Accurate ab-initio quartic force-fields, vibrational frequencies, and heats of formation for FCN, FNC, CLCN, and CLNC

Abstract

The XCN and XNC (X = F, Cl) isomers have been investigated using the CCSD(T) method in conjunction with correlation consistent basis sets. Equilibrium geometries, harmonic frequencies, anharmonic constants, fundamental frequencies, and heats of formation have been evaluated. Agreement with experiment for the fundamental frequencies is very good, even for nu(2) for ClCN, which is subject to a strong Fermi resonance with 2 nu(3). It is also shown that a second-order perturbation theory approach to solving the nuclear Schrodinger equation gives results in excellent agreement with essentially exact variational calculations. This is true even for nu(2) Of ClCN, provided that near-singular terms are eliminated from the perturbation theory formulas and the appropriate Fermi interaction energy matrix is then diagonalized. A band at 615 cm(-1), tentatively assigned as the Cl-N stretch in ClNC in matrix isolation experiments, is shown not to be due to ClNC. Accurate atomization energies are determined and are used to evaluate accurate heats of formation (3.1 +/- 1.5, 33.2 +/- 1.5, 72.6 +/- 1.5, and 75.9 +/- 1.5 kcal/mol for FCN, ClCN, FNC, and ClNC, respectively). It is expected that the theoretical heats of formation for FCN, FNC, and ClNC are the most accurate available.