Origin-independent sum over states simulations of magnetic and electronic circular dichroism spectra via the localized orbital/local origin method
© 2015 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 36(2015), 10 vom: 15. Apr., Seite 723-30 |
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| Format: | Online-Aufsatz |
| Sprache: | English |
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2015
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| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article density functional theory electronic circular dichroism magnetic circular dichroism origin-dependence |
| Zusammenfassung: | © 2015 Wiley Periodicals, Inc. Although electronic and magnetic circular dichroism (ECD, MCD) spectra reveal valuable details about molecular geometry and electronic structure, quantum-chemical simulations significantly facilitate their interpretation. However, the simulated results may depend on the choice of coordinate origin. Previously (Štěpánek and Bouř, J. Comput. Chem. 2013, 34, 1531), the sum-over-states (SOS) methodology was found useful for efficient MCD computations. Approximate wave functions were "resolved" using time-dependent density functional theory, and the origin-dependence was avoided by placing the origin to the center of mass of the investigated molecule. In this study, a more elegant way is proposed, based on the localized orbital/local origin (LORG) formalism, and a similar approach is also applied to generate ECD intensities. The LORG-like approach yields fully origin-independent ECD and MCD spectra. The results thus indicate that the computationally relatively cheap SOS simulations open a new way of modeling molecular properties, including those involving the origin-dependent magnetic dipole moment operator |
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| Beschreibung: | Date Completed 11.05.2015 Date Revised 10.03.2015 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.23845 |