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 ν1 = 2502.3 cm−1, ν2 = 1147.2 cm−1, ν3 = 2602.1 cm−1, and ν4 = 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 re = 1.1867 Å. © 2005 Wiley Periodicals, Inc. J Comput Chem 26: 1106–1112, 2005

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