On 03. 05. 13 14:47, Robert Hanson wrote:
Dear Bob,
Thanks a lot for your reply !
[...]
Q: Are you OK with ignoring the g orbitals?
Yes. They should contribute little to the molecular orbitals, which
I am interested in. Actually, if proceeding so, would it possible to
ignore 'h' and 'i' functions as well ?
sure. What are the number of orbitals in h/i cartesian/spherical sets?
For h: we have 11 spherical and 21 cartesian functions; and for i: we
have 13 spherical and cartesian functions... if I'm not wrong. For a
given L, there are (2L+1) spherical harmonic and (L+1)*(L+2)/2
Cartesian functions [Schlegel and Frisch, Int. J. Quantum Chem, 54,
83-87 (1995]
There seems to be something I'm missing. There are only 492
listed MO coefficients, but there are 711 listed atomic orbitals.
711 = 166 s + 84 p(x3) + 34 d(x5) + 15 f(x7) + 2 g(x10)
Those numbers should match. (NEED to match.)
Q: So what is 492?
This really is the number of basis functions: the basis set is made
of 492 contracted Gaussian functions, consisting each in a linear
combination of some of the 711 primitive Gaussian functions.
I guess that the manner in which the MOs are listen takes the
contractions into account.
I don't see it. Please explain this particular file set in detail.
There 301 Gaussian sets listed, not 492.
301 = 166 s + 84 p + 34 d + 15 f + 2 g
For example:
s 22 1.00
4316265.0000000 1.0000000000
646342.4000000 0.0000000000
147089.7000000 0.0000000000
41661.5200000 0.0000000000
13590.7700000 0.0000000000
4905.7500000 0.0000000000
1912.7460000 0.0000000000
792.6043000 0.0000000000
344.8065000 0.0000000000
155.8999000 0.0000000000
72.2309100 0.0000000000
32.7250600 0.0000000000
15.6676200 0.0000000000
7.5034830 0.0000000000
4.6844000 0.0000000000
3.3122230 0.0000000000
1.5584710 0.0000000000
1.2204000 0.0000000000
0.6839140 0.0000000000
0.1467570 0.0000000000
0.0705830 0.0000000000
0.0314490 0.0000000000
Each set may have more than one directional component, thus we have
total number of independent coefficients:
711 = 166 s + 84 p(x3) + 34 d(x5) + 15 f(x7) + 2 g(x10)
How do you figure that there are only 492 MO coefficients?
(1) My bad ! I was not clear at all. For the Fe atom, for instance, you
only
have 9 contracted basis functions in the s shell and they are given by
linear
combinations of the 22 primitive Gaussian listed above: this can be noted
(22s) -> [9s]. In the example file, I used
for Fe, the cc-pwCVTZ-DK basis set: (22s,18p,10d,3f,2g) ->
[9s,8p,6d,3f,2g]
for the 6 N and 6 C atoms, the cc-pVTZ-DK basis set: (10s,5p,2d,1f)
-> [4s,3p,2d,1f]
for the 6 H atoms, the cc-pVDZ-DK basis set: (4s,1p) -> [2s,1p]
This is why I am expecting 492 MO coefficients
69 s + 50 p(x3) + 30 d(x5) + 15 f(x7) + 2 g(x9) = 492
(2) MY VERY BAD!! I finally get it... I am missing that the output is
actually
simply broken!!! Indeed, looking again and calmly at the example file,
I do
see that the output does not make sense! As you noticed: for each MO,
492 coefficients are given, but there is no information that may help
connect
them with the given primitive Gaussians... Sorry! I was only staring at
the g
functions issue ..
I will look into the sources to try to fix how the basis functions are
written.
Thanks a lot for your valuable help and for your time.
All the best,
Max
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