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Merge branch 'dev-stable' of github.com:QuantumPackage/qp2 into dev-stable
This commit is contained in:
commit
3319d78816
@ -4,13 +4,15 @@ casscf
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|CASSCF| program with the CIPSI algorithm.
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Example of inputs
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-----------------
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Example of inputs for GROUND STATE calculations
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-----------------------------------------------
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NOTICE :: FOR EXCITED STATES CALCULATIONS SEE THE FILE "example_casscf_multistate.sh"
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a) Small active space : standard CASSCF
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---------------------------------------
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Let's do O2 (triplet) in aug-cc-pvdz with the following geometry (xyz format, Bohr units)
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3
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2
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O 0.0000000000 0.0000000000 -1.1408000000
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O 0.0000000000 0.0000000000 1.1408000000
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@ -45,3 +47,4 @@ qp set casscf_cipsi small_active_space False
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qp run casscf | tee ${EZFIO_FILE}.casscf_large.out
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# you should find around -149.9046
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@ -54,14 +54,24 @@ subroutine run
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call write_time(6)
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call write_int(6,iteration,'CAS-SCF iteration = ')
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call write_double(6,energy,'CAS-SCF energy = ')
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call write_double(6,energy,'State-average CAS-SCF energy = ')
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! if(n_states == 1)then
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! call ezfio_get_casscf_cipsi_energy_pt2(E_PT2)
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! call ezfio_get_casscf_cipsi_energy(PT2)
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double precision :: delta_E_istate, e_av
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e_av = 0.d0
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do istate=1,N_states
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call write_double(6,E_PT2(istate),'E + PT2 energy = ')
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call write_double(6,PT2(istate),' PT2 = ')
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e_av += state_average_weight(istate) * Ev(istate)
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if(istate.gt.1)then
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delta_E_istate = E_PT2(istate) - E_PT2(1)
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write(*,'(A6,I2,A18,F16.10)')'state ',istate,' Delta E+PT2 = ',delta_E_istate
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endif
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write(*,'(A6,I2,A18,F16.10)')'state ',istate,' E + PT2 energy = ',E_PT2(istate)
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write(*,'(A6,I2,A18,F16.10)')'state ',istate,' PT2 energy = ',PT2(istate)
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! call write_double(6,E_PT2(istate),'E + PT2 energy = ')
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! call write_double(6,PT2(istate),' PT2 = ')
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enddo
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call write_double(6,e_av,'State-average CAS-SCF energy bis = ')
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call write_double(6,pt2_max,' PT2_MAX = ')
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! endif
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@ -99,8 +109,8 @@ subroutine run
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mo_coef = NewOrbs
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mo_occ = occnum
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call save_mos
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if(.not.converged)then
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call save_mos
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iteration += 1
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if(norm_grad_vec2.gt.0.01d0)then
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N_det = N_states
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66
src/casscf_cipsi/example_casscf_multistate.sh
Executable file
66
src/casscf_cipsi/example_casscf_multistate.sh
Executable file
@ -0,0 +1,66 @@
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# This is an example for MULTI STATE CALCULATION STATE AVERAGE CASSCF
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# We will compute 3 states on the O2 molecule
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# The Ground state and 2 degenerate excited states
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# Please follow carefully the tuto :)
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##### PREPARING THE EZFIO
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# Set the path to your QP2 directory
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QP_ROOT=my_fancy_path
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source ${QP_ROOT}/quantum_package.rc
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# Create the EZFIO folder
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qp create_ezfio -b aug-cc-pvdz O2.xyz -m 3 -a -o O2_avdz_multi_state
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# Start with ROHF orbitals
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qp run scf # ROHF energy : -149.619992871398
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# Freeze the 1s orbitals of the two oxygen
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qp set_frozen_core
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##### PREPARING THE ORBITALS WITH NATURAL ORBITALS OF A CIS
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# Tell that you want 3 states in your WF
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qp set determinants n_states 3
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# Run a CIS wave function to start your calculation
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qp run cis | tee ${EZFIO_FILE}.cis_3_states.out # -149.6652601409258 -149.4714726176746 -149.4686165431939
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# Save the STATE AVERAGE natural orbitals for having a balanced description
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# This will also order the orbitals according to their occupation number
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# Which makes the active space selection easyer !
