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I've been using standard deviation as a direct/simple approach to calculate volatility of a given intraday feed data. My question is it logical/sensible that using root mean square (RMS), which is the square root of mean of squared return as an estimation of volatility?

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It can be used if your intra day data has a mean very close to 0. $$ \sigma=\sqrt{E(x^2)-E(x)^2} $$ if we have $$E(x) \approx 0 \Rightarrow E(x)^2 \approx 0$$ then $$ \sigma = \sqrt{E(x^2)}$$

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