The Interplay of Pauli Repulsion, Electrostatics, and Field Inhomogeneity for Blueshifting and Redshifting Vibrational Probe Molecules

TL;DR

This study computationally analyzes how Pauli repulsion, electrostatics, and field inhomogeneity influence vibrational frequency shifts in probe molecules, clarifying their responses in complex environments.

Contribution

It reveals the conditions under which vibrational probes exhibit redshifting or blueshifting, emphasizing the roles of electrostatic strength and field inhomogeneity.

Findings

Redshifting occurs when electrostatic interactions overcome Pauli repulsion.

Field inhomogeneity can significantly reinforce or weaken vibrational shifts.

Probe response depends on atomic mass and electric field sign.

Abstract

Many molecules' vibrational frequencies are sensitive to intermolecular electric fields, enabling them to probe the field in complex molecular environments. However, it is often unclear whether the probe is responding to the local electric field or other types of intermolecular interactions, inhibiting interpretation of the frequency and effectiveness as probes. This is especially true of molecules whose vibrational frequencies blueshift instead of the more typical redshift in hydrogen bonding configurations. Here we computationally investigate the causes of redshifting versus blueshifting over a range of vibrational reporters. First, we apply adiabatic energy decomposition analysis to a paradigmatic set of probes, finding that redshifting only occurs when electrostatic interactions are strong enough to overcome the dominant and large blueshifting contribution of Pauli repulsion. Furthermore, we demonstrate that field inhomogeneity can further shift the frequency of many probes substantially to either reinforce or counteract the shift expected from a homogeneous field. We find that redshifting is reinforced by electric field inhomogeneity, otherwise field inhomogeneity further weakens the electrostatic contribution relative to Pauli repulsion, leading to blueshifting. Further calculations indicate that the probe's response to field inhomogeneity can be understood by considering the mass of the atoms involved in the stretching mode and sign of the electric field. In explaining the interplay of different intermolecular interactions and field inhomogeneity for many probes, our results should enable the use and interpretation of spectroscopic probes and their connection to electric fields in more complex systems.