Hi there,
I am trying to optimize a structure of a complex (with Ni)
in its triplet state. (using dft/pbe,svp)
So what I did was a eht with establishing a triplet occupation.
The geometry optimization resulted in a negative HOMO-LUMO Gap, according to "eiger".
Then I added
$fermi tmstrt=350.00 tmend=150.00 tmfac=0.980 hlcrt=1.0E-01 stop=1.0E-03 nue=2
to the control file (I found in in the forum and it already helped me for other problems)
and run a singlepoint.
Running eiger again resulted in having no negative HOMO-LUMO Gap anymore.
But when I looked up the orbitals in the control file it says I have 0.5 electrons in
one of the orbital.
Eiger says:
Total energy = -2494.4305946070 H = -67876.9486821 eV
HOMO-LUMO Separation
HOMO: 143. a 10 b1g -0.15037398 H = -4.09189 eV
LUMO: 144. a 5 eg -0.10644927 H = -2.89663 eV
Gap : +0.04392471 H = +1.19525 eV
Number of MOs= 578, Electrons= 188.00, Symmetry: d4h
Nr. Orbital Occupation Energy
160. b 20 eu +0.050570 H = +1.376 eV
159. a 20 eu +0.050381 H = +1.371 eV
158. b 17 a1g +0.046001 H = +1.252 eV
157. a 17 a1g +0.045317 H = +1.233 eV
156. b 2 a1u +0.033028 H = +0.899 eV
155. a 2 a1u +0.032031 H = +0.872 eV
154. b 16 a1g +0.026476 H = +0.720 eV
153. a 16 a1g +0.024691 H = +0.672 eV
152. b 6 eg +0.022742 H = +0.619 eV
151. a 6 eg +0.020931 H = +0.570 eV
150. b 3 b2u +0.007446 H = +0.203 eV
149. a 3 b2u +0.005272 H = +0.143 eV
148. b 2 b1u -0.059352 H = -1.615 eV
147. a 2 b1u -0.060003 H = -1.633 eV
146. b 10 b1g -0.084731 H = -2.306 eV
145. b 5 eg -0.104036 H = -2.831 eV
144. a 5 eg -0.106449 H = -2.897 eV
143. a 10 b1g 1.000 -0.150374 H = -4.092 eV
142. b 4 eg 1.000 -0.172941 H = -4.706 eV
141. b 5 a2u 1.000 -0.181115 H = -4.928 eV
140. a 5 a2u 1.000 -0.182430 H = -4.964 eV
139. b 1 a1u 1.000 -0.187253 H = -5.095 eV
138. a 1 a1u 1.000 -0.187689 H = -5.107 eV
137. b 15 a1g 1.000 -0.193000 H = -5.252 eV
136. b 9 b2g 1.000 -0.201739 H = -5.490 eV
135. a 4 eg 2.000 -0.212609 H = -5.785 eV
134. b 2 b2u 1.000 -0.219447 H = -5.971 eV
133. a 2 b2u 1.000 -0.222073 H = -6.043 eV
132. a 15 a1g 1.000 -0.226051 H = -6.151 eV
131. b 3 eg 2.000 -0.231343 H = -6.295 eV
130. a 9 b2g 1.000 -0.231398 H = -6.297 eV
129. b 4 a2u 1.000 -0.232780 H = -6.334 eV
128. a 4 a2u 1.000 -0.234912 H = -6.392 eVand the control file says:
$alpha shells
a1g 1-15 ( 1 )
a2g 1-6 ( 1 )
b1g 1-10 ( 1 )
b2g 1-9 ( 1 )
eg 1-4 ( 1 )
a1u 1 ( 1 )
a2u 1-5 ( 1 )
b1u 1 ( 1 )
b2u 1-2 ( 1 )
eu 1-19 ( 1 )
$beta shells
a1g 1-15 ( 1 )
a2g 1-6 ( 1 )
b1g 1-9 ( 1 )
b2g 1-9 ( 1 )
eg 1-3 ( 1 )
eg 4 ( 0.5 )
a1u 1 ( 1 )
a2u 1-5 ( 1 )
b1u 1 ( 1 )
b2u 1-2 ( 1 )
eu 1-19 ( 1 )So I dont understand these lines in eiger:
135. a 4 eg 2.000
and
131. b 3 eg 2.000
And I dont understand the 0.5 in the control file.
And when I count all the electrons in the control file section I get 142.5
but eiger says there are 188 electrons.
I had something similar before but there I had two beta orbitals with 0.5 occupation
what at least made a bit sense as it still results in 1 electron in total.
When I then delete the fermi again in the control file
and run a optimization job my structure converges.
But what can I do to get a proper triplet optimization without a 0.5 occupation?
I would expect to find a optimized structure with integer occupation numbers.
Or are those with non integer occupation numbers are proper results already?
The structure with the neg. homo-lumo gap and that one with the 0.5 occupation only differ by ~200 cal/mol. (The latter has a lower energy).
I read in the manual that I can adjust tmend to low temperature to obtain integer occupation numbers.
I set it to 10, but it didnt help, I still revieve 0.5 and 0.9999999756 and sth like that.
Thanks in advance,
moere
The structure I am trying to optimize in its triplett state:
37
Energy = -2494.430594607
C 2.8641677 1.1020613 0.0000000
N 2.0323199 0.0000000 0.0000000
C 4.2517123 0.6874939 0.0000000
C 4.2517123 -0.6874939 0.0000000
C 2.8641677 -1.1020613 0.0000000
C 2.4355508 2.4355508 0.0000000
C 1.1020613 2.8641677 0.0000000
C 0.6874939 4.2517123 0.0000000
C -0.6874939 4.2517123 0.0000000
C -1.1020613 2.8641677 0.0000000
N 0.0000000 2.0323199 0.0000000
Ni 0.0000000 0.0000000 0.0000000
N 0.0000000 -2.0323199 0.0000000
C -1.1020613 -2.8641677 0.0000000
C -0.6874939 -4.2517123 0.0000000
C 0.6874939 -4.2517123 0.0000000
C 1.1020613 -2.8641677 0.0000000
C -2.4355508 2.4355508 0.0000000
C -2.8641677 1.1020613 0.0000000
C -4.2517123 0.6874939 0.0000000
C -4.2517123 -0.6874939 0.0000000
C -2.8641677 -1.1020613 0.0000000
N -2.0323199 0.0000000 0.0000000
C -2.4355508 -2.4355508 0.0000000
C 2.4355508 -2.4355508 0.0000000
H -1.3698557 5.1126219 0.0000000
H 1.3698557 5.1126219 0.0000000
H -5.1126219 1.3698557 0.0000000
H -5.1126219 -1.3698557 0.0000000
H 1.3698557 -5.1126219 0.0000000
H -1.3698557 -5.1126219 0.0000000
H 5.1126219 1.3698557 0.0000000
H 5.1126219 -1.3698557 0.0000000
H -3.2143272 -3.2143272 0.0000000
H 3.2143272 3.2143272 0.0000000
H 3.2143272 -3.2143272 0.0000000
H -3.2143272 3.2143272 0.0000000
