[molpro-user] CaF ground state HF and UHF calculation problems with Molpro2015.1.8
Peterson, Kirk
kipeters at wsu.edu
Thu Nov 17 07:48:57 CET 2016
Dear Dr. Hou,
I’m not sure if this is the problem, but starting from long range and working inwards is sometimes not the best idea for ionic molecules. Also for open shell systems, often one should really completely specify the wavefunction using occ, closed, and wf directives. See my example below.
regards,
-Kirk
***, CaF
memory,100,m
print orbitals
basis={
default,vdz
F=avdz
}
r=[3.0,3.2,3.4,3.5,3.6,3.7,3.75,3.8,3.9,4.0]
geom={
Ca
F 1 r(i)}
do i=1,#r
{hf;occ,9,3,3;closed,8,3,3;wf,29,1,1}
eval(i)=energy
enddo
table,r,eval
digit,2,7
---
On Nov 16, 2016, at 4:28 AM, 侯世林 <slhou at ouc.edu.cn<mailto:slhou at ouc.edu.cn>> wrote:
Dear all:
I have some troubles when calculating CaF with HF and UHF method, and this will consequently influence the results of the related post-HF approaches. I use the version of Molpro 2015.1.8.
Both HF and UHF can do optimization successfully and give reasonable results. However, when a set of internuclear separations R are given, the UHF can finish calculations with no computational errors but the final results are wrong, because the obtained potential curve is repulsive for CaF ground state.
With HF method, reasonable results can be obtained only for the first R, and then the following error message present:
' Molecular orbitals read from record 2100.2 Type=RHF/CANONICAL (state 1.1)
Incorrect occupation. noc= 15 ncl= 15 nelec= 29 ms2= 1
ICLOS
1- 8 9 3 3 0 0 0 0 0
NOCC
1- 8 9 3 3 0 0 0 0 0
'
The input file for HF calculation reads
r=[25.0 18.0 ... ]
geometry={F;Ca,F,$r(l)}
basis=v5z; F=av5z
do l=1,#r
HF
e(1) = energy
method(1) = program
dip(1) = dmz
bond(1) = $r(l)
table,method,bond,e,dip
enddo
For UHF, the 'HF' is just replaced with 'UHF', the output data in units a.u. are: .
METHOD BOND E DIP
UHF-SCF 25.00 -775.9654195 -0.00017432
UHF-SCF 18.00 -775.9653928 -0.00069340
UHF-SCF 12.00 -775.9652089 -0.00390148
UHF-SCF 11.50 -775.9651646 -0.00469214
UHF-SCF 11.00 -775.9651097 -0.00568491
UHF-SCF 10.50 -775.9650412 -0.00694651
UHF-SCF 10.00 -775.9649553 -0.00857887
UHF-SCF 9.50 -775.9648472 -0.01069510
UHF-SCF 9.00 -775.9647107 -0.01349033
UHF-SCF 8.50 -775.9645376 -0.01720938
UHF-SCF 8.00 -775.9643176 -0.02216390
UHF-SCF 7.50 -775.9640366 -0.02871871
UHF-SCF 7.00 -775.9636746 -0.03732960
UHF-SCF 6.50 -775.9632006 -0.04848223
UHF-SCF 6.00 -775.9625529 -0.06287766
UHF-SCF 5.80 -775.9622145 -0.06969148
UHF-SCF 5.60 -775.9618031 -0.07716052
UHF-SCF 5.00 -775.9596775 -0.10355852
UHF-SCF 4.50 -775.9551436 -0.12986174
UHF-SCF 4.20 -775.9491519 -0.14710620
UHF-SCF 4.00 -775.9423734 -0.15892108
UHF-SCF 3.90 -775.9376989 -0.16481988
UHF-SCF 3.80 -775.9318805 -0.17064276
UHF-SCF 3.75 -775.9284576 -0.17349700
UHF-SCF 3.70 -775.9246395 -0.17630598
UHF-SCF 3.60 -775.9156343 -0.18171688
UHF-SCF 3.50 -775.9044483 -0.18673182
UHF-SCF 3.40 -775.8905774 -0.19116755
UHF-SCF 3.20 -775.8522514 -0.19723968
UHF-SCF 3.00 -775.7944646 -0.19696011
The UHF optimization result is:
R E1 DIP1
3.73815213 -776.3297329 1.07225773
The HF optimization result is:
METHOD BOND E DIP
HF-SCF 3.73818011 -776.3296065 1.06723713
How to solve such problems?
Thank you!
Dr. Shilin HOU
Department of Physics,
Ocean University of China
238 Songling Road, Qingdao,
Shandong, 266100_______________________________________________
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