We present a study of extremal entanglement witnesses on a bipartite composite quantum system. We define the cone of witnesses as the dual of the set of separable density matrices, thus [Formula: see text] when [Formula: see text] is a witness and [Formula: see text] is a pure product state, [Formula: see text] with [Formula: see text]. The set of witnesses of unit trace is a compact convex set, uniquely defined by its extremal points. The expectation value [Formula: see text] as a function of vectors [Formula: see text] and [Formula: see text] is a positive semidefinite biquadratic form. Every zero of [Formula: see text] imposes strong real-linear constraints on f and [Formula: see text]. The real and symmetric Hessian matrix at the zero must be positive semidefinite. Its eigenvectors with zero eigenvalue, if such exist, we call Hessian zeros. A zero of [Formula: see text] is quadratic if it has no Hessian zeros, otherwise it is quartic. We call a witness quadratic if it has only quadratic zeros, and quartic if it has at least one quartic zero. A main result we prove is that a witness is extremal if and only if no other witness has the same, or a larger, set of zeros and Hessian zeros. A quadratic extremal witness has a minimum number of isolated zeros depending on dimensions. If a witness is not extremal, then the constraints defined by its zeros and Hessian zeros determine all directions in which we may search for witnesses having more zeros or Hessian zeros. A finite number of iterated searches in random directions, by numerical methods, leads to an extremal witness which is nearly always quadratic and has the minimum number of zeros. We discuss briefly some topics related to extremal witnesses, in particular the relation between the facial structures of the dual sets of witnesses and separable states. We discuss the relation between extremality and optimality of witnesses, and a conjecture of separability of the so-called structural physical approximation (SPA) of an optimal witness. Finally, we discuss how to treat the entanglement witnesses on a complex Hilbert space as a subset of the witnesses on a real Hilbert space.
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