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Ab initio molecular orbital study of ground and low-lying electronic states of CoCN
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Image of FIG. 1.
FIG. 1.

Potential energy profiles of low-lying electronic states of CoCN plotted as functions of the Co–C distance . The electronic energy is determined at the /[Roos ANO (Co), aug-cc-pVQZ (C, N)] level of theory with fixed at , i.e., of CoCN, and bond angle : (a) Triplet manifold and (b) quintet manifold. The energy zero is at the equilibrium energy of CoCN.

Image of FIG. 2.
FIG. 2.

Occupation patterns of the dominant electronic configurations (with total weights of approximately 88% and 93%, respectively) for the and states of CoCN, calculated at the SA-CASSCF level of theory. The ordinate represents the relative location of an NO in terms of the diagonal elements of the effective Fock matrix in the NO basis (see Sec. II). The main character of each MCSCF NO is given in parentheses, where , , and denote atomic orbitals of Co, the largest component comes first, and the minor components are shown in smaller fonts. Two highest valence NOs, and , at 0.353 and 1.189 or 0.343 and 1.165 , respectively, are not included since they are located high above the given ordinate scale.

Image of FIG. 3.
FIG. 3.

A model for the large amplitude bending motion for CoCN. is the center of mass of the CN moiety, and the numbers in parentheses are approximate masses, in , of Co and CN.

Image of FIG. 4.
FIG. 4.

Spin-orbit interaction, in units of , between and nearby states predicted at the level of MR-SDCI/[ (Co), aug-cc-pVTZ (C, N)] for the equilibrium geometry of the CoCN state. The energy levels for the and states are shifted to those obtained by the /[Roos ANO (Co), aug-cc-pVQZ (C, N)] method. The levels marked by an asterisk will be further perturbed by spin-substates with the same value, not only in the state at , but also in the state at , where energies are for the equilibrium geometry. Thus, the perturbed level at will be pushed further down to by the spin-substate. The predicted values of the for the state and the perturbing state are and , respectively, at the equilibrium geometry.


Generic image for table
Table I.

Vertical excitation energies (in ) given relative to the energy of CoCN, calculated at the /[Roos ANO (Co), aug-cc-pVQZ (C, N)] and /[Roos ANO (Co), aug-cc-pVQZ (C, N)] levels of theory.

Generic image for table
Table II.

Molecular constants for the electronic ground state and for the lowest and states of CoCN.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Ab initio molecular orbital study of ground and low-lying electronic states of CoCN