Quantitative agreement between experiment and theory for Vibrational Circular Dichroism enhanced by electronically excited states

TL;DR

This study demonstrates that vibrational circular dichroism (VCD) enhancement in transition metal complexes can be accurately modeled by treating excitation energies as adjustable parameters, enabling reliable spectral simulations and chiral structure analysis.

Contribution

The paper introduces a parameter optimization approach for excitation energies in VCD simulations, improving agreement with experimental spectra for transition metal complexes.

Findings

VCD intensity is highly sensitive to excitation energies.

Standard quantum chemistry methods struggle to predict these energies accurately.

Optimizing excitation energies yields simulated spectra with high similarity to experiments.

Abstract

Intensity enhancement in vibrational circular dichroism (VCD) arises in open-shell transition metal complexes from coupling between ground-state vibrational transitions and magnetic dipole-allowed transitions to low-lying excited states (LLESs). In this work we apply Nafie's vibronic coupling theory to M(II)-(-)-sparteine-Cl$_2$ (M=Zn, Co, Ni) complexes to investigate these enhancement effects. We show that the VCD intensity is extremely sensitive to the excitation energies that neither time-dependent density functional theory (TDDFT) nor state-averaged complete active space self consistent field (SA-CASSCF) calculations can predict with sufficient accuracy. We argue that instead of using more accurate quantum chemistry methods these excitation energies can be treated as parameters and optimized against experimental spectra. With this approach we obtain simulated VCD similarity scores above 0.4, a threshold considered reliable for absolute configuration assignment. The ability to quantitatively reproduce enhanced experimental spectra with computations opens up new research areas, offering amongst else unique possibilities for the study of chiral structure of systems such as transition metal complexes and metalloproteins that so far remained intractable.