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Multiconfiguration quantum chemical calculation of geometry and electron properties of Fe
_{2}Si
_{18} cluster indicates on the predictable change of spin states as a function of the excitation energy beginning from ground state with the total spin S = 4. The charges on the two Fe atoms are quite different as well as the charge distribution on the surrounding Si atoms. Nevertheless the total dipole moment of the cluster is a monotonically decreasing function of the excitation energy and it reaches practically zero value in the first singlet state in which the cluster represents a new version of a quibit system.

Some number of bi-center clusters of the T_{2}Si_{n} type were primarily studied for the transition metals (T = Cr, Mn) [_{2}Si_{n} is characterized by large number of local minima what prevents the predictable change of different spin states with the increasing of excitation energy of a system. The property of Fe_{2} molecule inside a large siliceous cluster seems to be more controlled in the case of its “good packing” into the cluster. The later can be achieved in the case of Fe_{2}Si_{18} cluster, which electronic properties are investigated below in a framework of multireference configuration interaction approach with the singlet and double replacements into the external space. The DFT methods are not suitable enough for obtaining the correct sequence of exited states and especially for the description of a singlet state in the systems containing the transition elements, the Fe-atom especially, see in this connection the table 6 in [_{4} cluster.

The search of the two-state systems represents intriguing story in the modern investigations of a quantum computer systems. We mention here the point-like NV defect state in diamond [_{Si}-V_{C}) in carbide [_{2}Si_{18} cluster would have a special interest in this connection.

The accuracy of multiconfigurational method for the Si subsystem can be demonstrated for Si_{2} molecule with the ground state configuration _{2}] means the closed shell of the neon dimer in the Hartree-Fock approximation. The competing ^{3}Õ_{u}. The calculations were performed using the GAMESS (2011, 2013) program [_{g} 2p_{u}]^{4} active space was used with averaging over two terms with the weights: 1/3 for the ^{3}Õ_{u}. Based on the obtained canonized MOs we considered the SOCI type excitations from the reference space [4s_{g} 4s_{u} 5s_{g} 2p_{u}]^{8} for the whole virtual space. After optimization of bond Si?Si length in accordance with the spectroscopic data [_{2} ground electronic state is^{3}Õ_{u} with the vertical excitation energy of 0.273 eV at a bond length of the ground state.

For the subsequent calculations of the Fe_{2}Si_{18} clusters a special basis set was constructed for the iron atom. The core was treated with the 6-31G(f) basis set to which three additional s, p, and d type Gaussian functions were then added. The exponents of the added functions were optimized with retaining all other functions of the 6-31G(f) basis set. Various methods (ROMP2, MCQDPT [^{5}D_{g}); in the CR-CC(2,3) method all indices proved to be z(s) = 0.280829, z(p) = 0.120767, z(d) = 0.136335.

The calculation scheme looks as following. The total spin S of the Fe_{2} molecule is equal to S = 4 in the ground state and it can induce some spin polarization effect on the surrounding Si atoms. We performed first UHF calculations to take into account this possibility into the consideration with a sufficiently large value of a spin projection M_{S} = 10 that suppose the presence of 8 unpaired electrons in 3d-shells of both Fe-atoms and 12 ones of spin-polarized Si atoms. The obtained UHF natural orbitals were used as the starting orbitals for the next CASSCF calculation with a single high-spin configuration with S = 10 including 20 singly occupied molecular orbitals (MOs) as active orbitals. The obtained CASSCF MOs were transformed to the canonic form with the use of the GAMESS algorithm procedure. These canonized active MOs were divided into three subsets: 6 orbitals with the lowest orbital energies, 8 orbitals resembling 3d-shell states of iron atoms and 6 orbitals with the highest orbital energies. After that three subsets were used to construct three orbital subspaces of the restricted active space self-consistent field (RASSCF) method. The maximum electronic excitation levels between subspaces were allowed to be 2, for the details see also [

