flat (it agree B3LYP∕6 - 311 ++ (3df, 3pd) and MP2∕6-311 ++ (3df, 3pd)), and its structure falls into to point group C_{2v}. Close arrangement C^{e}H_{2}и NO_{2}в the yielded connection result ins strong vzaimodejyostviju electronic clouds of trailer oxygen and «free valency» - them soyoprjazheniju (see the Chapter III), that is expressed in the significant size of barrier Vglob equal

29.07 and 22.66 kdzh/MOLE (B3LYP and MP2 accordingly, Table 4.116). We will notice, that if in mother compound with a selfcontained cover (CH_{3}NO_{2}) size V_{g}ι_{ob} calculated poyosredstvom МР2 (0.05 kdzh/MOLE), exceeds that for DFT (0.03 kdzh/MOLE), in C*H_{2}NO_{2}наблюдается the return.

_{2}-N

_{o2predpolagaet}an explanation in terms of "stabilising linking», as in initial molecule C

_{h3-No2barer}V

_{g}I

_{ob}на two orders less (see above and [1]). As well in C*H

_{2}-CH

_{3}where peyorekryvaetsja inductive influence of endgroups, but is absent linking, V

_{g}l

_{o}bмал and 0.23 kdzh/MOLE [4] is equal. Approximating (4.142) points of section PPE found with pomoyoshchju MP2/6-311 ++ (3df, 3pd) for C*H

_{2}-NO

_{2}, result ins to badly converging number (4.142 [1] that is reflected in value are nonviscous Δ ≈ 1 kdzh/MOLE, (at B3LYP in 5 times it is less). KoeffitsiYOenty V (φ) in that and other decomposition (MP2 and DFT) are significant (Table 4.116). It speaks about essential redistribution ρ (r) at change of two-sided angle φ, connected, in bolshej to a measure, with the form curve V (φ) (Drawing 4.19).

The phenomenon of "linking" essentially increasing a barrier of rotation, from the point of view of quantum mechanics can be presented as consequence of distribution chayosti P_{e}. (r) in basins of the next groups, in this case NO_{2}, and on the contrary (see Chapter 2).

Interaction of kernels with the electronic density distributed on different basins, stabilises structure (stiffens it). Kernels "feel" each other posredyostvom delokalizovannoj ρ (r). Such interaction affects all distribution rg), and not just on local parts p_{R} (r), where R - fragments making a molecule, causing the co-ordinated movement of kernels and result ining significant work on them peremeshcheyoniju in electronic clouds - to internal rotation barriers (Drawings 4.19 and 4.20).

The barrier of turn of group NO_{2} (Table 4.116, Drawing 4.21) at following homologue C_{2}H_{4}-N_{o2rezko} decreases till 0.60 a kdzh/MOLE (0.37 kdzh/MOLE also is small and equal in mother compound C_{2}H_{5}-N_{o2on} [1]). Most likely, it is connected with increased lokalizatsiyoej not coupled electron е* on radical centre S*N_{2} (Chapters 2 and 3 see) and smaller perturbation p_{m}, _{ι} (r) from the side е*. I.e. kernels turn together with electron atmospheres falling into with it p_{R} (r), and the basic deformation ρ (r) occurs in the field of communication. In the subsequent molecules nitrogroup rotation (since C3H6-NO2) is weak zayovisit from chain length, and, hence, from distribution of electronic density, otnoyosimoj to е* (Table 4.116, Drawing 4.21 see). With increase in number of groups SN_{2} the parametres describing internal rotation, converge quickly to corresponding sizes in n - alkanes, n-alkilnyh radicals [4, 3, 24] and n-nitroalkanes [1]. So, characteristics vrayoshchenija groups NO2 in initial molecules and radicals coincide (with the account pogreshnoyo

sti), since C^{e}H_{2} (CH_{2}) _{5}-N_{o2i} CH_{3} (CH_{2}) _{3}-NO_{2}. I.e. electronic density nitrogrupyopy p_{NO} (it is poorly subject to action of the next groups, that allows to use for it the term "isolation" (compactness p_{NO} (r)). The Same concerns and system of atoms C^{e}H_{2}CH_{2} - (the previous partitions and [4] see also). Similar supervision result in survivabilities NO_{2}и of other fragments, and from here to shipping of their partial properties, including, falling into to internal rotation.

Linking infringement between electron atmospheres of endgroups not otmeyonjaet their interactions, though and weakened by inclusion between them "neutral" fragments CH_{2}. Display of it is the double gosh-effect [232] in C^{e}H_{2} (CH_{2}) _{3}NO_{2} - equality energy a trance and gosh "conformstions at rotation about communications C^{e}H_{2}CH_{2} - (CH_{2}) _{2}NO_{2}и C^{e}H_{2} (CH_{2}) _{2}-CH_{2}NO_{2} (see more low), and also difference in structure C^{e}H_{2} (CH_{2}) _{n}NO_{2}, with n

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