MOLPRO

34 PROPERTIES AND EXPECTATION VALUES 260
No account is taken of symmetry; every site in a symmetry-equivalent set must be specified
explicitly. The radius of the site may also be specified (default 1.0).
DELETE,name
Delete all atoms with the name given from consideration as a multipole site. Note that original
atoms from the integral program have names 1,2,3,... as printed in integral output. DELETE,ALL
deletes all atoms and gives the multipoles with respect to the origin only.
34.2.7 Defining the radius of multipole sites (RADIUS)
RADIUS,name,r;
Assign radius r to all sites with the name given. The program moves multipoles at an overlap
centre P to the site S for which the value of |P−S|/r(S) is smallest. In the absence of a RADIUS
directive, all sites are given radius 1.
34.2.8 Notes and references
The multipoles produced by this analysis are given in their spherical harmonic definitions.
Explicit formulae for translating between the cartesian and spherical harmonic definitions of
the multipole moments are given in, Explicit formulae for the electrostatic energy, forces and
torques between a pair of molecules of arbitrary symmetry, S. L. Price, A. J. Stone, and M.
Alderton, Molec. Phys., 52, 987 (1984).
For examples of the use of DMA analysis see, Price and Stone, Chem. Phys. Lett., 98, 419
(1983); Buckingham and Fowler, J. Chem. Phys., 79, 6426 (1983).
34.2.9 Examples
The following input calculates SCF multipole moments for water.
***,h2o distributed multipole analysis
geometry={o;h1,o,r;h2,o,r,h1,theta} !Z-matrix geometry input
r=1 ang !bond length
theta=104
!bond angle
basis=6-311g**
hf
!do scf calculation
{dma;limit,,4}
!results for total multipoles are
http://www.molpro.net/info/current/examples/h2o_dma.com
34.3 Mulliken population analysis
34.3.1 Calling the population analysis program (POP)
POP;
Invokes Mulliken analysis program, which analyses any density matrix into its contributions
from s,p,d,f... basis functions on each atom. The density matrix is taken from the last dump
record, unless overridden with the DENSITY card. The subcommands may be abbreviated by
the first four characters. The atomic charges are stored in the MOLPRO variable ATCHARGE.
The i’th element in ATCHARGE corresponds to the i’th row of the Z-matrix input.