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What does the transmission matrix values (Tvv, Tvh, Thv, Thh) represent?
The transmission matrix evaluates both cases (Tx with V pol and with H pol) even if you defined a Tx with V pol in your project. The transmission matrix is independent from the defined Tx polarization and provides the four components Tvv, Tvh, Thv, Thh.
The first letter stands for the Tx polarization and the second letter for the Rx polarization, so Tvh is for vertically polarized transmission with horizontally polarized reception and Thv evaluates the case for Tx H pol with Rx V pol.
The individual transmission matrix components (linear factors) indicate how of the radiated signal is received by the receiver (including the Tx and Rx polarizations).