FROM CLUSTER TO CRYSTAL - ABINITIO CALCULATIONS OF THE OH- FREQUENCY IN LITHIUM HYDROXIDE MONOHYDRATE
1992 (English)In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 159, no 1, 67-73 p.Article in journal (Refereed) Published
The fundamental O-H stretching frequency of the OH- ion in crystalline LiOH.H2O has been calculated by ab initio methods at the MP2 level. The experimental and calculated wavenumbers are 3575 and 3602 cm-1, respectively. This frequency is shown to result from a delicate balance of several important interactions between the OH- ion and its surroundings: the two cations in the (Li+)2.OH- cluster produce an upshift of 75 cm-1 with respect to the isolated ion, while the whole nearest-neighbour cluster, (Li+)2(H2O)2.OH-.OH-, gives a frequency downshift of -570 cm-1. The crystal field outside the nearest-neighbour cluster produces an upshift of 610 cm-1. This behaviour conforms well with the frequency versus field correlation curves calculated for simple hydroxide point charge complexes.
Place, publisher, year, edition, pages
1992. Vol. 159, no 1, 67-73 p.
IdentifiersURN: urn:nbn:se:uu:diva-228777DOI: 10.1016/0301-0104(92)80060-9ISI: A1992GY70000006OAI: oai:DiVA.org:uu-228777DiVA: diva2:734862