Measurement of the electric quadrupole moment of CO

Measurements of the temperature dependence of the Buckingham effect (electric-field-gradient-induced birefringence, EFGIB) for gaseous carbon monoxide are presented. The measurements span the temperature range 301.2-473.9 K, which allows for separation of the temperature-independent hyperpolarizability contribution from the temperature-dependent quadrupole contribution. It is demonstrated that in the case of carbon monoxide, quantization of the rotational motion of the molecules needs to be considered, the analysis yielding a quadrupole moment of Theta = (-8.77 +/- 0.31) x 10(-40) C m(2) and a hyperpolarizability term of b' = (-0.1243 +/- 0.0078) x 10(-60) C(3) m(4) J(-2). For dipolar molecules, the quadrupole moment is origin dependent, and the value reported here is referred to an origin called the effective quadrupole center. Comparison of this value with the center-of-mass quadrupole moment obtained from other experiments yields information about the dynamic dipole-quadrupole and dipole-magnetic dipole polarizabilities. The temperature-independent term, which contributes (7.0 +/- 0.6)% to the EFGIB at room temperature, is by no means insignificant, and must necessarily be accounted for if the quadrupole moment is to be definitively established. The measured Theta and b' are compared with the best available ab initio calculated values. (C) 2011 American Institute of Physics. [doi:10.1063/1.3585605]