Computer package for microscopic spin Hamiltonian analysis of the 3d4 and 3d6 (spin S = 2) ions at orthorhombic and tetragonal symmetry sites

EMR Data on Mn(III; S=2) Ions in MnTPPCl Complex Modelled by Microscopic Spin Hamiltonian Approach

“…The physical zero-field splitting (ZFS) within the states of an orbital singlet ground state |Γ 0 |S = 2, M s is due to the combined action of the spin-orbit coupling (SOC) and the electronic spin-spin (SS) coupling acting within the CF states. In the MSH approach only the states arising from the ground 5 D (S = 2) multiplet are considered [6,7,15]. Using the complete matrix diagonalization incorporated into the crystal field analysis (CFA) package [21] and its extension CFA/MSH package [22] all states within the whole 3d 4 and 3d 6 configuration are taken into account.…”

“…1 and those in the notation |L, ±M L defined in the MSH/VBA package [6,15] is provided in [20]. Guided by the predictions of the ELs [11], an initial set of input (i.e.…”

“…microscopic) parameters for our calculations is selected as (in cm −1 ): ∆ 1 = ∆ 2 = 22500, ∆ 3 = 25000, ∆ 4 = 21500, the SOC constant λ in the range 50 to 110, and the SSC constant ρ = 0.18 [28]. Additionally, for tetragonal symmetry the mixing coefficients [6,15] satisfy the relations: q = 1, s = 0. Note that the SOC constant λ in crystal is reduced from the free ion value λ 0 : λ = k × λ 0 , k ≤ 1, due to the orbital (covalency) reduction [16,17,19].…”

“…1) correspond to the energy level scheme denoted as "case 2" in the MSH/VBA program [6,15], which is utilized for MSH modelling of the ZFSPs and the g-tensor components for Mn(III) ions in MnTPPCl.Calculations carried out using the initial set of input parameters (see above) yielded the variation of the total ZFSPs versus λ depicted in Fig. 2, whereas the specific contributions of the ZFSPs are listed in Table I.…”

“…* corresponding author; e-mail: krztad@amu.edu.pl † On leave of absence from: Institute of Physics, West Pomeranian University of Technology, al. Piastów 17,Poland In this paper we present preliminary results of semiempirical modeling of the SH parameters for Mn(III) ions in tetraphenylporphyrinato chloride complexes utilizing the MSH approach developed up to fourth-order perturbation theory [6,15] for 3d 4 and 3d 6 systems with S = 2 within the ground 5 D multiplet. Calculations of the ZFSPb 0 2 (= D) and the Zeeman electronic (Ze) factors g i are carried out for wide ranges of values of the microscopic parameters using the MSH/VBA package [6].…”