Assessing the Partial Hessian Approximation in QM/MM-Based Vibrational Analysis.

Abstract

The partial Hessian approximation is often used in vibrational analysis of quantum mechanics/molecular mechanics (QM/MM) systems because calculating the full Hessian matrix is computationally impractical. This approach aligns with the core concept of QM/MM, which focuses on the QM subsystem. Thus, using the partial Hessian approximation implies that the main interest is in the local vibrational modes of the QM subsystem. Here, we investigate the accuracy and applicability of the partial Hessian vibrational analysis (PHVA) approach as it is typically used within QM/MM, i.e., only the Hessian belonging to the QM subsystem is computed. We focus on solute-solvent systems with small, rigid solutes. To separate two of the major sources of errors, we perform two separate analyses. First, we study the effects of the partial Hessian approximation on local normal modes, harmonic frequencies, and harmonic IR and Raman intensities by comparing them to those obtained using full Hessians, where both partial and full Hessians are calculated at the QM level. Then, we quantify the errors introduced by QM/MM used with the PHVA by comparing normal modes, frequencies, and intensities obtained using partial Hessians calculated using a QM/MM-type embedding approach to those obtained using partial Hessians calculated at the QM level. Another aspect of the PHVA is the appearance of normal modes resembling the translation and rotation of the QM subsystem. These pseudotranslational and pseudorotational modes should be removed as they are collective vibrations of the atoms in the QM subsystem relative to a frozen MM subsystem and, thus, not well-described. We show that projecting out translation and rotation, usually done for systems in isolation, can adversely affect other normal modes. Instead, the pseudotranslational and pseudorotational modes can be identified and removed.