Cavity Ring-Down Spectroscopy at Benchmark-Level Sub-Permille Accuracy Enabled by a System-Level Detection Transfer Function
Cavity ring-down spectroscopy (CRDS) is widely used for sensitive optical absorption measurements, but its quantitative accuracy can be limited at the few-percent level by systematic distortions originating in the CRDS detection system, particularly at short ring-down times. These limitations can restrict demanding spectroscopic applications requiring sub-permille accuracy, including atmospheric sensing, tests of ab initio theory and fundamental physics, and quantum-based optical gas standards. Here we develop a methodology based on a system-level detection transfer function describing the complete CRDS detection-system response, including detector, electronics, and digitization stages, and use it to correct previously unaccounted-for instrumental distortions in retrieved absorption. We demonstrate the method on a CO absorption line measured down to very short ring-down times using multiple independent CRDS detection configurations, initially exhibiting line-area biases of up to 14%. After applying the transfer-function correction, all systems converge to a common value, with the bias relative to the most accurate ab initio-validated reference data reaching the sub-permille level and the accuracy improving by a factor of 41--87. The proposed framework brings well-established CRDS to the level of the most accurate reference methods without requiring specialized measurement schemes or external calibration standards, making benchmark-quality measurements more widely accessible.