The Mechanism of Magnetically Tuned Singlet-Triplet Avoided Crossings in the Ã(1)A(2)-&Xtilde;(1)A(1) 4(1)(0) Band of Thioformaldehyde H(2)C&dbond;S.
Magnetically tuned singlet-triplet perturbations in the 4(1)Ã(1)A(2)-2(1)3(1)ã(3)A(2) system of thioformaldehyde, found in ortho-rotational states (I = 1, the two hydrogen spins parallel) have been identified as being caused by vibronic spin-orbit coupling. This perturbation mechanism has been confirmed in several avoided crossings observed in this work for para states (I = 0, hydrogen spins antiparallel) which are much stronger. Parametrization of the theory has led to a quantitative understanding of the experimental frequency-field relations, and to an accurate prediction of the rovibrational energies of the triplet state. This in turn permitted the detection of about 100 Doppler-limited 2(1)3(1)ã(3)A(2)-0(0) &Xtilde;(1)A(1) rovibronic transitions which led into fine structure states. The combined data was then used to determine a set of rotational, fine, and hyperfine triplet-state parameters, the term value T(0)(2(1)3(1)ã(3)A(2)) = (16 685.385 +/- 0.002) cm(-1), and the spin-orbit vibronic singlet-triplet coupling constant, W(ST) = (0.0691 +/- 0.0016) cm(-1). A large number of frequency perturbations observed in the crossings, ranging from 2 to 300 MHz, can be explained with this single parameter. Copyright 2000 Academic Press.
Ulrich
W
Abteilung Chemische Physik, Universität Ulm, Ulm, D-89069, Germany
Hüttner
W