Definitely it's better to do this once you are admitted. Before you're admitted, most questions about a program can be answered via a Google search.
I've emailed students in the past without problems. I don't start with a flood of questions, just an introductory email asking if they want to chat. If a current student doesn't want to reply they don't have to. It's an email, not a threat.
I've asked about flaws of the program (e.g., is there something they wish the program could improve? Is there friction between certain professors?) but I never email their responses to the department chair. Often it's harder to ask these types of questions in a panel-like setting.
I've picked students to contact based on shared research interests. I ask questions about my POI's advising style. My peers who are underrepresented minorities in the field contact students who are involved in oSTEM, women in STEM, etc to get an idea of the non-academic activities one could get involved with. I've also contacted someone because they were in the same undergrad research group as me (two years before me, so our paths didn't cross then), and I wanted a comparison of our undergrad environment with their grad one.