E.S.R. experiments performed at 1"3 K by optical detection are reported for the photo-excited triplet state of palladiumporphin in a single crystal of n-octane, and the observation of a level anticrossing signal is described.In the crystal the orbital degeneracy of the 3Eu state of the free molecule is lifted by the crystal field and in n-octane the energy difference between the two orbital components Ix) and [y) is found to be 58_+ 2 cm -1. The spinorbit coupling (SOC) and the orbital Zeeman interaction couple the triplet manifolds of. Ix) and [y), and for a proper understanding of the magnetic properties of these states it is necessary to work in the basis of the six spin-orbit functions deriving from the aEu state of the free molecule. It is shown that either of the two triplet states can be described by an effective spin hamiltonian of the common form and expressions for the zero-field parameters D and E and the principal values of the g tensor are given. The experimental values of the parameters in the lowest triplet state are D=-24.38+0'03 GHz, [E[= 320+60 MHz, g, =1"677-+0"001 and g• The matrix element of the SOC connecting the Ix) and l Y) triplet manifolds amounts to qZ= 15 + 3 cm -x and the vibronic orbital angular momentum (in units of h) in the 3Eu state of the free molecule to qA = 1"5 _+ 0"3. A tentative value of 0"63 for the orbital reduction factor q is obtained by comparison with a theoretical estimate of A. The value of q is indicative of weak Jahn-Teller coupling.

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