TY - JOUR

T1 - Matrix Isolation ESR and Theoretical Study of ZnN

AU - Hearne, Thomas S.

AU - Yates, Sally A.

AU - Wild, Duncan A.

AU - McKinley, Allan J.

PY - 2019/5/2

Y1 - 2019/5/2

N2 - The (ZnN)-N-14, (ZnN)-Zn-67-N-14, (ZnN)-N-15, and (6)7Zn(15)N 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)Sigma(-) using electron spin resonance spectroscopy. The following magnetic parameters were determined experimentally for ZnN: g(perpendicular to) = 1.9998(3), g(parallel to) = 2.0018(3), vertical bar D vertical bar = 7268(8) MHz, A(perpendicular to)(N-14) =-17.9(20) MHz, A(parallel to)(14N) = 1.5(20) MHz, A(parallel to)(15N) = 25.1(20) MHz, A(parallel to)(N-15)=-2.0(20) MHz, A(perpendicular to) (Zn-67) = 156(3) MHz, and A(parallel to)(Zn-67) = 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 8 sigma(2)9 sigma(2)10 sigma(1)4 pi(2) were determined, including r(e) = 2.079 angstrom and D-e = 1.0 kcal/mol.

AB - The (ZnN)-N-14, (ZnN)-Zn-67-N-14, (ZnN)-N-15, and (6)7Zn(15)N 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)Sigma(-) using electron spin resonance spectroscopy. The following magnetic parameters were determined experimentally for ZnN: g(perpendicular to) = 1.9998(3), g(parallel to) = 2.0018(3), vertical bar D vertical bar = 7268(8) MHz, A(perpendicular to)(N-14) =-17.9(20) MHz, A(parallel to)(14N) = 1.5(20) MHz, A(parallel to)(15N) = 25.1(20) MHz, A(parallel to)(N-15)=-2.0(20) MHz, A(perpendicular to) (Zn-67) = 156(3) MHz, and A(parallel to)(Zn-67) = 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 8 sigma(2)9 sigma(2)10 sigma(1)4 pi(2) were determined, including r(e) = 2.079 angstrom and D-e = 1.0 kcal/mol.

KW - ELECTRON-SPIN-RESONANCE

KW - CORRELATED MOLECULAR CALCULATIONS

KW - ORGANOMETALLIC FREE-RADICALS

KW - LASER-INDUCED FLUORESCENCE

KW - GAUSSIAN-BASIS SETS

KW - GAS-PHASE SYNTHESIS

KW - INFRARED-SPECTRA

KW - AB-INITIO

KW - NEON MATRICES

KW - VAPORIZATION GENERATION

U2 - 10.1021/acs.jpca.9b00601

DO - 10.1021/acs.jpca.9b00601

M3 - Article

C2 - 30929444

VL - 123

SP - 3709

EP - 3717

JO - The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - The Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

SN - 1089-5639

IS - 17

ER -