Scientifically analyzing ancient and unique objects of antiquity such as pottery and paintings is necessary to answer many questions of interest to the field of cultural heritage. This field encompasses diverse disciplines including anthropology, archaeology, conservation and art history. In many instances, it is of interest to identify specific targets or molecular markers to evaluate, for example, what pigment colors a paint layer or what foodstuff pottery may have held. While today's standard spectroscopy and mass spectrometry methods are highly effective, specific questions remain difficult to answer and the development of laser desorbed, jet-cooled, REMPI laser ionized, time-of-flight mass spectrometry (REMPI laser MS) as an alternate analytical technique to simplify and improve cultural heritage object analysis is presented in this dissertation. By combining multiphoton ionization and double resonance spectroscopy with mass spectrometry, both exceptionally well resolved vibronic spectroscopy and fragment-free mass spectrometry for molecules of interest can be performed simultaneously. In doing so, this technique offers two advantages over commercial equipment: First, wavelength selectivity in the ionization step is utilized so that only the analyte of interest is ionized, irrespective of matrix or mixture complexity; this eliminates the need for either sample preparation or chromatography. Secondly, gas phase mass spectrometry allows for immediate differentiation between molecules considered spectroscopically indistinguishable in the aqueous phase based on an inherent characteristic, molecular mass, rather than by often highly variable instrumental parameters, such as retention time. These advantageous characteristics of REMPI laser MS allow smaller sample sizes than commercial MS instruments, which in turn require less damage to objects of cultural heritage.

REMPI laser MS was applied as an analytical tool for cultural heritage initially in the fields of archaeology and anthropology, using theobromine and caffeine as molecular markers to identify ceremonial chocolate beverages in Mesoamerican pottery. Preparation of extracts and pottery sherds for analysis, as well as instrumental parameters for the detection of theobromine were optimized extensively. Theobromine in samples from two different Mesoamerican archaeological sites was successfully identified, and this method will be expanded to analyze pottery sherds for wine residues. REMPI laser MS will be applied to the field of art to analyze examine painting cross-sections and threads from tapestries for dye and pigment analyses in a new microscope-REMPI laser mass spectrometer.