Accurate bond dissociation energy of water determined by triple-resonance vibrational spectroscopy and ab initio calculations

Triple-resonance vibrational spectroscopy is used to determine the lowest dissociation energy, D0, for the water isotopologue HD16O as 41 239.7 ± 0.2 cm−1 and to improve D0 for H216O to 41 145.92 ± 0.12 cm−1. Ab initio calculations including systematic basis set and electron correlation convergence studies, relativistic and Lamb shift effects as well as corrections beyond the Born–Oppenheimer approximation, agree with the measured values to 1 and 2 cm−1 respectively. The improved treatment of high-order correlation terms is key to this high theoretical accuracy. Predicted values for D0 for the other five major water isotopologues are expected to be correct within 1 cm−1.


Published in:
Chemical Physics Letters, 568-569, 14-20
Year:
2013
Publisher:
Amsterdam, Elsevier
ISSN:
0009-2614
Keywords:
Laboratories:




 Record created 2013-04-25, last modified 2018-09-13


Rate this document:

Rate this document:
1
2
3
 
(Not yet reviewed)