The most laborious part in the calculations is of course the investigation of electronic properties in the first singlet state, its description takes Q = 22065484 determinant functions compared to Q = 295795 determinant functions for the ground S = 4 state. Electronic properties are found to be well understandable, the 8 once occupied MOs are well localized on the two Fe atoms, hence all spin states with S = 4, 3, 2, 1, 0 represent the same electronic configuration. Some number of natural orbitals (NOs) with the occupation numbers n = 2, 1, 0 are represented in the

The most important data are summarized below in the

S = 4 | r(Fe_{1}Si_{14}) = 3.027, r(Fe_{1}Si_{17}) = 3.029, r(Fe_{1}Si_{15}) = 2.578, r(Fe_{1}Si_{18}) = 2.578, r(Fe_{1}Si_{16}) = 2.591, r(Fe_{1}Si_{19}) = 2.591, r(Fe_{1}Si_{8}) = 2.906, r(Fe_{1}Si_{5}) = 2.908, r(Fe_{1}Si_{3}) = 2.951, r(Fe_{1}Si_{6}) = 2.952, r(Fe_{1}Si_{4}) = 2.934, r(Fe_{1}Si_{7}) = 2.933, r(Fe_{1}Fe_{2}) = 2.817, r(Fe_{2}Si_{8}) = 3.535, r(Fe_{2}Si_{5}) = 3.537, r(Fe_{2}Si_{3}) = 2.833, r(Fe_{2}Si_{6}) = 2.834, r(Fe_{2}Si_{4}) = 2.829, r(Fe_{2}Si_{7}) = 2.829, r(Fe_{2}Si_{20}) = 2.768, r(Fe_{2}Si_{11}) = 2.768, r(Fe_{2}Si_{9}) = 2.647, r(Fe_{2}Si_{12}) = 2.648, r(Fe_{2}Si_{10}) = 2.646, r(Fe_{2}Si_{13}) = 2.645 | |
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E = −7725.150016а.е. (0эВ) | q(Fe_{1}) = 1.749, q(Fe2) = 0.889, q(Si14) = 0.306, q(Si17) = 0.308, q(Si15) = −0.432, q(Si18) = −0.433, q(Si16) = −0.422, q(Si19) = −0.420, q(Si8) = −0.003, q(Si5) = −0.002, q(Si3) = −0.284, q(Si6) = −0.282, q(Si4) = −0.298, q(Si7) = −0.300, q(Si20) = 0.162, q(Si11) = 0.163, q(Si9) = −0.175, q(Si12) = −0.176, q(Si10) = −0.175, q(Si13) = −0.174 | |

S = 0 | r(Fe_{1}Si_{14}) = 3.008, r(Fe_{1}Si_{17}) = 3.008, r(Fe_{1}Si_{15}) = 2.581, r(Fe_{1}Si_{18}) = 2.581, r(Fe_{1}Si_{16}) = 2.588, r(Fe_{1}Si_{19}) = 2.588, r(Fe_{1}Si_{8}) = 2.922, r(Fe_{1}Si_{5}) = 2.922, r(Fe_{1}Si_{3}) = 2.974, r(Fe_{1}Si_{6}) = 2.974, r(Fe_{1}Si_{4}) = 2.964, r(Fe_{1}Si_{7}) = 2.964, r(Fe_{1}Fe_{2}) = 2.845, r(Fe_{2}Si_{8}) = 3.546, r(Fe_{2}Si_{5}) = 3.546, r(Fe_{2}Si_{3}) = 2.830, r(Fe_{2}Si_{6}) = 2.830, r(Fe_{2}Si_{4}) = 2.839, r(Fe_{2}Si_{7}) = 2.839, r(Fe_{2}Si_{20}) = 2.769, r(Fe_{2}Si_{11}) = 2.769, r(Fe_{2}Si_{9}) = 2.648, r(Fe_{2}Si_{12}) = 2.648, r(Fe_{2}Si_{10}) = 2.645, r(Fe_{2}Si_{13}) = 2.645 | |

