The ab initio limit quartic force field of BH3

The complete quartic force field of BH3 has been converged to the ab initio limit by extrapolation of core-valence correlation-consistent basis set series (cc-pCVXZ, X = T, Q, 5) of all-electron CCSD(T) (coupled-cluster singles and doubles with perturbative triples) energy points. Additional computations including full coupled-cluster treatments through quadruple excitations (CCSDTQ), scalar relativistic effects, and diagonal Born-Oppenheimer corrections (DBOC) were concurrently executed. Within second-order vibrational perturbation theory (VPT2) our quartic force field yields the fundamental frequencies v(1) = 2502.3 cm(-1), v(2) = 1147.2 cm(-1), v(3) = 2602.1 cm(-1), and v(4) = 1196.5 cm(-1), in excellent agreement with observed gas-phase fundamentals, displaying a mean absolute error of only 0.3 cm(-1). Our converged prediction for the equilibrium bond length of BH3 is r(e) = 1.1867 angstrom. (c) 2005 Wiley Periodicals, Inc.