Matrix Isolation ESR and Theoretical Study of ZnN

The Zn¹⁴N, ⁶⁷Zn¹⁴N, Zn¹⁵N, and ⁶⁷Zn¹⁵N radicals have been formed by the reaction of a plume of zinc metal produced with laser ablation and either ammonia vapor or nitrogen atoms isolated in an inert neon matrix at 4.3 K. The ground electronic state of ZnN was determined to be ⁴∑^– using electron spin resonance spectroscopy. The following magnetic parameters were determined experimentally for ZnN: g_⊥ = 1.9998(3), g_∥ = 2.0018(3), |D| = 7268(8) MHz, A_⊥(¹⁴N) = −17.9(20) MHz, A_∥(¹⁴N) = 1.5(20) MHz, A_⊥(¹⁵N) = 25.1(20) MHz, A_∥(¹⁵N)= −2.0(20) MHz, A_⊥(⁶⁷Zn) = 156(3) MHz, and A_∥(⁶⁷Zn) = 168(12) MHz. The low-lying electronic states of ZnN were also investigated using the complete active space self-consistent field technique. By plotting the potential energy surface, theoretical parameters for the ground state with a configuration of 8σ²9σ²10σ¹4π² were determined, including r_e = 2.079 Å and D_e = 1.0 kcal/mol.