In LabVIEW it is possible to set the trigger slope using niDMM Configure Trigger Slope.vi, but in Python, there is no such function or property. I tried the following workaround that uses the private _set_attribute function, but this did not work - the hardware continues triggering on the rising edge which is the default for the PXIe-4081.
session._set_attribute_vi_int32(NIDMM_ATTR_TRIGGER_SLOPE, NIDMM_VAL_NEG)