E = −7725.147837а.е. (0.059эВ) | q(Fe1) = 1.723, q(Fe2) = 0.816, q(Si14) = 0.293, q(Si17) = 0.293, q(Si15) = −0.415, q(Si18) = −0.415, q(Si16) = −0.430, q(Si19) = −0.430, q(Si8) = 0.032, q(Si5) = 0.032, q(Si3) = −0.302, q(Si6) = −0.302, q(Si4) = −0.294, q(Si7) = −0.294, q(Si20) = 0.171, q(Si11) = 0.171, q(Si9) = −0.161, q(Si12) = −0.161, q(Si10) = −0.165, q(Si13) = −0.165 |

NO #143 n = 1.997 | NO #151 n = 1.012 | NO #154 n = 1.000 | NO #162 n = 0.005 |

NO #143 n = 1.999 | NO #154 n = 0.993 | NO #155 n = 0.950 | NO #162 n = 0.004 |

Spin number | Δq (e) | ΔΕ (eV) | |
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S = 0 | 0.005 | 0.907 | 0.059 |

S = 1 | 0.012 | 0.900 | 0.056 |

S = 2 | 0.033 | 0.886 | 0.048 |

S = 3 | 0.059 | 0.883 | 0.033 |

S = 4 | 0.124 | 0.860 | 0.000 |

We conclude: 1) the excitation energy between neighboring spin states is a decreasing function of the transition energy, 2) the charge difference Δq is nearly stable, 3) the total dipole moment is a drastically decreasing function of the transition energy ΔΕ. The last observation is most importance and it can be understood as following. The large positive charge on one Fe-atom, it denoted by number 1 in the _{2} molecule in the DFT (B3P86) approach [

The symmetric charge distribution is unstable, there arise some kind of “up and down states” in the sense of the charge distribution in the degenerate electronic state. This conclusion can be checked by the measurement of Mössbauer spectra on the two Fe-atoms. Only the stable electronic structures were described above, the problem of their transformations is to be discussed separately.

S = 3 | S = 2 | S = 1 |
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E = −7725.148819 ΔΕ = 0.033 | E = −7725.148235 ΔΕ = 0.048 | E = −7725.147953 ΔΕ = 0.056 |

