Perhaps pip is not installed on your system, only pip3.
My system showed that I only have pip3, not pip. Use which pip3 and which pip to see if you have one.
I decided to upgrade pip3 by first trying pip3 install --upgrade pip3 which, oddly enough, returned: ERROR: No matching distribution found for pip3
Then I ran pip3 install --upgrade pip and now PyCharm can install packages from the GUI.
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