Vibrational circular dichroism and vibrational optical rotatory dispersion in molecular crystals. II. Selection rules

Abstract

The selection rules for the contribution of the electric and magnetic dipole and electric quadrupole moments of the optical active vibrations to the gyrotropy of molecular crystals are derived by group-theoretical analysis. The peculiarities of nondegenerate and degenerate vibration modes are discussed. The selection rules for k → 0 case are tabulated for all 32 crystal classes, taking into account the time-reversal symmetry and Wigner co-representation theory.

Accurate and efficient prediction of vibrational circular dichroism spectra of condensed-phase systems with the generalized energy-based fragmentation method

“…First, we will validate the accuracy of the GEBF method for VCD spectra of large molecules compared with results from conventional molecular quantum chemistry calculations, mainly because periodic VCD calculations are unavailable at the moment. The two large molecules are star-like barrel [42] (System 1) and a helix peptide [43] (System 2, truncated from ubiquitin, residues [22][23][24][25][26][27][28][29][30][31][32][33][34]. Our results reveal that the GEBF-VCD protocol can reproduce the conventional quantum chemical VCD spectra with good accuracy and efficiency.…”

“…This simplified model can substantially reduce the computational costs but fails to reflect the physics behind VCD activity. Planewave-based theory [25][26][27][28] for VCD spectra has been suggested for more than three decades. However, its computational program has not been implemented to date due to the extremely expensive computational costs of required tensors.…”