|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Lithium
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Introduction
|
|
|
|
|
|
|
|
|
|
|
|
|
|
In
the Tables that follow, RSD is the residual standard deviation of the
linear regression analysis of the calculated efg's versus the
experimental nqcc's for the molecules given on the previous
page.
This may be taken as a conservative estimate of the
uncertainty
in the calculated nqcc's. (Note: A RSD of 10 kHz is 5 % of
the
average absolute experimental nqcc for the molecules used for
calibration.) All three diagonal components of the efg
tensors
are plotted against the corresponding components of the experimental
nqcc tensors. This assures, because the tensors are traceless, that the
linear regression line pass through the origin. The slope of
this
line is eQeff/h from which the value
of Qeff is extracted. Qeff
is the model
dependent nuclear electric quadrupole moment effective
for calculation of the nqcc's. For comparison, the currently
recommended Q for 7Li
is -40.1 mb.
It is our goal to reproduce accurately as well as efficiently
the
experimental nqcc's - not Q. It is sufficient - indeed, all that can be
expected at the level of theory in this work - that Qeff
and
Q agree to within a few percent. Note that, in this
case,
the Dunning cc-pVQZ bases, which
give the smaller RSD's, give values of Qeff
that
differ
from Q by ~15-25 %. With the cc-pVTZ bases, on the other
hand, Qeff
= Q (within the standard error in Qeff) in many
cases, but
the RSD's are larger. |
|
|
|
|
|
|
|
|
|
|
|
|
|
For
the Dunning correlation consistent basis sets, G03 and EMSL indicate
the source of the bases used for the calculation. G03 is
Gaussian
03, which contains these bases somewhat modified to increase
computational efficiency. EMSL is the online EMSL Basis Set
Library. Note: Diffuse functions "aug" are not defined for
lithium. |
|
|
|
|
|
|
|
|
|
|
|
|
|
FC
= Frozen core, FULL = All electron correlation.
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table
1. Calibration of
Method/cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL). RSD (kHz) and
Qeff (mb). |
|
|
|
|
|
Method
|
RSD
|
-Qeff
|
|
|
|
|
|
HF
|
7.3
|
40.41(31)
|
|
MP2(FC)
|
20.2
|
44.49(93)
|
|
MP2(FULL)
|
17.5
|
43.03(78)
|
|
MP3(FC)
|
12.6
|
43.08(56)
|
|
MP3(FULL)
|
10.9
|
41.81(47)
|
|
MP4(SDQ)
|
15.3
|
43.94(70)
|
|
CCSD(FULL)
|
11.6
|
42.54(51)
|
|
QCISD(FULL)
|
12.5
|
42.78(55)
|
|
|
|
|
|
B1LYP
|
11.0
|
39.77(45)
|
|
B3LYP
|
11.7
|
39.74(48)
|
|
B3P86
|
12.6
|
39.85(52)
|
|
B3PW91
|
12.2
|
39.72(50)
|
|
mPW1PW91
|
10.6
|
39.75(44)
|
|
PBE1PBE
|
11.1
|
39.44(45)
|
|
B98
|
12.8
|
40.23(54)
|
|
B971
|
13.5
|
40.10(56)
|
|
B972
|
11.9
|
41.36(51)
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table
2. Calibration of HF/Basis. RSD
(kHz) and
Qeff (mb). |
|
|
|
|
|
HF/
|
RSD
|
-Qeff
|
|
|
|
|
|
cc-pCVDZ(Li)/aug-cc-pVDZ
(EMSL)
|
26.5
|
38.9(11)
|
|
|
|
