The R ratio is a useful diagnostic of the X-ray emitting astrophysical plasmas defined as the intensity ratio of the forbidden over the inter- combination lines in the Kα line complex of He-like ions. The value is altered by excitation processes (electron impact or UV photoexcitation) from the metastable upper level of the forbidden line, thereby constraining the electron density or UV field intensity. The diagnostic has been applied mostly in electron density constraints in collisionally ionized plasmas using low-Z elements as was originally proposed for the Sun (Gabriel & Jordan (1969a, MNRAS, 145, 241)), but it can also be used in photoionized plasmas. To make use of this diagnostic, we need to know its value in the limit of no excitation of metastables (R0 ), which depends on the element, how the plasmas are formed, how the lines are propagated, and the spectral resolution affecting line blending principally with satellite lines from Li-like ions. We benchmark R0 for photoionized plasmas by comparing calculations using radiative transfer codes and observation data taken with the Resolve X-ray microcalorimter onboard XRISM. We use the Fe XXV Heα line complex of the photo-ionized plasma in Centaurus X-3 observed during eclipse, in which the plasma is expected to be in the limit of no metastable excitation. The measured R = 0.65 ± 0.08 is consistent with the value calculated using xstar for the plasma parameters derived from other line ratios of the spectrum. We conclude that the R ratio diagnostic can be used for high-Z elements such as Fe in photoionized plasmas, which has wide applications in plasmas around compact objects at various scales.