Black-Box Simulations of Anharmonic Vibrational Chiroptical Spectra: Problems with Property Third Derivatives and the Solvent.

ABSTRACT: Chiroptical methods, including vibrational circular dichroism (VCD) and Raman optical activity (ROA), reveal details about molecular structure. For three model molecules, α-pinene, camphor, and fenchone, we show that increased sensitivity of modern spectrometers makes it possible to record even fine spectral features, such as overtone and combination bands. However, understanding, interpretation, and simulation of them require relatively expensive computations, going beyond the harmonic approximation. For this purpose, vibrational perturbation theory at the second order (VPT2) has proven to provide an excellent price-performance balance. As it becomes more common, inconsistencies in electronic structure calculations, hidden by error compensation at the harmonic level, emerge. In particular

SUBMITTER: Yang Q 

PROVIDER: S-EPMC12573746 | biostudies-literature | 2025 Oct

REPOSITORIES: biostudies-literature