r(Fe_{1}Si_{14}) = 3.030, r(Fe_{1}Si_{17}) = 3.021, r(Fe_{1}Si_{15}) = 2.579, r(Fe_{1}Si_{18}) = 2.579, r(Fe_{1}Si_{16}) = 2.590, r(Fe_{1}Si_{19}) = 2.590, r(Fe_{1}Si_{8}) = 2.913, r(Fe_{1}Si_{5}) = 2.914, r(Fe_{1}Si_{3}) = 2.962, r(Fe_{1}Si_{6}) = 2.962, r(Fe_{1}Si_{4}) = 2.947, r(Fe_{1}Si_{7}) = 2.946, r(Fe_{1}Fe_{2}) = 2.827, r(Fe_{2}Si_{8}) = 3.539, r(Fe_{2}Si_{5}) = 3.539, r(Fe_{2}Si_{3}) = 2.834, r(Fe_{2}Si_{6}) = 2.834, r(Fe_{2}Si_{4}) = 2.831, r(Fe_{2}Si_{7}) = 2.831, r(Fe_{2}Si_{20}) = 2.769, r(Fe_{2}Si_{11}) = 2.769, r(Fe_{2}Si_{9}) = 2.647, r(Fe_{2}Si_{12}) = 2.647, r(Fe_{2}Si_{10}) = 2.645, r(Fe_{2}Si_{13}) = 2.645 | r(Fe_{1}Si_{14}) = 3.009, r(Fe_{1}Si_{17}) = 3.009, r(Fe_{1}Si_{15}) = 2.580, r(Fe_{1}Si_{18}) = 2.580, r(Fe_{1}Si_{16}) = 2.589, r(Fe_{1}Si_{19}) = 2.589, r(Fe_{1}Si_{8}) = 2.919, r(Fe_{1}Si_{5}) = 2.919, r(Fe_{1}Si_{3}) = 2.974, r(Fe_{1}Si_{6}) = 2.974, r(Fe_{1}Si_{4}) = 2.962, r(Fe_{1}Si_{7}) = 2.961, r(Fe_{1}Fe_{2}) = 2.845, r(Fe_{2}Si_{8}) = 3.539, r(Fe_{2}Si_{5}) = 3.539, r(Fe_{2}Si_{3}) = 2.831, r(Fe_{2}Si_{6}) = 2.831, r(Fe_{2}Si_{4}) = 2.832, r(Fe_{2}Si_{7}) = 2.832, r(Fe_{2}Si_{20}) = 2.770, r(Fe_{2}Si_{11}) = 2.770, r(Fe_{2}Si_{9}) = 2.648, r(Fe_{2}Si_{12}) = 2.648, r(Fe_{2}Si_{10}) = 2.646, r(Fe_{2}Si_{13}) = 2.646 | r(Fe_{1}Si_{14}) = 3.009, r(Fe_{1}Si_{17}) = 3.009, r(Fe_{1}Si_{15}) = 2.581, r(Fe_{1}Si_{18}) = 2.581, r(Fe_{1}Si_{16}) = 2.588, r(Fe_{1}Si_{19}) = 2.588, r(Fe_{1}Si_{8}) = 2.921, r(Fe_{1}Si_{5}) = 2.921, r(Fe_{1}Si_{3}) = 2.973, r(Fe_{1}Si_{6}) = 2.973, r(Fe_{1}Si_{4}) = 2.963, r(Fe_{1}Si_{7}) = 2.963, r(Fe_{1}Fe_{2}) = 2.846, r(Fe_{2}Si_{8}) = 3.545, r(Fe_{2}Si_{5}) = 3.545, r(Fe_{2}Si_{3}) = 2.831, r(Fe_{2}Si_{6}) = 2.831, r(Fe_{2}Si_{4}) = 2.838, r(Fe_{2}Si_{7}) = 2.838, r(Fe_{2}Si_{20}) = 2.769, r(Fe_{2}Si_{11}) = 2.769, r(Fe_{2}Si_{9}) = 2.647, r(Fe_{2}Si_{12}) = 2.647, r(Fe_{2}Si_{10}) = 2.645, r(Fe_{2}Si_{13}) = 2.644 |

q(Fe1) = 1.738, q(Fe2) = 0.855, q(Si14) = 0.301, q(Si17) = 0.302, q(Si15) = −0.428, q(Si18) = −0.429, q(Si16) = −0.423, q(Si19) = −0.422, q(Si8) = 0.012, q(Si5) = 0.012, q(Si3) = −0.289, q(Si6) = −0.288, q(Si4) = −0.298, q(Si7) = −0.299, q(Si20) = 0.166, q(Si11) = 0.167, q(Si9) = −0.169, q(Si12) = −0.170, q(Si10) = −0.170, q(Si13) = −0.169 | q(Fe1) = 1.720, q(Fe2) = 0.834, q(Si14) = 0.293, q(Si17) = 0.293, q(Si15) = −0.424, q(Si18) = −0.424, q(Si16) = −0.426, q(Si19) = −0.426, q(Si8) = 0.027, q(Si5) = 0.027, q(Si3) = −0.291, q(Si6) = −0.291, q(Si4) = −0.293, q(Si7) = −0.294, q(Si20) = 0.168, q(Si11) = 0.168, q(Si9) = −0.165, q(Si12) = −0.165, q(Si10) = −0.167, q(Si13) = −0.166 | q(Fe1) = 1.721, q(Fe2) = 0.821, q(Si14) = 0.293, q(Si17) = 0.293, q(Si15) = −0.416, q(Si18) = −0.416, q(Si16) = −0.429, q(Si19) = −0.429, q(Si8) = 0.031, q(Si5) = 0.031, q(Si3) = −0.300, q(Si6) = −0.300, q(Si4) = −0.294, q(Si7) = −0.294, q(Si20) = 0.170, q(Si11) = 0.170, q(Si9) = −0.162, q(Si12) = −0.162, q(Si10) = −0.165, q(Si13) = −0.165 |