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

Abstract

Abstract The vibrational circular dichroism (VCD) spectra could determine the molecular chirality of condensed-phase systems, but their quantum chemistry calculations are costly. The fragment-based methods have not been applied to the VCD spectra of periodic systems yet. In this work, we have extended the generalized energy-based fragmentation (GEBF) approach to accurately and efficiently compute the VCD spectra of chiral molecular crystals under periodic boundary conditions (PBCs) and macromolecules in solutions. In this approach, the Hessian matrices, atomic polar/axial tensors of a target system, are evaluated as a linear combination of the corresponding quantities from a series of small electrostatically embedded subsystems. Comparisons of GEBF and conventional VCD spectra of two large molecules show that this approach can satisfactorily reproduce the conventional computational results. Then, we applied the PBC-GEBF method to calculate the VCD spectra of a chiral molecular crystal and two macromolecules in solutions. Our results show that the experimental VCD spectrum can be roughly reproduced in terms of both band shape and vibrational peaks. The GEBF-VCD and PBC-GEBF-VCD approaches are expected to be practical tools to investigate the chirality of molecular crystals and macromolecules in solutions.