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qp run save_natorb | tee ${EZFIO_FILE}.natorb_3states.out
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##### PREPARING A CIS GUESS WITHIN THE ACTIVE SPACE
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# Set an active space which has the most of important excitations
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# and that maintains symmetry : the ACTIVE ORBITALS are from """6 to 13"""
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# YOU FIRST FREEZE THE VIRTUALS THAT ARE NOT IN THE ACTIVE SPACE
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# !!!!! WE SET TO "-D" for DELETED !!!!
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qp set_mo_class -c "[1-5]" -a "[6-13]" -d "[14-46]"
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# You create a guess of CIS type WITHIN THE ACTIVE SPACE
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qp run cis | tee ${EZFIO_FILE}.cis_3_states_active_space.out # -149.6515472533511 -149.4622878024821 -149.4622878024817
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# You tell to read the WFT stored (i.e. the guess we just created)
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qp set determinants read_wf True
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##### DOING THE CASSCF
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### SETTING PROPERLY THE ACTIVE SPACE FOR CASSCF
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# You set the active space WITH THE VIRTUAL ORBITALS !!!
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# !!!!! NOW WE SET TO "-v" for VIRTUALS !!!!!
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qp set_mo_class -c "[1-5]" -a "[6-13]" -v "[14-46]"
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# You tell that it is a small actice space so the CIPSI can take all Slater determinants
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qp set casscf_cipsi small_active_space True
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# You specify the output file
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output=${EZFIO_FILE}.casscf_3states.out
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# You run the CASSCF calculation
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qp run casscf | tee ${output} # -149.7175867510 -149.5059010227 -149.5059010226
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# Some grep in order to get some numbers useful to check convergence
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# State average energy
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grep "State-average CAS-SCF energy =" $output | cut -d "=" -f 2 > data_e_average
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# Delta E anticipated for State-average energy, only usefull to check convergence
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grep "Predicted energy improvement =" $output | cut -d "=" -f 2 > data_improve
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# Ground state energy
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grep "state 1 E + PT2 energy" $output | cut -d "=" -f 2 > data_1
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# First excited state energy
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grep "state 2 E + PT2 energy" $output | cut -d "=" -f 2 > data_2
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# First excitation energy
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grep "state 2 Delta E+PT2" $output | cut -d "=" -f 2 > data_delta_E2
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# Second excited state energy
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grep "state 3 E + PT2 energy" $output | cut -d "=" -f 2 > data_3
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# Second excitation energy
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grep "state 3 Delta E+PT2" $output | cut -d "=" -f 2 > data_delta_E3
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@ -226,27 +226,28 @@ BEGIN_PROVIDER [real*8, Umat, (mo_num,mo_num) ]
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end do
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! Form the exponential
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call exp_matrix_taylor(Tmat,mo_num,Umat,converged)
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Tpotmat(:,:)=0.D0
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Umat(:,:) =0.D0
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do i=1,mo_num
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Tpotmat(i,i)=1.D0
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Umat(i,i) =1.d0
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end do
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iter=0
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converged=.false.
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do while (.not.converged)
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iter+=1
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f = 1.d0 / dble(iter)
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Tpotmat2(:,:) = Tpotmat(:,:) * f
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call dgemm('N','N', mo_num,mo_num,mo_num,1.d0, &
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Tpotmat2, size(Tpotmat2,1), &
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Tmat, size(Tmat,1), 0.d0, &
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Tpotmat, size(Tpotmat,1))
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Umat(:,:) = Umat(:,:) + Tpotmat(:,:)
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converged = ( sum(abs(Tpotmat(:,:))) < 1.d-6).or.(iter>30)
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end do
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! Tpotmat(:,:)=0.D0
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! Umat(:,:) =0.D0
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! do i=1,mo_num
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! Tpotmat(i,i)=1.D0
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! Umat(i,i) =1.d0
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! end do
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! iter=0
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! converged=.false.
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! do while (.not.converged)
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! iter+=1
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! f = 1.d0 / dble(iter)
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! Tpotmat2(:,:) = Tpotmat(:,:) * f
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! call dgemm('N','N', mo_num,mo_num,mo_num,1.d0, &
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! Tpotmat2, size(Tpotmat2,1), &
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! Tmat, size(Tmat,1), 0.d0, &
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! Tpotmat, size(Tpotmat,1))
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! Umat(:,:) = Umat(:,:) + Tpotmat(:,:)
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!
