Department of Chemistry, University of Virginia , Charlottesville, Virginia 22904-4319, United States.
J Phys Chem A. 2013 Dec 19;117(50):13399-411. doi: 10.1021/jp406691e. Epub 2013 Sep 23.
An optimized nonlinear least-squares fit algorithm for data processing in cavity ring-down spectroscopy (CRDS) is discussed, which improves the calculation efficiency substantially over using a general purpose fitting package. Theoretical absorption sensitivity limits for both the detector noise and the shot noise limited situations are derived and compared with experimental results. The effect of limiting the bandwidth of detection system on ring-down signal is discussed and compared with real ring-down data. The optimal trigger level and fitting interval are obtained for continuous wave cavity ring-down spectroscopy (cw-CRDS) in both the detector noise and shot noise limits, with the resulting sensitivity in units of cm(-1) per (Hz(1/2)) derived. Interestingly, it is found that the optimized shot noise limited sensitivity in cw-CRDS method is, in principle, comparable with the ultimate sensitivity of noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS).
讨论了一种用于腔衰荡光谱(CRDS)数据处理的优化非线性最小二乘拟合算法,与使用通用拟合程序包相比,该算法大大提高了计算效率。推导并比较了探测器噪声和散粒噪声限制情况下的理论吸收灵敏度极限。讨论了限制检测系统带宽对衰荡信号的影响,并与实际衰荡数据进行了比较。在探测器噪声和散粒噪声限制下,获得了连续波腔衰荡光谱(cw-CRDS)的最佳触发水平和拟合区间,并以 cm(-1) / (Hz(1/2))为单位得出了灵敏度。有趣的是,发现在 cw-CRDS 方法中,优化的散粒噪声限制灵敏度原则上可与噪声免疫腔增强光外差分子光谱学(NICE-OHMS)的极限灵敏度相媲美。