MOLPRO

25 EXCITED STATES WITH EQUATION-OF-MOTION CCSD (EOM-CCSD) 191
25.4 Examples
25.4.1 PES for lowest excited states for hydrogen fluride
This example shows how to calculate potential energy surfaces for several excited states using
restart from a previous calculation.
***, PES for several lowest states of hydrogen fluoride
memory,2,m
basis=avdz
! define basis set
geometry={h;f,h,r}
! z-matrix
r=0.8 Ang
! start from this distance
do n=1,100
! loop over distances
rr(n)=r
! save distance for table
hf
! do SCF calculation
ccsd
! do CCSD calculation, try to restart
start,4000.2,save,4000.2
! and save final T amplitudes
eom,-2.1,-1.2,-1.4,start=6000.2,save=6000.2 ! do EOM-CCSD calculation, try to restart
! and save final excited states’ amplitudes
ebase(n)=energy(1)
e2(n)=energy(2)-energy(1)
e3(n)=energy(3)-energy(1)
e4(n)=energy(4)-energy(1)
r=r+0.01
! increment distance
enddo
! end of do loop
table,rr,ebase,e2,e3,e4
! make table with results
digits,2,8,5,5,5,5,5,5,5,5
! modify number of digits
head,R(Ang),EGRST,E_EXC(2.1),E_EXC(1.2),E_EXC(1.4)! modify headers of table
! title of table
! save ground state energy for this geometry
! save excitation energies for this geometry
title,EOM-CCSD excitation energies for hydrogen fluoride (in hartree), basis $basis
save,hf_eom_ccsd.tab
! save table in file
http://www.molpro.net/info/current/examples/hf_eom_pes.com
This calculation produces the following table:
EOM-CCSD excitation energies for hydrogen fluoride (in hartree), basis AVDZ
R(ANG) EGRST E_EXC(2.1) E_EXC(1.2) E_EXC(1.4)
0.80 -100.23687380 0.56664 0.41204 0.56934
0.81 -100.24094256 0.56543 0.40952 0.56812
0.82 -100.24451598 0.56422 0.40695 0.56690
etc.
25.4.2 EOM-CCSD transition moments for hydrogen fluoride
This example shows how to calculate and store CCSD and EOM-CCSD density matrices, calculate
dipole and quadrupole moments (transition moments from the ground to excited states
are calculated), and how to use the EOM-CCSD excited state density for Mulliken population
analysis.