Sunday, 22 November 2015

molecular orbital theory - Why does the PH3 geometry deviate more from the trigonal planar one, than does NH3?


PHX3 has a more bent structure than NHX3. The HOMO-LUMO gap for PHX3 is smaller than for NHX3, and so the distortion from the trigonal planar geometry is said to be larger. However, why is the HOMO-LUMO gap smaller for PHX3?


It should be possible, I suppose, to argue for why this is so by using qualitative molecular orbital theory, and from looking at the construction of the molecular orbital diagrams, but I am not sure how to construct accurate MO diagrams for PHX3 and NHX3.


In the answer to the possible duplicate question, it seems to be taken for granted that some distortion from the planar structure is stabilizing. In my question, the starting point is the planar structure, and then looking at why PHX3 is in a more distorted geometry than NHX3, relative to the planar structures.


This distortion is often explained in terms of the "HOMO-LUMO gap", but I fail to see how the HOMO-LUMO gap can be assessed qualitatively in order to predict which of NHX3 and PHX3 is in a more distorted geometry. So what factor ultimately leads to the smaller HOMO-LUMO gap in PHX3? BHX3 exists in a trigonal planar geometry - why is not this molecule pyramidalized?




No comments:

Post a Comment

readings - Appending 内 to a company name is read ない or うち?

For example, if I say マイクロソフト内のパートナーシップは強いです, is the 内 here read as うち or ない? Answer 「内」 in the form: 「Proper Noun + 内」 is always read 「ない...