MOLPRO

34 PROPERTIES AND EXPECTATION VALUES 258
34.1.6 Examples
The following example computes the dipole quadrupole moments of water and prints an orbital
analysis. By default, the origin is at the centre of mass, and this is taken as origin for the
quadrupole moments.
***,h2o properties
geometry={o;h1,o,r;h2,o,r,h1,theta} !Z-matrix geometry input
r=1 ang !bond length
theta=104
!bond angle
hf
!do scf calculation
property
!call property program
orbital
!read scf orbitals
density
!read scf density matrix
dm
!compute dipole moments and print orbital contributions
qm
!compute quadrupole moments and print orbital contributio
{multi;state,2;dm
!do full-valence CASSCF
natorb,state=1.1 !compute natural orbitals for state 1.1
natorb,state=2.1} !compute natural orbitals for state 2.1
{property
!call property program
orbital,state=1.1 !read casscf natural orbitals for state 1.1
density,state=1.1 !read casscf density matrix for state 1.1
dm
!compute dipole moments and print orbital contributions
qm}
!compute quadrupole moments and print orbital contributi
{property
!call property program
orbital,state=2.1 !read casscf natural orbitals for state 2.1
density,state=2.1 !read casscf density matrix for state 2.1
dm
!compute dipole moments and print orbital contributions
qm}
!compute quadrupole moments and print orbital contributio
http://www.molpro.net/info/current/examples/h2o_property.com
Alternatively, the dipole and quadrupole moments can be computed directly in the SCF and
MCSCF programs, but in this case no orbital contributions are printed:
***,h2o properties
geometry={o;h1,o,r;h2,o,r,h1,theta} !Z-matrix geometry input
r=1 ang !bond length
theta=104
!bond angle
gexpec,dm,qm
!global request of dipole and quadrupole moments
hf
!do scf calculation
{multi;state,2
!do full-valence CASSCF
natorb,state=1.1 !compute natural orbitals for state 1.1
natorb,state=2.1} !compute natural orbitals for state 2.1
http://www.molpro.net/info/current/examples/h2o_gexpec1.com
34.2 Distributed multipole analysis
Any density matrix can be analysed using the distributed multipole analysis described by Stone,
Chem. Phys. Letters (1981), 83, 233. The multipole moments arising from the overlap of each
pair of primitives are calculated with respect to the overlap centre, and then shifted to the nearest
of a number of multipole sites. By default these comprise all atoms specified in the integral input.
However the list of multipole sites can be modified by deleting and/or adding sites, and also by
restricting the rank of multipole which may be transferred to any given site. The atomic charges