Howdy
Jim Watson is correct. The 'freeing groove' was a feature of the early Double Acton models only. Here are some photos that will explain it. This is a pair of Double Action 44s, both chambered for 44 Russian. You can see the clearance grooves on both cylinders. The revolver at top in this photo was made in 1895, the one at the bottom is a very early one made in 1881.
These guns had an unusual mechanism. The locking device in this photo is actually a knob on the end of the trigger. With the trigger in the forward position, the knob protrudes up through a window in the frame and engages the forward set of cuts on the cylinder. The reason for the clearance grooves is because there is no spring, other than the trigger spring, that would allow the knob to retract if the cylinder was closed on it. So if the shooter closes the gun out of battery, the knob will find clearance in the vertical grooves around the cylinder.
This photo shows the position of the bolt with the hammer back. The trigger has rocked back, like all double action revolvers, and the knob at its tip has retracted with it. The actual spring loaded bolt (Smith usually calls it a Cylinder Stop) is visible poking up from the frame where it engages the second set of notches. These notches are conventional, with a lead in, and the bolt is spring loaded like any other revolver.
So in the photo at the top, both revolvers have their hammers down, and it is the knob at the front of the trigger that is holding them from rotating. When the hammers are cocked, either double action or single action, the bolt pops up to secure the cylinder before the trigger knob completely retracts. It's a pretty nifty system, but more complicated than it had to be.
With the 32 and 38 double actions, S&W changed the mechanism at the 3rd models in 1883 and 1884 respectively, simplifying to just a conventional spring loaded bolt and the vertical grooves were eliminated.
There were only around 53,000 of the 44s manufactured from 1881 until 1913, and S&W never updated the design, the 'double bolt' design persisted through the entire run of the Double Action 44s.