The use of localized molecular orbitals and the polarization propagator to identify transmission mechanisms in nuclear spin‐spin couplings

International Journal of Quantum Chemistry - Tập 37 Số 5 - Trang 663-677 - 1990
A. C. Diz1, Martín C. Ruiz de Azúa1, Claudia G. Giribet1, Rubén H. Contreras1
1Depto. de Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pab. 1, (1428) Buenos Aires, Argentina

Tóm tắt

AbstractAn extension of the IPPP (inner projections of the polarization propagator) method to theoretically analyze transmission mechanisms of indirect nuclear spin‐spin couplings is presented. The localization technique used is modified so that all the canonical molecular orbitals of a compound may be localized to represent chemical bonds, lone pairs, and the corresponding antibonding molecular orbitals. These localized molecular orbitals, together with the polarization propagator, are used to obtain an intuitive picture of how a coupling is generated as a sum of terms, each one consisting of two particle‐hole single excitations. This picture can be used to identify underlying transmission mechanisms and quantitatively evaluate their importance toward the total coupling. The paramagnetic spin‐orbit and the spin‐dipole interactions are studied in detail.

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Tài liệu tham khảo

Emsley J. W., 1965, High Resolution NMR spectroscopy

10.1016/0009-2614(67)85076-0

10.1063/1.1676166

10.1063/1.1679049

10.1021/cr60262a001

Cunliffe A. V., 1975, J. Magn. Reson., 3, 1729

10.1021/ja00403a007

10.1007/BF00574433

Engelmann A. R., 1982, Quantum Chem. Program Exchange Bull., 2, 14

10.1021/ja00330a002

10.1002/qua.560230327

10.1016/0009-2614(84)85060-5

10.1016/0010-4655(86)90097-4

Contreras R. H., 1985, Magn. Reson. Rev., 9, 239

10.1002/mrc.1270220614

Pople J. A., 1970, Approximate Molecular Orbital Theory

10.1016/0079-6565(77)80013-7

10.1002/qua.560300752

10.1071/CH9871923

10.1016/0166-1280(88)80001-0

10.1002/mrc.1260251011

10.1016/0301-0104(79)80115-9

10.1103/PhysRev.91.303

Oddershede J., 1978, Advances in Quantum Chemistry

Linderberg J., 1973, Propagators in Quantum Chemistry

10.1063/1.1733693

CNINDO 3.3.3 Program by M. D. Beer NMR Program Library Daresbury Warrington WA4 4AD U. K.

10.1002/mrc.1260240809

10.1002/mrc.1270060903

10.1016/0009-2614(75)85179-7

10.1007/BF00551364

10.1016/0166-1280(85)85011-9

10.1002/mrc.1260230510

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Thông tin xuất bản

International Journal of Quantum Chemistry

Tập 37 Số 5

663-677

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