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VNN is required to perform an A-to-S rail transition during operation according to the APL EDS (IBL#557555). The Cold Boot (Figure 4-1 in the EDS) shows VNN coming up first as an "A" rail.
After the PMIC release PCH_PWROK, VNN becomes an "S" rail, meaning it is disabled when the processor enters sleep states. As a result, it becomes one of the first to power down per the Cold Off sequence (Figure 4-5 in the EDS).