Pseudo

DESCRIPTION

This keyword requests that a model potential be substituted for the core electrons. The Cards option is by far its most-used mode. Gaussian supports a new effective core potential (ECP) input format (similar to that used by ExtraBasis) which is described below. When reading-in pseudopotentials, do not give them the same names as any internally-stored pseudopotentials: CEP, CHF, LANL1, LANL2, LP-31, SDD and SHC.

If used with ONIOM, the Pseudo keyword applies to all layer of the ONIOM. If you want to read in ECPs only for one ONIOM layer, then use the GenECP keyword instead.

Pseudo without any options defaults to Pseudo=Read.

OPTIONS

Read
Read pseudopotential data from the input stream. Input is described in the next subsection below. Cards is a synonym for Read.

Old
Read pseudopotential data using the old format (used by Gaussian 92 and earlier versions).

CHF
Requests the Coreless Hartree-Fock potentials. This option is normally used with the LP-31G basis sets.

SHC
Requests the SHC potentials.

LANL1
Requests the LANL1 potentials.

LANL2
Requests the LANL2 potentials.

FULL ECP INPUT FORMAT

Effective Core Potential operators are sums of products of polynomial radial functions, Gaussian radial functions and angular momentum projection operators. ECP input therefore specifies which potential to use on each atomic center, and then includes a collection of triplets of:

        (coefficient, power of R, exponent)

for each potential for each term in each angular momentum of the ECP. Since only the first few angular momentum components have different terms, the potential is expressed as (1) terms for the general case, typically d or f and higher projection, and (2) the extra terms for each special angular momentum. Thus for an LP-31G potential, which includes special s and p projected terms, the input includes the general (d and higher) term, the s-d term (i.e., what to add to the general term to make the s component) and the p-d term.

All ECP input is free-format. Each block is introduced by a line containing the center numbers (from the molecule specification) and/or atomic symbols, specifying the atoms and/or atoms types to which it applies (just as for general basis set input-see the discussion of the Gen keyword). The list ends with a value of 0.

The pseudopotential for those centers/atoms follows:

Name,Max,ICore
Name of the potential, maximum angular momentum of the potential (i.e., 2 if there are special s and p projections, 3 if there are s, p, and d projections), and number of core electrons replaced by the potential. If Name matches the name of a previous potential, that potential is reused and no further input other than the terminator line (see below) is required.

For each component (I=1 to Max) of the current potential, a group of terms is read, containing the following information:

Title
A description of the block, not otherwise used.

NTerm
Number of terms in the block.

NPower,Expon,Coef
Power of R, exponent, and coefficient for each of the NTerm terms. NPower includes the R² Jacobian factor.

An example of an input file which includes a nonstandard ECP with its associated basis set is given below.

SIMPLIFIED ECP INPUT FORMAT

Gaussian adds flexibility to ECP input by allowing it to include pre-defined basis sets names. An ECP definition may be replaced by a line containing the standard keyword for a pre-defined basis set. In this case, the ECPs within the specified basis set corresponding to the specified atom type(s) will be used for that atom (see the examples).

KEYWORDS FOR STUTTGART/DRESDEN ECP INPUT

In Pseudo input, keywords for these ECPs are of the form XYn where n is the number of core electrons which are replaced by the pseudopotential and X denotes the reference system used for generating the pseudopotential (S for a single-valence-electron ion or M for a neutral atom).

Y specifies the theoretical level of the reference data: HF for Hartree-Fock, WB for Wood-Boring quasi-relativistic and DF for Dirac-Fock relativistic. For one- or two-valence electron atoms SDF is a good choice; otherwise MWB or MDF is recommended (although for small atoms or for the consideration of relativistic effects, the corresponding SHF and MHF pseudopotentials may be useful).

AVAILABILITY

The Stuttgart/Dresden ECPs are not uniformly available across the periodic table. The following table shows the availability of the various XY combinations, along with valid values for n. The Defaults columns list the equivalencies for the SDD keyword (which selects an all electron basis set through Cl and ECPs thereafter) and when IOp(3/6) is set to 6 (which selects ECPs for all elements).

Note: These ECPs are not available for elements 87 (Fr), 88 (Ra), and 105 and higher.

RELATED KEYWORDS

ChkBasis, ExtraBasis, Gen, GenECP

EXAMPLES

Specifying an ECP. This input file runs an RHF/LP-31G calculation on hydrogen peroxide, with the basis set and ECP data read from the input file:

# HF/Gen Pseudo=Read Test
 
Hydrogen peroxide

0,1
O
H,1,R2
O,1,R3,2,A3
H,3,R2,1,A3,2,180.,0
 
R2=0.96
R3=1.48
A3=109.47
 
General basis set input
****
 
O 0                        ECPs for the oxygen atoms.
OLP 2 2                    ECP name=OLP, applies to d & higher, replaces 2 electrons.
D component                Description for the general terms.
3                          Number of terms to follow.
1 80.0000000  -1.60000000
1 30.0000000  -0.40000000
2  1.0953760  -0.06623814
S-D projection             Corrections for projected terms (lowest angular momentum).
3
0  0.9212952   0.39552179
0 28.6481971   2.51654843
2  9.3033500  17.04478500
P-D                        Corrections for projected terms (highest angular momentum).
2
2 52.3427019  27.97790770
2 30.7220233 -16.49630500 
                           Blank line indicates end of the ECP block.

The basis set data follows the molecule specification section. The first line of the ECP data requests that a potential be read in (type 7) for atoms number 1 and 3 (the oxygen atoms). No potential is to be used for atoms 2 and 4 (the hydrogen atoms).

The second line of ECP data begins the input for the centers requiring a read-in potential: in this case, oxygen atoms. The potential on these centers is named OLP, it is a general term and applies to angular momentum 2 (d) and higher, and the potential replaces two electrons. Next comes a title for the general term (D component), and the number of components of that term (3); the individual components follow on the next 3 lines. Next come the corrections for the projected terms in two sections, lowest angular momentum first. Each section again consists of a title line, the number of terms to follow, and then the terms themselves.

Using Standard Basis Set Keywords to Specify ECPs. The following input file illustrates the use of the simplified ECP input format:

# Becke3LYP/Gen Pseudo=Read Opt Test
 
HF/6-31G(d) Opt of Cr(CO)6
 
0 1
Cr 0.0  0.0  0.0
molecule specification continues …
 
C O 0
6-31G(d)
****
Cr 0
LANL2DZ
****
 
Cr 0                                  ECP for chromium atom.
LANL2DZ                               Use the ECP in this basis set.

Last update: 23 April 2013