Why are the IR-Active Frequencies Wrong in MOLPRO 2000.1?
Jun Li
junli at chemistry.ohio-state.edu
Thu Dec 21 14:47:34 GMT 2000
Dear MOLPRO experts,
I am using MOLPRO 2000.1. As a test of frequency calculations of
heavy-element systems, I tried to repeat the frequency calculation of UF6
published in J. Chem. Phys. 1998, 109, 3875-3881 (Hay & Martin). While I
can get the same optimized structure and RHF energy as the literature data,
the calculated frequencies for the IR-active modes are all wrong, but those
for the Raman and other modes are actually the same as in the literature.
I also have this problem for some other molecules.
I am attaching here the input file and some simple output of UF6. I would
appreciate it very much if any of you could let me know whether this is a
bug of the code or my input file is actually wrong? Thanks.
Merry Christmas to all,
Jun Li
--------input file-----------------
***, MOLPRO 2000.02 Calculations of UF6
memory 50, m
geomtyp=xyz
geometry={
7 ! Number of Atoms
example of cartesian XYZ coordinate input for MOLPRO
U 0.0 0.0 0.0
F 1.99 0.0 0.0
F -1.99 0.0 0.0
F 0.0 1.99 0.0
F 0.0 -1.99 0.0
F 0.0 0.0 1.99
F 0.0 0.0 -1.99
}
basis={
! URANIUM LANL2DZ (6S,5P,2D,2F) -> [3S,3P,2D,2F]
s,U, 0.244400000E+01,0.143300000E+01,0.667700000E+00,0.255600000E+00,
0.244400000E+01,0.143300000E+01,0.667700000E+00,0.255600000E+00,0.120000000E
+00,0.400000000E-01
c,1.4, 0.280278000E+00,-0.132311000E+01, 0.139499900E+01, 0.453123000E+00
c,5.9, -0.837540000E-01,
0.608236000E+00,-0.818433000E+00,-0.905753000E+00, 0.123402000E+01
c,10.10, 0.100000000E+01
p,U, 0.113800000E+01,0.687400000E+00,0.250600000E+00,
0.113800000E+01,0.687400000E+00,0.250600000E+00,0.120000000E+00,0.400000000E-01
c,1.3, -0.558150000E+00, 0.970172000E+00, 0.541903000E+00
c,4.7, 0.225763000E+00,-0.420469000E+00,-0.545903000E+00, 0.742936000E+00
c,8.8, 0.100000000E+01
d,U ,0.382600000E+00,0.147300000E+00
c,1.1, 0.100000000E+01
c,2.2, 0.100000000E+01
f,U ,0.411300000E+01,0.169700000E+01,0.677400000E+00,0.251000000E+00
c,1.2, 0.218993000E+00, 0.459539000E+00
c,3.4, 0.421699000E+00, 0.179066000E+00
! LANL2DZ Effective Core Potentials
ECP,u ,78,4;
7; ! g potential
0, 4.51627250,-.22527100;
1, 368.687695,-53.780570;
2, 112.757671,-516.30521;
2, 30.2032915,-202.67382;
2, 10.2978355,-62.564405;
2, 3.49105150,-21.558956;
2, 1.26683910,-1.5390545;
8; ! s-g potential
0, 257.352944,2.61188160;
1, 83.1605428,81.2356657;
2, 29.7200513,353.246536;
2, 6.24821320,311.929223;
2, 4.16346720,-423.55258;
2, 3.00015110,293.216084;
2, 1.56000000,-21.344255;
2,0.870000000,1.66925480;
8; ! p-g potential
0, 288.729825,1.84143880;
1, 76.7838420,75.7054755;
2, 24.8252003,288.460167;
2, 5.12487350,250.728943;
2, 3.76033000,-318.89681;
2, 2.97617060,160.084492;
2, 1.99190170,33.7801891;
2,0.973883200,-2.0699997;
6; ! d-g potential
0, 350.469941,2.90820640;
1, 166.709130,74.3577628;
2, 85.8206119,587.114033;
2, 26.9842255,317.254368;
2, 7.15655920,102.842212;
2, 1.28408550,22.4214278;
7; ! f-g potential
0, 251.267075,3.93503390;
1, 108.010922,64.9434120;
2, 114.802189,265.180478;
2, 39.9112545,389.428409;
2, 11.9039784,153.476722;
2, 3.38507720,12.0807444;
2, 1.26776070,-1.3510138;
spd, F, 6-31g*; c
}
gprint, basis, orbitals
rhf
print 3, 0
optg;
frequencies;
thermo sym=Oh;
print thermo;
---
--------output-----------------
1 2 3 4
5
Wavenumbers [cm-1] 217.27 217.27 217.27 260.70
260.70
Intensities [km/mol] .00 .00 .00 26.08
26.08
Intensities [relative] .00 .00 .00 2.82
2.82
6 7 8 9
10
Wavenumbers [cm-1] 260.70 582.65 582.65 760.67
1043.98
Intensities [km/mol] 26.08 .00 .00 .00
926.07
Intensities [relative] 2.82 .00 .00 .00
100.00
11 12
Wavenumbers [cm-1] 1043.98 1043.98
Intensities [km/mol] 926.07 926.07
Intensities [relative] 100.00 100.00
Normal Modes of imaginary frequencies
1 2 3
Wavenumbers [cm-1] 2.61 2.34 2.05
Intensities [km/mol] .00 .00 .00
Intensities [relative] .00 .00 .00
Normal Modes of low/zero frequencies
1 2 3 4
5
Wavenumbers [cm-1] 22.91 22.91 22.91 157.49
157.49
Intensities [km/mol] .00 .00 .00 .00
.00
Intensities [relative] .00 .00 .00 .00
.00
6
Wavenumbers [cm-1] 157.49
Intensities [km/mol] .00
Intensities [relative] .00
The published Gaussian results are: 157(t2u), 216(t2g), 209(t1u), 702(t1u),
582(eg), 761(a1g), where the T1u modes are IR-active. The MOLPRO IR
freqeuncies listed above are 261 and 1043 cm-1 (comparing with 209 and 702
cm-1)!
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Homepage: http://chemistry.ohio-state.edu/~junli
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