A spectrum of models that estimate assimilation rate A from intercellular carbon dioxide concentration (Ci) and measured stomatal conductance to CO2 (gc) were investigated using leaf-level gas exchange measurements. The gas exchange measurements were performed in a uniform loblolly pine stand (Pinus taeda L.) using the Free Air CO2 Enrichment (FACE) facility under ambient and elevated atmospheric CO2for 3 years. These measurements were also used to test a newly proposed framework that combines basic properties of the A–Ci curve with a Fickian diffusion transport model to predict the relationship between Ci/Ca and gc, where Ca is atmospheric carbon dioxide concentration. The widely used Ball–Berry model and five other models as well as the biochemical model proposed by Farquhar et al. (1980) were also reformulated to express variations in Ci/Ca as a function of their corresponding driving mechanisms. To assess the predictive capabilities of these approaches, their respective parameters were estimated from independent measurements of long-term stable carbon isotope determinations (δ13C), meteorological variables, and ensemble A–Ci curves. All eight approaches reproduced the measured Areasonably well, in an ensemble sense, from measured water vapour conductance and modeled Ci/Ca. However, the scatter in the instantaneous A estimates was sufficiently large for both ambient and elevated Ca to suggest that other transient processes were not explicitly resolved by all eight parameterizations. An important finding from our analysis is that added physiological complexity in modeling Ci/Ca (when gc is known) need not always translate to increased accuracy in predicting A. Finally, the broader utility of these approaches to estimate assimilation and net ecosystem exchange is discussed in relation to elevated atmospheric CO2.