Yes, it is possible. Orbitals are just a mathematical basis for a decomposition of charge distribution.
Some of them might be negative, but the total sum would be always positive.
As far as i remember, negative values might appear if you look at a single zetas of a complex DZ orbital, but when you sum them up into a full DZ it should be positive. I don't remember whether same is true for decomposition into L quantum numbers.
Alex.

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