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The 13 C and 15 N chemical shifts of the α and γ crystal forms of nylon 6 have been estimated
using ab initio calculations (GIAO method) with the B3LYP Density Functional and the
6-311G(d) basis set. Calculations were applied on proper model systems and the
agreement with experimental data was quite good in all cases. Comparison between the
results obtained for isolated chains and hydrogen bonded sheets allowed to elucidate the
influence of the conformation and packing forces in the chemical shifts. These results open
up new opportunities for the future use of quantum mechanical calculations as a
complementary tool in the determination of the crystal structure of polymers.
C 2002 Kluwer Academic Publishers
0022–2461
C 2002 Kluwer Academic Publishers 3589
Lindenmeyer by slight crystal structural changes de- expectation value of the molecule with respect to the
pending on the annealing conditions [10]. In this work exterior magnetic field B and the nuclear magnetic mo-
we used the unit cell deduced by Holmes et al. for the α ment µ of the nucleous M in question [11].
form: a = 9.56 Å, b (fiber axis) = 17.24 Å, c = 8.01 Å,
α = γ = 90◦ and β = 67.5◦ [6]. This unit cell contains ∂2 E
σαβ
M
= α, β = x, y, z (1)
four molecules, which adopt an all-trans conformation, ∂µαM ∂ Bβ
distributed in two hydrogen bonded sheets (Fig. 1a). It
is worth noting that polymer chains are arranged in anti- where E = H and H is the full Hamiltonian of the sys-
parallel within the sheets. tem including magnetic perturbations. For powder sam-
The structure reported by Arimoto [6] has been ples, MAS-NMR experiments only detect the isotropic
used for describing the γ form. This consists of two part of the tensor, σiso . Thus, in this case all orientations
molecules packed in antiparallel within a unit cell of the chemical shift tensor relative to the external mag-
of dimensions a = 9.33 Å, b (fiber axis) = 16.88 Å, netic field occur.
c = 4.78 Å, α = γ = 90◦ and β = 121◦ . In this case the σxx + σyy + σzz
chain axis is shorter than for the α form, since the two σiso = (2)
3
dihedral angles adjacent to the amide groups have sig-
nificantly smaller values, i.e., about ±120◦ (Fig. 1b). In Both carbon and nitrogen isotropic shielding constants,
contrast to the α form, hydrogen bonds are established σ (13 C) and σ (15 N), of nylon 6 were computed using
between sheets. perturbation theory and the GIAO method [12] im-
Molecular systems were built by replacing the poly- plemented in the Gaussian 94 program package [13].
mer chains at crystal structures described for the α and It should be emphasized that GIAO calculations are
γ forms by small model molecules (see below). The very expensive from a computational point of view
standard bond lengths and bond angles for polyamides and, therefore, they are usually applied to small model
were considered. systems.
The electronic structure of the molecular models was
2.2. GIAO calculations of chemical shifts determined using Density Functional Theory (DFT)
In quantum mechanical terms, the shielding constant methods, which include some electron correlation
σ is the mixed second-order perturbation of the energy effects not present at the Hartree-Fock level. More
specifically, the Becke’s [14] three-parameter hybrid
functional with gradient corrections provided by the
LYP functional [15] (B3LYP) was used. The Kohn-
Sham orbitals were constructed using Gaussian-type
atomic orbitals basis sets. All the calculations were per-
formed using the 6-311G(d) basis set [16] to describe
the C, H and O atoms of the models under study.
Theoretical calculations yield absolute values with
respect to the bare nucleous in vacuo whereas experi-
mental data refer to a references (TMS and NH3 for 13 C
and 15 N, respectively). Thus, the experimental scale δ
(chemical shift) is related to the theoretical scale σ via
δ = σ − σ0 (3)
where σ0 is the theoretical value of the reference. The
13
C isotropic shielding constant in TMS, σ (13 C)TMS =
184.2 ppm, was computed in a previous work at the
level of theory described above [17]. The 15 N shield-
ing constant in NH3 , σ (15 N)NH3 = 269.9 ppm, has been
computed in the same way for the present study.
No. C1 O C2 C3 C4 C5 C6 N H(N)
3593
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FORESMAN, C. Y. PENG, P. Y. AYALA, W. CHEN,
M. W. WONG, J. L. ANDRES, G. REPLOGLE, J. B. Received 26 October 2001
FORESMAN, C. Y. PENG, P. Y. AYALA, W. CHEN, M. and accepted 6 May 2002
3594