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  • Title: The highly anharmonic BH5 potential energy surface characterized in the ab initio limit.
    Author: Schuurman MS, Allen WD, Schleyer Pv, Schaefer HF.
    Journal: J Chem Phys; 2005 Mar 08; 122(10):104302. PubMed ID: 15836311.
    Abstract:
    The strong sensitivity to level of theory of the salient features of the ground state potential energy surface of BH(5) has been overcome by rigorously converged ab initio computations employing correlation-consistent basis sets cc-p(C)VXZ (X=2-6), explicitly correlated R12 corrections, and coupled-cluster theory complete through quadruple excitations (CCSDTQ). Extrapolations via our focal point method yield a C(s)-symmetry global minimum of BH(3)-H(2) type featuring interfragment B-H distances of (1.401, 1.414) A, an H(2) bond length elongated to 0.803 A, and a BH(3)+H(2) dissociation energy D(e)(D(0))=6.6 (1.2) kcal mol(-1). The classical barriers for H(2) internal rotation and hydrogen scrambling are 0.07 and 5.81 kcal mol(-1), respectively, above the BH(5) minimum. Our thermochemical computations yield Delta(f)H(0) ( degrees )[BH(5)(g)]=-111.3+/-0.2 kcal mol(-1)+Delta(f)H(0) ( degrees )[B(g)], which is limited in accuracy only by persistent uncertainties in the enthalpy of formation of gaseous boron. As a first step in investigating the extremely anharmonic 12-dimensional vibrational dynamics of BH(5), a complete quartic force field has been computed at the all-electron cc-pCVQZ CCSD(T) level of theory. Previous matrix isolation infrared assignments of the nu(2) and nu(9) stretching modes of BH(5) compare favorably with our computed vibrational fundamentals, but the experimental assignment of the nu(6) bending mode of the BH(3) moiety is not supported by computed isotopic shifts.
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