Wikipedia claims that space suits that use pure oxygen are pressurized to 4.7 psi, instead of 3.0 psi, to account for carbon dioxide and water vapor pressure as per the alveolar gas equation (although noting that the calculation has slight overcorrection).
NASA EMU is pressurized to 4.3 psi according to many sources. The rationale given for this is the same: to give the astronaut the same amount of oxygen as for normal air per the alveolar gas equation.
As for others, A7L Skylab space suits were pressurized to 3.7 psi. Russian Orlan space suits are pressurized to 5.8 psi.
However, none of these values seem to fit when actually viewing the alveolar gas equation. If breathing pure oxygen, the alveolar gas equation becomes simply:
$$\require{mhchem}p_A\ce{O2} = P_{atm} - p\ce{H2O} - p_a\ce{CO2}$$
where $p\ce{H2O}$ is 6.28 kPa at 37 °C and $p_a\ce{CO2}$ is normally 40 mmHg. Given that 104 mmHg is considered normal for $p_A\ce{O2}$, this is achieved with a pressure of 3.7 psi for pure oxygen.
So why 4.3 psi specifically? Are there benefits to having a slightly hyperoxic environment? Is this to allow for slow leaks or partial depressurization without the astronaut becoming hypoxic?
I will obviously be very happy to receive corrections if I have made a mistake in my calculations or if there's some physiological phenomena here that I don't understand. I would love to get a proper answer from someone who actually knows the real reason, but forgoing that I would be thankful for any well-founded arguments as to why this might be so.