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Jeppe Olsen

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

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AB-INITIO CALCULATION OF ELECTRONIC CIRCULAR-DICHROISM FOR TRANS-CYCLOOCTENE USING LONDON ATOMIC ORBITALS. / Bak, Keld L.; Hansen, Aage E.; Ruud, K.; Helgaker, T.; Olsen, Jeppe; Jørgensen, Poul.

In: Theoretica chimica acta, Vol. 90, No. 5-6, 03.1995, p. 441-458.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaperJournal articleResearchpeer-review

Harvard

Bak, KL, Hansen, AE, Ruud, K, Helgaker, T, Olsen, J & Jørgensen, P 1995, 'AB-INITIO CALCULATION OF ELECTRONIC CIRCULAR-DICHROISM FOR TRANS-CYCLOOCTENE USING LONDON ATOMIC ORBITALS', Theoretica chimica acta, vol. 90, no. 5-6, pp. 441-458.

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Author

Bak, Keld L. ; Hansen, Aage E. ; Ruud, K. ; Helgaker, T. ; Olsen, Jeppe ; Jørgensen, Poul. / AB-INITIO CALCULATION OF ELECTRONIC CIRCULAR-DICHROISM FOR TRANS-CYCLOOCTENE USING LONDON ATOMIC ORBITALS. In: Theoretica chimica acta. 1995 ; Vol. 90, No. 5-6. pp. 441-458.

Bibtex

@article{4b72453d8d5046f591ca7090711e3374,
title = "AB-INITIO CALCULATION OF ELECTRONIC CIRCULAR-DICHROISM FOR TRANS-CYCLOOCTENE USING LONDON ATOMIC ORBITALS",
abstract = "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.",
keywords = "ELECTRONIC CIRCULAR DICHROISM, TRANS-CYCLOOCTENE, LONDON ATOMIC ORBITALS, CORRELATED MOLECULAR CALCULATIONS, GAUSSIAN-BASIS SETS",
author = "Bak, {Keld L.} and Hansen, {Aage E.} and K. Ruud and T. Helgaker and Jeppe Olsen and Poul J{\o}rgensen",
year = "1995",
month = "3",
language = "English",
volume = "90",
pages = "441--458",
journal = "Theoretica chimica acta",
issn = "0040-5744",
publisher = "Springer Verlag",
number = "5-6",

}

RIS

TY - JOUR

T1 - AB-INITIO CALCULATION OF ELECTRONIC CIRCULAR-DICHROISM FOR TRANS-CYCLOOCTENE USING LONDON ATOMIC ORBITALS

AU - Bak, Keld L.

AU - Hansen, Aage E.

AU - Ruud, K.

AU - Helgaker, T.

AU - Olsen, Jeppe

AU - Jørgensen, Poul

PY - 1995/3

Y1 - 1995/3

N2 - 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.

AB - 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.

KW - ELECTRONIC CIRCULAR DICHROISM

KW - TRANS-CYCLOOCTENE

KW - LONDON ATOMIC ORBITALS

KW - CORRELATED MOLECULAR CALCULATIONS

KW - GAUSSIAN-BASIS SETS

M3 - Journal article

VL - 90

SP - 441

EP - 458

JO - Theoretica chimica acta

JF - Theoretica chimica acta

SN - 0040-5744

IS - 5-6

ER -