Nitrile Vibrational Lifetimes as Probes of Local Electric Fields.

Abstract

Optical measurements of electric fields have wide-ranging applications in the fields of chemistry and biology. Previously, such measurements focused on shifts in intensity or frequency. Here, we show that nitrile vibrational lifetimes can report local electric fields through ultrasensitive picosecond mid-infrared-near-infrared double-resonance fluorescence spectro-microscopy on Rhodamine 800. Using a robust convolution fitting approach, we observe that the nitrile vibrational lifetimes are strongly linearly correlated (R2 = 0.841) with solvent reaction fields. Supported by density functional theory, we rationalize this trend through a doorway model of intramolecular vibrational energy redistribution. This work provides new fundamental insights into the nature of vibrational energy flow in large polyatomic molecular systems and establishes a theoretical basis for electric field sensing with vibrational lifetimes, offering a new experimental dimension for probing intracellular electrostatics.