Yes voltage regulation is controlled by the PCM in modern vehicles.
My guess an intermittently bad alternator or a loose/worn/contaminated serpentine belt could be slipping on the alternator's pulley.
Turning on the AC compressor could of presented enough of a mechanical load on the belt to tighen it up some?
The AC compressor's pulley is free wheeling like an idler pulley until the AC is turned on.
Only a WA guess but i'd eliminate the simplest things first.
Before thinking on replacing the PCM i'd get the alternator tested first.
My guess an intermittently bad alternator or a loose/worn/contaminated serpentine belt could be slipping on the alternator's pulley.
Turning on the AC compressor could of presented enough of a mechanical load on the belt to tighen it up some?
The AC compressor's pulley is free wheeling like an idler pulley until the AC is turned on.
Only a WA guess but i'd eliminate the simplest things first.
Before thinking on replacing the PCM i'd get the alternator tested first.