This setting gives you the option of choosing between the DirectX 11 API (Direct3D 11) and the DirectX 12 API (Direct3D 12), the latter of which is known for better performance efficiency. Keep in mind, you'll need a DirectX 12-capable GPU to be able to reap the benefits.
Visually, DirectX 12 brings more in-depth shadowing and what seems like improved anti-aliasing, although this could be incidental. The result: a sharper, less flat scene.
The benchmark even on multiple runs yields puzzling numbers, to say the least: a 35 maximum frames per second (FPS) drop and 2 minimum FPS drop when moving to Direct3D 12, but a 13 average FPS increase. From this, we can surmise that while the overall framerate is lower with Direct3D 12, it's much more steady. For most, it should be the better of the two options, at least until patches smooth out performance (if that should happen).
Hitman's display modes are confusingly named: Windowed is the usual non-fullscreen mode intended for multitasking, while Fullscreen is actually what's commonly known as Fullscreen Borderless mode (which appears identical to Fullscreen, but allows for quick switching between the game and other tasks at the cost of game performance), and Exclusive Fullscreen is actually what's normally known as Fullscreen (allowing for the best performance at the cost of quick task switching and your undivided attention).
A note about the test environment for this setting: Direct3D 12 doesn't allow Fullscreen/Fullscreen Borderless mode to work as intended (switching quickly from the game to other tasks). For that, Direct3D 11 is required, so that's what I've used across this benchmark.
As expected, Exclusive Fullscreen performs better than fullscreen; what stands out is that Windowed performs much better than both, even across repeated tests – great news if you prefer it, but bad if not.
If your max framerate is struggling, Windowed mode serves as one way to increase it significantly while allowing you to attend to other tasks. If it really bothers you and/or you don't care about other tasks so much, choose one of the other two options according to your preference and needs.
The quality at which the scene is rendered, corresponding to the number of pixels; higher resolutions mean more pixels, which means higher quality.
Hitman is a unique case, however: 1920x1080 resolution is actually used regardless of what you choose, although significant image quality differences can be observed across the different options, indicating that automatic downsampling and upsampling are employed. Why exactly isn't clear.
Testing shows 3200x1800 is the only resolution to have a definitive impact on performance, and it's a huge one, to be sure: about 60 FPS comes off the maximum value and nearly 30 off the average. As such, use your native resolution unless you can spare a big performance hit and enable 4K through VSR/DSR.
This setting allows you to render the game at a higher resolution than your monitor natively supports, then downsample it to your native resolution through a process referred to as supersampling, thereby producing a sharper quality image. Unfortunately, you can't downsample to a lower resolution then upsample it for improved performance at the cost of image quality, unlike with some titles.
Visual results are strange here: the default setting with no supersampling is actually the sharpest image of the three. It's likely this is related to the game's apparent automatic downsampling and upsampling. Whatever the case, a patch is needed.
The benchmark displays a major impact on both average and maximum framerate as this setting is increased. Given the visual results, it's best to leave this setting at the default value.
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