The absorption spectrum of HD has been studied under high resolution in the vacuum ultraviolet to 840 Å, the emission spectrum to 1000 Å. The analysis of the latter gives accurate rotational constants and vibrational intervals of the ground state right up to the dissociation limit. Comparing these experimental data with calculations from ab initio theory, agreement to the same extent as was previously found for H2 and D2 is obtained. Extrapolation of the obs. – calc. values from H2 and D2 to infinite mass yields agreement with the recently revised theoretical values to within less than 0.1 for v < 7 and less than 0.5 cm−1 for the whole range of observed v values. The deviations for finite mass (H2 and D2) are clearly due to the non-adiabatic corrections neglected in the ab initio calculations. The results for HD are not halfway between H2 and D2 but are closer to H2. This apparent anomaly can be quantitatively accounted for, on the basis of recent calculations of Wolniewicz, by the effect of additional nonadiabatic corrections caused by the excited Σu states which in HD, unlike H2 and D2, can interact with the ground state.The rotational and vibrational constants of the excited states B1Σu+, C1Πu, and B′1Σu+ show somewhat larger deviations from ab initio values ranging for v0v from 5 to 120 cm−1, just as for H2 and D2. The electronic isotope shift of HD lies approximately half-way between the values of H2 and D2 as expected. In addition to the B–X, C–X, and B′–X systems the absorption spectrum of HD, unlike that of H2 and D2, shows an extensive progression of weak transitions to the double minimum state EF1Σg+ and a few very weak transitions to the G1Σg+ and I1Πg states. For the EF state both levels in the outer minimum (F) and levels above the maximum are observed. The correlation of the six excited states B, C, B′, EF, G, and I to the two close-lying dissociation limits corresponding to H + D* and H* + D is briefly discussed.
The electronically excited states of cyclooctatetraene—An analysis of the vacuum ultraviolet absorption spectrum by ab initio configuration interaction methods
