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Edward can read everybodies thoughts exceptBella's of course, but he heard Jessica say - "That's Edward Cullen, totally gorgious, obviously. But apparently nobody here is good enough for him. Like I care."

So Edward could tell how Jessica felt, and found it ammusing that she'd say that. He smiled because there was no one in the school, or anywhere, that he felt love towards. That is, before he meets Bella.

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Q: Why does Edward smile when Jessica explains to Bella that Edward is the only single Cullen from Twilight?
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