I was reviewing the TI white paper "Measuring the Thermal Performance of theTPS54620" (http://www.ti.com/lit/an/slva397/slva397.pdf). This white paper suggests using the FET body diode characterized over temperature (unpowered) to directly measure the Junction Temperature.
It would appear I can apply this method to the TPS54531 to determine junction temperature as the part is used in my circuit/PCB by measuring the voltage (under constant current) from "PH" (pin 8) to "Vin" (pin 2). I can also use the data sheet to estimate the power in the SMPS IC at various load currents.
What is NOT clear to me is how (assuming a constant ambient temperature ... e.g. room temperature) you load the circuit in operation AND continue to measure the forward drop across the internal FET body diode in order to relate that to temperature.