How does the closing of the ring affect the electric properties of sulphurdioxide? A comparison with the open and closed form of ozone

We have calculated the static polarizability and hyperpolarizability of the ring structure of sulphur dioxide. Our best values for the mean dipole pol arizability (alpha (alpha beta)), the first (beta (alpha beta gamma)) and s econd (gamma (alpha beta gamma delta)) hyperpolarizability, obtained at the CCSD(T) level of theory with alpha carefully optimized basis set, are <(<a lpha>)over bar>=28.94 e(2)a(0)(2)E(h)(-1), <(<beta>)over bar>=110.6 e(3)a(0 )(3)E(h)(-2) and <(<gamma>)over bar>=6117 e(4)a(0)(4)E(h)(-3). At the same level of theory with a basis set of exactly the same size, the relevant qua ntities for the open structure are <(<alpha>)over bar>=25.84 e(2)a(0)(2)E(h )(-1), <(<beta>)over bar>=30.1 e(3)a(0)(3)E(h)(-2) and <(<gamma>)over bar>= 3390 e(4)a(0)(4)E(h)(-3) [D. Xenides and G. Maroulis, Chem. Phys. Lett. 319 , 618 (2000)]. Thus, the ring structure of sulphur dioxide is significantly more polarizable than the isoelectronic open one. This is in marked contra distinction to ozone, in which case the open system represents the more pol arizable form. Electric polarizability and hyperpolarizability increases as O-3(ring)<O-3(open)< SO2(open)< SO2(ring). (C) 2001 American Institute of Physics.