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Poul Jørgensen

AB-INITIO CALCULATION OF ELECTRONIC CIRCULAR-DICHROISM FOR TRANS-CYCLOOCTENE USING LONDON ATOMIC ORBITALS

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The second-quantization magnetic dipole operator that arises when London atomic orbitals are used as basis functions is derived. In atomic units, the magnetic dipole operator is defined as the negative of the first derivative of the electronic Hamiltonian containing the interaction with the external magnetic field. It is shown that for finite basis sets, the gauge origin dependence of the resulting magnetic dipole operator is analogous to that of the exact operator, and that the derived operator converges to the exact operator in the limit of a complete basis set. It is also demonstrated that the length expression for the rotatory strength in linear response calculations gives gauge-origin-independent results. Sample calculations on ti ans-cyclooctene and its fragments are presented. Compared to conventional orbitals, the basis set convergence of the rotatory strengths calculated in the length form using London atomic orbitals is favourable. The rotatory strength calculated for trans-cyclooctene agrees nicely with the corresponding experimental circular dichroism spectrum, but the spectra for the fragment molecules show little resemblance with that of trans-cyclooctene.

OriginalsprogEngelsk
TidsskriftTheoretica chimica acta
Vol/bind90
Nummer5-6
Sider (fra-til)441-458
Antal sider18
ISSN0040-5744
StatusUdgivet - mar. 1995

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