Beruflich Dokumente
Kultur Dokumente
Also see the following link (EMSL Basis Set Exchange) for easy accessibility of basis sets:
https://bse.pnl.gov/bse/portal
1.2 Density functional
For calculating geometries, all of our work suggests that B3LYP is fairly robust. There is a
series of papers by Michael Buhl (see for example J. Chem. Theory Comput. 2008, 4, 14491459) in which they evaluate a whole lot of functionals. Apart from B3LYP, other
functionals which give good (perhaps slightly better) geometries are BP86, TPSS, B3P86 or
M06. BP86 and TPSS have the advantage of being computationally faster (non-hybrid DFT).
So the choices are:
a) B3LYP
b) BP86
c) M06
Interestingly, the spd functions are almost the same as what you would get if you used even
tempered extrapolation, and the f polarisation function is almost identical to Frenking's (this
is true for Pd at least). The extra f diffuse function looks funny to me, but it is consistent with
the protocol used by Dunning for his aug-cc basis sets. These augmented basis sets for SDD
are recommended to be used with Dunning's cc-pVDZ and aug-cc-pVDZ basis sets on main
group elements.
Thus the choices are:
a) LANL2TZ(f):6-311+G(2d,p)
b) SDD(f):6-311+G(2d,p)
Includes Frenking f polarisation
c) SDD def2-QZVP:6-311+G(2d,p) Different basis set to default SDD in Gaussian,
download from the EMSL library (bse.pnl.gov).
d) New SDD aug-cc-pVnZ-PP:6-311+G(2d,p)
n = D, T, Q, 5
These are very extensive, very flexible basis sets, good for CBS
calculations. But:
- requires new SDD ecp
- optimised for HF and CCSD(T) (not DFT)
- only for second row TM at the moment (1st row is all electron)
e) aug-SDB-cc-pVDZ
I have tested these options:
a) and b) are doable and give reasonable results.
c) is a reasonable option and it sticks to a defined (and well-matched) ecp and basis set.
d) and e) may be useful for very high level calculations.
These two articles suggest that we should routinely do our single point calculations with, say,
three different functionals and see if they give consistent results. We have done this using
B3LYP, TPSS and BP86 and it worked out quite well. It is fairly easy to set up the three
calculations as different steps within the same job in Gaussian. So one recommended
approach is to do the single-point calculations with several functionals and see if the resulting
potential energy surfaces are consistent. This consensus approach certainly helps to satisfy
the wishes of referees!
There are errors introduced into the DFT calculations for very bulky systems due to
dispersion energy issues. There are some new functionals that take account of dispersion
energy in a better way; see Grimme (BP86-D, B3LYP-D), Head-Gordon (wB97XD) and
Truhlar (M06).
PCCP, 2009, 11, 10757-10816
This is a very useful paper by Cramer and Truhlar which gives a good overview of DFT for
transition metal chemistry.
Thus some recommended functionals to try for organometallic chemistry are:
a) BP86 (or BP86-D)
b) B3LYP (or B3LYP-D)
c) M06
Energies
Ligands
6-31G(d)
(or 6-31+G(d) )
6-311+G(2d,p)
Transition
metals
LANL2DZ
LANL2TZ(f)
SDD
SDD Def2-QZVP
B3LYP
B3LYP
M06
M06
Basis sets
Density functionals
b) Single-point energy
%mem=4gb
%nproc=8
# M06 genecp (include scf=tight if Gaussian03 is used)
Title
(charge) (multiplicity)
Atomic coordinates
D
D
1
1
1.00
0.49787892886
1.00
0.21481968266
1.00
0.85666751170E-01
1.00
2.8246600
1.00
0.9431400
1.00
0.3149100
1.00
1.0093000
1.0000000
1.0000000
1.0000000
1.0000000
1.0000000
1.0000000
1.0000000
****
-Ru 0
SDD
4. Lanthanide calculations
(Written by Damien Stringer, former PhD student)
When undertaking lanthanide calculations using Gaussian, the following tips may be helpful:
Select the appropriate level of theory:
DFT provides good results at reasonable computational expense. The B3LYP functional is
used frequently and provides good results. For spin unrestricted calculations, use the
unrestricted version, uB3LYP.
Basis set choice is important:
Incorporation of the lanthanide f electrons into an effective core potential (ECP) has a great
benefit on computational time, and for conformational studies/reaction pathways provides an
appropriate level of agreement with experiment. For higher level electronic/energetic studies,
the f electrons should be treated explicitly. The SDD basis sets are well proven for
lanthanides the MWB## keyword specifies the SDD basis set where ## = number of
electrons in the effective core. Typically this number is 28 for lanthanide calculations where f
electrons are treated explicitly (core involves 1s 3d electrons), but may be larger for
calculations where f electrons are included in the core (e.g. MWB51 for Sm(III)). If a large
core is used, the GUESS=CORE keyword must be specified in the initial single point
calculation. Typically SCF convergence takes longer for lanthanide calculations and the
default number of iterations is insufficient. Specify SCF=(maxcycles=512) to circumvent this
problem.
A general basis set is also often employed. This allows the SDD (or similar) basis set to be
used for the lanthanide and an alternative basis set for the remaining elements (e.g. 6-31G(d)).
As an ECP is required we specify the general basis set with the GENECP keyword.
Undertake a low level single point calculation first:
In order to achieve SCF convergence, a lower level basis set should be used for the first
single point calculation.
E.g. if you are aiming for a final level of theory of MWB28/6-31G(d,p), you might first carry
out a single point calculation at MWB51/3-21G(d). The resulting wavefunction may then be
used as a starting point for the single point calculation at the higher level using the
GUESS=READ keyword.
Check you have obtained a stable wavefunction:
Due to the large number of similar energy-level molecular orbitals that result in lanthanide
calculations, the resulting wavefunction may not be the true minimum, and may cause
problems with further calculations (e.g. geometry optimisations). To ensure the wavefunction
is correct, use the STABLE=OPT keyword. In the resulting output you will see the
wavefunction check, and after the final cycle it should print the wavefunction is already
stable. The stable wavefunction may then be used for geometry optimisations etc. using
GUESS=READ.
If a large core ECP is used, SCF convergence is generally much easier. If problems remain
after employing the above methods, the SCF=QC keyword may be used. This uses a
quadratic convergence algorithm to achieve SCF convergence rather than the default method,
and it is very reliable. This benefit however comes at a significantly greater computational
expense.
An example input file for a problematic single point calculation in a lanthanide study is given
below:
%mem=4gb
%nproc=8
# ub3lyp genecp guess=core scf=(qc, maxcycles=512) stable=opt
Title
(charge) (multiplicity)
Atomic coordinates
10