CHARACTERIZATION OF CRYSTALLINE PIGMENTS WITH LOW-FREQUENCY VIBRATIONAL SPECTROSCOPY AND SOLID-STATE DENSITY FUNCTIONAL THEORY
Date of Award
Doctor of Philosophy (PhD)
Timothy M. Korter
historical pigments, Low-frequency Raman spectroscopy, solid-state density functional theory, Terahertz time-domain spectroscopy
Physical Sciences and Mathematics
Although historical pigments are seldom found in the modern artist’s palette, their characterization is a critical aspect of designing effective conservation and restoration protocols, establishing provenance, and detecting forgeries. Ideal characterization methods are nondestructive, noninvasive, and able to distinguish between pure and mixed pigment samples. Spectroscopic techniques are commonly used to identify pigment composition because of their non-ionizing nature, rapid acquisition times, and safety. Unfortunately, the majority of these methods have difficulty distinguishing between pigments with similar chemical and physical properties. Recent advancements in instrument technology have increased the broader availability of terahertz time-domain spectroscopy (THz-TDS) and low-frequency Raman spectroscopy (LFRS). In this work, the capabilities of THz-TDS and LFRS for identification and characterization of historic and modern pigments were evaluated. These experimental studies were supported with solid-state density functional theory (ss-DFT) simulations of the pigment structures and vibrations to gain insight into the molecular and intermolecular origins of the observed spectral features. These results demonstrate the powerful combination of low-frequency (≤ 200 cm-1) vibrational spectroscopic methods and computational techniques for the identification and characterization of pigments and establish the compelling abilities of THz-TDS and LFRS as new tools for characterization of pigment components in artworks and artifacts.
Kleist, Elyse M., "CHARACTERIZATION OF CRYSTALLINE PIGMENTS WITH LOW-FREQUENCY VIBRATIONAL SPECTROSCOPY AND SOLID-STATE DENSITY FUNCTIONAL THEORY" (2020). Dissertations - ALL. 1230.