MOs OF COMMON METAL FRAGMENTS OF ORGANOMETALLICS

This page connects you to the pages with frontier molecular orbitals of small molecules undergoing a geometric distortion

The energy changes of various frontier orbitals can be plotted to understand why a particular geometry is preferred. This is called a Walsh diagram.

To see molecules with different numbers of ligands, go to the master table: COMFORT

A Walsh diagram for the bending of a H3 molecule

Data for the Walsh Diagram of H-H-H]+ bending

Variation of orbital energies (in Hartrees) with H-H-H bending





H-H-H Angle in deg. 180 160 140 120 100 80 60
HOMO -0.95482 -0.95248 -0.96475 -0.98506 -1.01039 -1.03612 -1.04967
LUMO -0.51383 -0.51304 -0.50417 -0.48469 -0.45107 -0.40117 -0.33811
LUMO+1 -0.11317 -0.12963 -0.16267 -0.20199 -0.24162 -0.28338 -0.33773









A Walsh diagram for the bending of a CH2 molecule

Data for the Walsh Diagram for a CH2 bending motion

MOLECULE (Geometrical Parameter Varied) Relative Free Energy of bent CH2  in Hartrees Energy of HOMO-2 (Hartrees) Energy of HOMO-1 (Hartrees) Energy of HOMO (Hartrees) Energy of LUMO (Hartrees) Energy of LUMO+1 (Hartrees) Energy of LUMO+2 (Hartrees)
CH2  Singlet Carbene (H-C-H) H-C-H





80 0.01113 -0.68274 -0.36196 -0.27581 -0.12591 0.10558 0.13862
84 0.00703 -0.67936 -0.37106 -0.26926 -0.12501 0.10844 0.14219
88 0.00391 -0.67629 -0.37976 -0.26275 -0.12411 0.11074 0.14595
92 0.00174 -0.67344 -0.38804 -0.2563 -0.12322 0.11245 0.14981
96 0.00046 -0.6708 -0.39592 -0.2499 -0.12233 0.11361 0.15372
100 0.0 -0.66836 -0.40339 -0.24355 -0.12145 0.11422 0.15765
104 0.00045 -0.66606 -0.41046 -0.23727 -0.12058 0.11429 0.16154
108 0.0016 -0.66389 -0.41714 -0.23106 -0.11972 0.11383 0.16537
112 0.00345
 -0.66182 -0.42342 -0.22494 -0.11886 0.11289 0.16909
116 0.00593
 -0.65983 -0.42932 -0.21895 -0.11801 0.1115 0.17269
120 0.00897
 -0.65788 -0.43484 -0.2131 -0.11715 0.10972 0.17613

A plot of the free energy of the CH2 fragment vs. angle is given in this link

A diagram where the orbital energies given above are plotted as a function of the bending angle is the Walsh diagram and can be viewed here:  WALSH

All web pages were generated using WEBMO and the calculations were carried out using GAUSSIAN suite of programs. Clicking on the molecule name goes to the page showing the MOLECULAR ORBITALS.