This work presents the first simulations of the full optical rotation (OR) tensor at coupled cluster with single and double excitations (CCSD) level in the modified velocity gauge (MVG) formalism. The CCSD‐MVG OR tensor is origin independent, and each tensor element can in principle be related directly to experimental measurements on oriented systems. We compare the CCSD results with those from two density functionals, B3LYP and CAM‐B3LYP, on a test set of 22 chiral molecules. The results show that the functionals consistently overestimate the CCSD results for the individual tensor components and for the trace (which is related to the isotropic OR), by 10%–20% with CAM‐B3LYP and 20%–30% with B3LYP. The data show that the contribution of the electric dipole–magnetic dipole polarizability tensor to the OR tensor is on average twice as large as that of the electric dipole–electric quadrupole polarizability tensor. The difficult case of (1
The importance of the electric‐dipole—electric‐quadrupole polarizability contribution to the vibrational Raman optical activity (VROA) and dimensionless circular intensity difference spectra of (1
- NSF-PAR ID:
- 10457452
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Journal of Raman Spectroscopy
- Volume:
- 51
- Issue:
- 4
- ISSN:
- 0377-0486
- Page Range / eLocation ID:
- p. 669-679
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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