화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.123, No.7, 1423-1433, 2019
Optical Stark and Zeeman Spectroscopy of Thorium Fluoride (ThF) and Thorium Chloride (ThCl) Published as part of The Journal of Physical Chemistry virtual special issue "Hanna Reisler Festschrift"
Experimentally and theoretically determined magnetic and electric dipole moments, bond distances, and vibrational spacings are used for a comparative study of the bonding in ThF and ThCl. Numerous bands in the visible electronic spectra between 16 400 and 18 800 cm(-1) of supersonically cooled molecular beam samples have been detected using medium-resolution (Delta upsilon approximate to 0.1 cm(-1)) 2D spectroscopy. High-resolution (Delta upsilon < 20 MHz) field-free, Stark, and Zeeman spectroscopy of the detected [18.6]Omega = 3/2 - X-2 Delta(3/2) band of ThF near 538.4 nm and the [18.2]Omega = 3/2 - X-2 Delta(3/2) band of ThCl near 551.0 nm have been recorded and analyzed. Stark shifts and splitting were analyzed to produce Weil values of 1.453(7) D and 0.588(9) D for the X-2 Delta(3/2) and [18.6]Omega = 3/2 states of ThF, respectively, and 2.022(35) D and 3.020(55) D for the X-2 Delta(3/2) and [18.2]Omega = 3/2 states of ThCl. Zeeman splittings and shifts were analyzed to produce g(e) values of 1.038(4) and 1.079(4) for the X-2 Delta(3/2) and [18.6]Omega = 3/2 states of ThF and 1.130(4) and 1.638(4) for the X-2 Delta(3/2)and [18.2]Omega = 3/2 states of ThCl. Analysis of g(e) values demonstrates that the X-2 Delta(3/2)and [18.6]Omega = 3/2 states of ThF and the X-2 Delta(3/2) state of ThCl are predominately (2)A(3/2) spin-orbit components, whereas the [18.2]Omega = 3/2 state of ThCl is an admixture of (2)Delta(3/2) and 2 Pi(3/2) spin-orbit components. A molecular orbital description of the ground states is used to rationalize the observed vertical bar<($mu)over right arrow>e(l)vertical bar values for the ThX (X = F, Cl, O, and S) series and garner insight into the bonding mechanism. The dipole moments in the ground state of ThF and ThCl have been calculated using relativistic coupled-cluster methods. It is demonstrated that the systematic inclusion of electron-correlation contributions plays an essential role in obtaining accurate predictions for the dipole-moment values in ThF and ThCl.