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An opinion article in Time has this subheading:

CEO is the profession with the most psychopaths.

This may have been added by a headline editor though, because the article body doesn't flesh out the fact that well, besides this (ordered?) list

It's not impossible that the book cited may have made that claim too though (I didn't check.) Anyway, is there high quality empirical to back up this claim that CEOs have the most (or at least a large number) of psychopaths compared to other occupations?

(I do note that Time marked the article as opinion, perhaps to distance itself from the claims therein. Nevertheless, the claim in question is stated as a bare fact therein.)

The table provided is directly copied from Page 173 of The Wisdom of Psychopaths.

It explains the source is The Great British Psychopath Study, where self-selected people submit their own Levenson Self-Report Psychopathy Scale, and categorise themselves according to a list of a hundred or so occupations.

The occupations listed notably do not include "manager" or "CEO", but do include "Chairman/President of company" and "Managing Director".

Given the self-selection and the lack of validation of the data (e.g. people might deliberately skew the results with fake data), the results should be treated with some skepticism.