화학공학소재연구정보센터
Journal of Physical Chemistry, Vol.100, No.32, 13466-13473, 1996
Electric Polarizability and Hyperpolarizability of Carbon-Monoxide
We report an extensive ab initio study of the electric dipole polarizability and hyperpolarizability of carbon monoxide. The bond length dependence of the molecular properties has been determined from finite-field complete fourth-order many-body perturbation theory and coupled cluster calculations with very large, well-optimized basis sets of Gaussian functions. The mean dipole polarizability <(alpha)over bar> and the anisotropy Delta alpha vary around the experimental bond length of R(e) = 2.132221 a(0) as <(alpha)over bar>(R)/e(2)a(0)(2)E(h)(-1) = 13.19 + 5.52(R - R(e)) + 1.74(R - R(e))(2) - 0.35(R - R(e))(3) - 0.33(R - R(e))(4) and Delta alpha(R)/e(2)a(0)(2)E(h)(-1) = 3.66 + 8.28(R - R(e)) + 3.32(R - R(e))(2) - 0.24(R - R(e))(3) - 0.42(R - R(e))(4). The mean first dipole hyperpolarizability <(beta)over bar> varies as <(beta)over bar>(R)/e(3)a(0)(3)E(h)(-2) = 28.0 - 7.0(R - R(e)) - 5.6(R - R(e))(2) - 8.7(R - R(e))(3) + 2.1(R - R(e))(4) and the mean second dipole hyperpolarizability <(gamma)over bar> as 10(-2)<(gamma)over bar>(R)/e(4)a(0)(4)E(h)(-3) = 15.3 + 3.4(R - R(e)) + 13.3(R - R(e))(2) + 1.8(R - R(e))(3) - 2.6(R - R(e))(4). Our best values for the respective static Limits at the ground vibrational slate are <(alpha)over bar> = 13.15 e(2)a(0)(2)E(h)(-1), Delta alpha = 3.68 e(2)a(0)(2)E(h)(-1), <(beta)over bar> = 26.5 e(3)a(0)(3)E(h)(-2), and <(gamma)over bar> = 14.8 x 10(2) e(4)a(0)(4)E(h)(-3). Relying on previous estimates of the dispersion of the hyperpolarizability (Sekino, H.; Bartlett, R. J. J. Chem. Phys. 1993, 98, 3022), we estimate fur the hyperpolarizability the values of <(beta)over bar> = 30.1 +/- 0.6 e(3)a(0)(3)E(h)(-2) and <(gamma)over bar> = (17.9 +/- 0.9) x 10(2) e(4)a(0)(4)E(h)(-3) at 694.3 nm, in excellent agreement within the available experimental results of 30.2 +/- 3.2 e(3)a(0)(3)E(h)(-2) and 1730 +/- 50 e(4)a(0)(4)E(h)(-3), respectively.