Bond length dependence of the polarizability and hyperpolarizability of boron hydride

Abstract

AbstractWe have calculated the dipole properties of boron hydride relying on finite‐field Møller‐Plesset perturbation theory and coupled cluster calculations. Our best values for the properties at the equilibrium bond length Re = 2.32889831 a0 have been obtained at the CCSD(T) level of theory with a very large uncontracted basis set (19s14p9d3f/11s9p3d1f) and are: dipole moment, μz = 0.5328 ea0, mean dipole polarizability α = 21.40, and anisotropy Δα = 2.68 e2aE, mean first hyperpolarizability, β = 68.8 e3aE and mean second dipole hyperpolarizability, γ = 10836 e4aE. The bond‐length dependence of all properties has been determined with a large (19s14p9d1f/11s9p1d) basis set at all levels of theory. At the CCSD(T) level the dipole moment and polarizability around the equilibrium Re is very well represented by the expansions[μ(R) − μ(Re)]/ea0 = −0.6205(R − Re) − 0.1786(R − Re)2 + 0.0928(R − Re)3 + 0.0287(R − Re)4[α(R) − α(Re)]/e2aE = 2.97(R − Re) + 2.69(R − Re)2 + 0.70(R −Re)3 − 0.65(R − Re)4[Δα(R) − Δα(Re)]/e2aE = 17.04(R − Re) + 1.98(R − Re)2 – 2.02(R − Re)3 − 0.11(R − Re)4The derivative of the mean first hyperpolarizability at the CCSD(T)/(19s14p9d1f/11s9p1d) level of theory is estimated as $\left( {{{d \bar \beta } \over {dR}}} \right)_e /e^3 a_0^2E_h^{ - 2}$ = −62.7 ± 3.1. At the same level of theory the derivatives of the Cartesian components of the mean second hyperpolarizability are adequately estimated as, $\left( {{{d\gamma _{zzzz} } \over {dR}}} \right)_e$ = 9907 ± 991, $\left( {{{d\gamma _{xxxx} } \over {dR}}} \right)_e$ = −7441 ± 744, and $\left( {{{d\gamma _{xxzz} } \over {dR}}} \right)_e$ = 1340 ± 134/e4aE. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011