Well, you get a some voltage drop from the circuitry when the PWM generator is idle. The generator idles when input voltage is greater than or equal to output voltage. In that case, it's like a straight connection from the battery to the atomizer.
For a booster that uses a diode rectifier (instead of a MOSFET), you get around a half volt drop from the rectifier. That's in terms of the straight connection from battery to atomizer when the PWM generator is idle. Usable range for one of those is around 3.7V to whatever the limit is on the booster.
For a booster that uses a MOSFET rectifier, you don't get that big drop so with the PWM generator idle, you get around 4.05 to 4.1 volts at the atomizer with the battery at 4.2V. Since battery voltage normally falls off quickly from 4.2 to 4.1V, you can get away with a 4.0V setting.
With a freshly charged battery, the first couple drags may be somewhat above 4.0 volts until the battery discharges a little bit, but it also depends on the battery. For something like a 14500, you'll get a lot of sag so even the first drag off a freshly charged batt can drop down to 4.0V. For something like a LiPo batt that has little voltage sag, you'll be running out of spec longer. Of course, this is only for boosters that use a MOSFET rectifier. Most boosters use a diode rectifier so you have lower range, but a lot less efficiency.