Electric dipole moments of thietane in excited states of the ring puckering vibration: an experimental and ab initio study |
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Authors: | R. Hinze A. Guarnieri J. L. Alonso J. C. L pez |
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Affiliation: | a Institut für physikalische Chemie, Universität Kiel, 24098, Kiel, Germany b Departmento de Química Física, Facultad de Ciencias, Universidad de Valladolid, E-47005, Valladolid, Spain |
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Abstract: | The electric dipole moment in the ground state (vp = 0) and the first five excited states (vp = 1 … 5) of the ring puckering vibration of thietane have been determined from Stark shifts of rotational transitions. The results are: 0|μa|0 = 1.87583(16) D, 1|μa|1 = 1.87341(18) D, 2|μa|2 = 1.89759(28) D, 3|μa|3 = 1.88688(29) D, 4|μa|4 = 1.90036(18) D, 5|μa|5 = 1.88596(59) D. The dependence of these values on vp shows the zig-zagging behaviour typical of modes with double minimum potentials. A combined analysis of the ground and first excited states yielded also a precise value for the transition moment, 0|μc|1 = 0.24023(49) D. A potential and electric dipole moment function has been derived from ab initio calculations, using MP2 and the 6–31G** basis set. Expectation values of the dipole and transition moments were determined from these data. Absolute values are about 5% in error, but the variation with vibrational state is reproduced excellently by the theoretical values. |
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