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The LaTeX command for simeq (≃) is \simeq.
\simeqWrite \simeq inside math mode — that is, between $…$ for inline math or in a \[ … \] / equation block for display math. It is part of core LaTeX math, so no extra package is required.
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Use \simeq in math mode — it needs no extra package. For example, $a \simeq b$.
None — \simeq is built into LaTeX's math mode, so no extra package is required.