|
|
cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) |
7.3
|
40.41(31)
|
|
cc-pCVTZ(Li)/cc-pVTZ
(EMSL) |
9.6
|
41.77(42)
|
|
cc-pVTZ(Li)/aug-cc-pVTZ
(EMSL)
|
7.5
|
33.52(26)
|
|
cc-pVTZ(Li)/aug-cc-pVTZ
(G03) |
7.9
|
33.40(27)
|
|
cc-pVTZ (EMSL)
|
9.9
|
35.34(36)
|
|
cc-pVTZ (G03) |
9.9
|
35.34(36)
|
|
|
|
|
|
cc-pCVQZ(Li)/aug-cc-pVQZ
(EMSL) |
7.9
|
36.19(30)
|
|
cc-pCVQZ(Li)/cc-pVQZ
(EMSL) |
7.6
|
36.42(29)
|
|
cc-pVQZ(Li)/aug-cc-pVQZ
(EMSL) |
9.2
|
32.60(31)
|
|
cc-pVQZ
(EMSL) |
9.3
|
32.74(31)
|
|
|
|
|
|
6-311++G(3df,3pd)
|
12.4
|
38.40(50)
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table
3. Calibration of HF-DFT/Basis. RSD (kHz) and
Qeff (mb). |
|
|
|
|
|
B1LYP/
|
RSD
|
-Qeff
|
|
|
|
|
|
cc-pCVDZ(Li)/aug-cc-pVDZ
(EMSL)
|
27.1
|
38.3(11)
|
|
cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) |
11.0
|
39.77(45)
|
|
cc-pCVQZ(Li)/aug-cc-pVQZ
(EMSL) |
8.5
|
37.07(33)
|
|
cc-pCVQZ(Li)/cc-pVQZ
(EMSL) |
9.2
|
37.37(36)
|
|
cc-pVQZ(Li)/aug-cc-pVQZ
(EMSL) |
4.8
|
31.06(15)
|
|
cc-pVQZ (EMSL)
|
5.5
|
33.25(19)
|
|
|
|
|
|
6-31+G(df,p)
|
23.8
|
50.6(12)
|
|
6-311+G(d,p)
|
30.1
|
40.4(13)
|
|
6-311++G(3df,3pd)
|
31.8
|
44.1(15)
|
|
|
|
|
|
B3LYP/
|
|
|
|
|
|
|
|
cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) |
11.7
|
39.74(48)
|
|
cc-pCVQZ(Li)/aug-cc-pVQZ
(EMSL) |
8.6
|
36.82(33)
|
|
|
|
|
|
mPW1PW91
|
|
|
|
|
|
|
|
cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) |
10.6
|
39.75(44)
|
|
cc-pCVQZ(Li)/aug-cc-pVQZ
(EMSL) |
4.4
|
34.91(16)
|
|
cc-pCVQZ(Li)/cc-pVQZ
(EMSL) |
5.9
|
35.40(22)
|
|
cc-pVQZ(Li)/aug-cc-pVQZ
(EMSL) |
3.0
|
29.68(9)
|
|
cc-pVQZ (EMSL) |
4.0
|
31.38(13)
|
|
|
|
|
|
PBE1PBE
|
|
|
|
|
|
|
|
cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) |
11.1
|
39.44(45)
|
|
cc-pCVQZ(Li)/aug-cc-pVQZ
(EMSL) |
5.4
|
35.46(20)
|
|
cc-pCVQZ(Li)/cc-pVQZ
(EMSL) |
6.8
|
35.95(25)
|
|
cc-pVQZ(Li)/aug-cc-pVQZ
(EMSL) |
3.2
|
30.13(10)
|
|
cc-pVQZ (EMSL) |
4.5
|
31.96(15)
|
|
|
|
|
|
B972/
|
|
|
|
|
|
|
|
cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) |
11.9
|
41.36(51)
|
|
cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) |
4.6
|
35.47(17)
|
|
cc-pCVQZ(Li)/cc-pVQZ
(EMSL) |
5.9
|
36.12(22)
|
|
cc-pVQZ(Li)/aug-cc-pVQZ
(EMSL) |
4.7
|
30.31(15)
|
|
cc-pVQZ (EMSL) |
4.5
|
31.89(15)
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
HF/cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) PDF
|
|
|
|
|
|
|
HF/cc-pCVQZ(Li)/aug-cc-pVQZ
(EMSL) PDF
|
|
|
|
|
|
|
mPW1PW91/cc-pCVTZ(Li)/aug-cc-pVTZ
(EMSL) PDF |
|
|
|
|
|
|
mPW1PW91/cc-pCVQZ(Li)/aug-cc-pVQZ
(EMSL) PDF |
|
|
|
|
|
|
mPW1PW91/cc-pCVQZ(Li)/cc-pVQZ
(EMSL) PDF |
|
|
|
|
|
|
mPW1PW91/cc-pVQZ(Li)/aug-cc-pVQZ
(EMSL) PDF |
|
|
|
|
|
|
mPW1PW91/cc-pVQZ
(EMSL) PDF
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Go
back
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Table
of Contents
|
|
|
|
|
|
|
Molecules/Lithium
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|