F1 can occur naturally if conditions are right (a natural cross, for instance, between two wild varieties). However, the F1 hybrid seeds (from pure lines pair-wise crosses) are different from wild crossed seeds in that their resultant plants have reproducible and predictable characteristics that can be duplicated over and over. Not so for most wild crosses.
You can find some useful information about Chemical Hybridization Agents (CHA) suitable for commercialhybrid seed production in specific vegetable crops from https://ru.scribd.com/doc/62470606/Chemical-Hybridizing-Agents-Report1