화학공학소재연구정보센터
Journal of Chemical Physics, Vol.118, No.6, 2673-2687, 2003
Accurate electric multipole moment, static polarizability and hyperpolarizability derivatives for N-2
We report accurate values of the electric moments, static polarizabilities, hyperpolarizabilities and their respective derivatives for N-2. Our values have been extracted from finite-field Moller-Pleset perturbation theory and coupled cluster calculations performed with carefully designed basis sets. A large [15s12p9d7f] basis set consisting of 290 CGTF is expected to provide reference self-consistent-field values of near-Hartree-Fock quality for all properties. The Hartree-Fock limit for the mean hyperpolarizability is estimated at (gamma)over-bar =715+/-4e(4)a(0)(4)E(h)(-3) at the experimental bond length R-e=2.074 32a(0). Accurate estimates of the electron correlation effects were obtained with a [10s7p6d4f] basis set. Our best values are Theta=-1.1258ea(0)(2) for the quadrupole and Phi=-6.75ea(0)(4) for the hexadecapole moment, (alpha)over-bar =11.7709 and Deltaalpha=4.6074e(2)a(0)(2)E(h)(-1) for the mean and the anisotropy of the dipole polarizability, (C)over-bar =41.63e(2)a(0)(4)E(h)(-1) for the mean quadrupole polarizability and (gamma)over-bar =927e(4)a(0)(4)E(h)(-3) for the dipole hyperpolarizability. The latter value is quite close to Shelton's experimental estimate of 917+/-5e(4)a(0)(4)E(h)(-3) [D. P. Shelton, Phys. Rev. A 42, 2578 (1990)]. The R dependence of all properties has been calculated with a [7s5p4d2f] basis set. At the CCSD(T) level of theory the dipole polarizability varies around R-e as (alpha)over-bar (R)/e(2)a(0)(2)E(h)(-1)=11.8483+6.1758(R-R-e)+0.9191(R-R-e)(2)-0.8212(R-R-e)(3)-0.0006(R-R-e)(4), Deltaalpha(R)/e(2)a(0)(2)E(h)(-1)=4.6032+7.0301(R-R-e)+1.9340(R-R-e)(2)-0.5708(R-R-e)(3)+0.1949(R-R-e)(4). For the Cartesian components and the mean of gamma(alphabetagammadelta), (dgamma(zzzz)/dR)(e)=1398, (dgamma(xxxx)/dR)(e)=867, (dgamma(xxzz)/dR)(e)=317, and (d (gamma)over-bar/dR)(e)=994e(4)a(0)(3)E(h)(-3). For the quadrupole polarizability C-alphabeta,C-gammadelta, we report (dC(zz,zz)/dR)(e)=19.20, (dC(xz,xz)/dR)(e)=16.55, (dC(xx,xx)/dR)(e)=10.20, and (dC/dR)(e)=23.31e(2)a(0)(3)E(h)(-1). At the MP2 level of theory the components of the dipole-octopole polarizability (E-alpha,E-betagammadelta) and the mean dipole-dipole-octopole hyperpolarizability (B)over-bar we have obtained (dE(z,zzz)/dR)(e)=36.71, (dE(x,xxx)/dR)(e)=-12.94e(2)a(0)(3)E(h)(-1), and (d (B)over-bar/dR)(e)=-108e(3)a(0)(3)E(h)(-2). In comparison with some other 14-electron systems, N-2 appears to be less (hyper)polarizable than most, as near the Hartree-Fock limit we observe (alpha)over-bar (N-2)<(alpha)over-bar>(CO)<(alpha)over-bar>(HCN)<(alpha)over-bar>(BF)<(alpha)over-bar>(HCCH) and (gamma)over-bar (N-2)<(gamma)over-bar>(CO)<(gamma)over-bar>(HCN)<(gamma)over-bar<(gamma)over-bar(HCCH)<(gamma)over-bar(BF). (C) 2003 American Institute of Physics.