Bellatrix Lestrange is also a likely candidate. Her encounter with Hermione would be extremely intense. Given her loyalty to Voldemort and her rather unhinged nature, she would likely pose a serious threat to Hermione, but Hermione might also find a way to use Bellatrix's madness against her.
Bellatrix Lestrange's younger brother or some other minor Death Eater character could be used. This would allow for the creation of a new character with his own motives and backstory. He could be betrothed to Hermione as part of a larger plot by Voldemort to gain control over Hermione's knowledge and magic. This would put Hermione in a very difficult position as she would be tied to a very dark and dangerous family.
There's also a possibility that it could be a minor Death Eater that we don't know much about from the original series. The author of the fanfiction could create a new character who was a Death Eater but is now having doubts. Hermione could be the one to find this person and start their journey of change. This would give the author a lot of creative freedom to develop the character's backstory and their relationship with Hermione.
It could be someone who has a hidden good side, like Draco Malfoy. He was from a Death Eater family but showed signs of not fully embracing the dark side. Maybe in this fanfiction, he decides to protect Hermione for some unforeseen reason, perhaps because he has developed a new understanding of the value of life and friendship.
One possible motive could be a deep - seated dissatisfaction with the wizarding world's status quo. Maybe she felt that the Ministry of Magic was corrupt and that the Death Eaters had a better vision for change, although a very dark one. Another could be some sort of personal vendetta against someone in the Order of the Phoenix or Hogwarts faculty that made her side with the Death Eaters.
In some fanfictions, Percy Weasley may be depicted as a Death Eater, but this is a departure from the original canon. Fanfiction allows for creative reinterpretations, and some authors might explore this dark turn for his character to add drama and new plotlines.
In this type of fanfiction, the relationship between Hermione and the Death Eater could be very complex. Maybe it starts as a hostile one, but as the story progresses, they might find some common ground or mutual understanding. It could also be a story of redemption for the Death Eater through Hermione's influence.
It could also be that Hermione is on a mission to gather information. By helping the Death Eater, she hopes to gain insider knowledge about the Death Eater's group or their plans. This would be a strategic move on her part, using the situation to her advantage in the fight against the dark forces.
Another idea could be that she is somehow brainwashed. There could be a dark spell or a powerful magical object that alters her perception and makes her believe in the Death Eater ideology. In this scenario, her friends would have to find a way to break the spell and bring her back to her true self.
It's a really wild concept in fanfic. Hermione is always associated with knowledge, justice, and the side of good. However, some fanfic authors might be trying to subvert the normal expectations. But in the canon, there's no way she could be a Death Eater. She detests everything they stand for, from their pure - blood mania to their use of dark magic.