[molpro-user] Problem with ZnCl2

[H. -J. Werner]

You get a wrong energy since the program converges to a wrong state.
We will submit a patch soon which fixes this problem. For the time being
please add an occ directive:

ks,b3lyp
occ,5,2,4,2

Then your input gives
    ALPHA       E
    180.0   -95.49198704
    170.0   -95.49152144
    160.0   -95.49005548
    150.0   -95.48747855
    140.0   -95.48355935
    140.0   -95.48355935
    120.0   -95.47088043
    110.0   -95.46143537
    100.0   -95.44893312

Best regards
Joachim werner
~
On So, 14 Nov 2004, Muller, Richard wrote:

>I'm having a problem computing geometries of ZnCl2. I certainly could 
>be doing something wrong, because although I've used molpro quite a 
>bit, this is the first time I've used either the Hay/Wadt ECP, or the 
>B3LYP DFT functionalities.
>
>Here's the jist of the problem: both Jaguar and GAMESS/US give a linear 
>geometry for ZnCl2, but molpro gives a bent geometry. To make sure I 
>didn't do something dumb in the optimization, I attach here a geometry 
>scan using a fixed Zn-Cl bond length (2.165 \AA) and angles from 90-180 
>degrees. I compare (left to right) Jaguar using the LACVP basis/ECP, 
>Gamess using the 6-31G** basis set, Gamess using the Hay/Wadt ECP, and 
>Molpro using the LANL2DZ (which I think is essentially the same basis 
>set/ECP as the Gamess Hay/Wadt). All programs use the B3LYP functional:
>
>Ang   Jag/LACVP      GMS/6-31G**   GMS/HW   MP/LANL2DZ
>90	-986.0182	-2699.2983	-95.4352	-95.1170
>100	-986.0356	-2699.3169	-95.4529	-95.0963
>110	-986.0478	-2699.3302	-95.4654	-95.0812
>120	-986.0575	-2699.3405	-95.4748	-95.0706
>130	-986.0650	-2699.3485	-95.4820	-95.0584
>140	-986.0704	-2699.3544	-95.4874	-95.0548
>150	-986.0746	-2699.3585	-95.4913	-95.0524
>160	-986.0776	-2699.3609	-95.4939	-95.0509
>170	-986.0791	-2699.3621	-95.4953	-89.0280
>180	-986.0794	                   	-95.4958	
>				
>(this will probably only look good in a fixed-width font).
>
>Am I doing something dumb here? Here's an example of the input file I'm 
>using:
>
>***,ZnCl2
>basis=LANL2DZ
>
>geometry={,
>  ANGSTROM
>  Zn
>  Cl1, Zn, 2.165
>  Cl2, Zn, 2.165, Cl1 170
>}
>ks,b3lyp
>
>I'd like to augment these calculations with some CC calculations, but I 
>wanted to figure out what I'm doing wrong first. Thanks in advance for 
>any help anyone can answer.
>
>
>Rick Muller
>rmuller at sandia.gov
>

-- 
Prof. Hans-Joachim Werner
Institute for Theoretical Chemistry
University of Stuttgart
Pfaffenwaldring 55
D-70569 Stuttgart, Germany
Tel.: (0049) 711 / 685 4400
Fax.: (0049) 711 / 685 4442
e-mail: werner at theochem.uni-stuttgart.de