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! converged = ( sum(abs(Tpotmat(:,:))) < 1.d-6).or.(iter>30)
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! end do
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END_PROVIDER
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@ -1,9 +1,9 @@
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BEGIN_PROVIDER [double precision, act_2_rdm_trans_spin_trace_mo, (n_act_orb,n_act_orb,n_act_orb,n_act_orb,N_states,N_states)]
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implicit none
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BEGIN_DOC
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! act_2_rdm_trans_spin_trace_mo(i,j,k,l,istate) = STATE SPECIFIC physicist notation for 2rdm_trans
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! act_2_rdm_trans_spin_trace_mo(i,j,k,l,istate,jstate) = STATE SPECIFIC physicist notation for 2rdm_trans
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!
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! \sum_{\sigma,\sigma'}<Psi_{istate}| a^{\dagger}_{i \sigma} a^{\dagger}_{j \sigma'} a_{l \sigma'} a_{k \sigma} |Psi_{istate}>
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! \sum_{\sigma,\sigma'}<Psi_{istate}| a^{\dagger}_{i \sigma} a^{\dagger}_{j \sigma'} a_{l \sigma'} a_{k \sigma} |Psi_{jstate}>
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!
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! WHERE ALL ORBITALS (i,j,k,l) BELONGS TO AN ACTIVE SPACE DEFINED BY "list_act"
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!
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@ -1897,3 +1897,140 @@ end do
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end subroutine pivoted_cholesky
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subroutine exp_matrix(X,n,exp_X)
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implicit none
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double precision, intent(in) :: X(n,n)
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integer, intent(in):: n
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double precision, intent(out):: exp_X(n,n)
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BEGIN_DOC
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! exponential of the matrix X: X has to be ANTI HERMITIAN !!
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!
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! taken from Hellgaker, jorgensen, Olsen book
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!
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! section evaluation of matrix exponential (Eqs. 3.1.29 to 3.1.31)
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END_DOC
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integer :: i
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double precision, allocatable :: r2_mat(:,:),eigvalues(:),eigvectors(:,:)
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double precision, allocatable :: matrix_tmp1(:,:),eigvalues_mat(:,:),matrix_tmp2(:,:)
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include 'constants.include.F'
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allocate(r2_mat(n,n),eigvalues(n),eigvectors(n,n))
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allocate(eigvalues_mat(n,n),matrix_tmp1(n,n),matrix_tmp2(n,n))
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! r2_mat = X^2 in the 3.1.30
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call get_A_squared(X,n,r2_mat)
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call lapack_diagd(eigvalues,eigvectors,r2_mat,n,n)
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eigvalues=-eigvalues
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if(.False.)then
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!!! For debugging and following the book intermediate
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! rebuilding the matrix : X^2 = -W t^2 W^T as in 3.1.30
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! matrix_tmp1 = W t^2
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print*,'eigvalues = '
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do i = 1, n
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print*,i,eigvalues(i)
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write(*,'(100(F16.10,X))')eigvectors(:,i)
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enddo
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eigvalues_mat=0.d0
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do i = 1,n
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! t = dsqrt(t^2) where t^2 are eigenvalues of X^2
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eigvalues(i) = dsqrt(eigvalues(i))
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eigvalues_mat(i,i) = eigvalues(i)*eigvalues(i)
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enddo
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call dgemm('N','N',n,n,n,1.d0,eigvectors,size(eigvectors,1), &
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eigvalues_mat,size(eigvalues_mat,1),0.d0,matrix_tmp1,size(matrix_tmp1,1))
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call dgemm('N','T',n,n,n,-1.d0,matrix_tmp1,size(matrix_tmp1,1), &
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eigvectors,size(eigvectors,1),0.d0,matrix_tmp2,size(matrix_tmp2,1))
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print*,'r2_mat new = '
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do i = 1, n
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write(*,'(100(F16.10,X))')matrix_tmp2(:,i)
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enddo
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endif
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! building the exponential
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! exp(X) = W cos(t) W^T + W t^-1 sin(t) W^T X as in Eq. 3.1.31
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! matrix_tmp1 = W cos(t)
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do i = 1,n
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eigvalues_mat(i,i) = dcos(eigvalues(i))
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enddo
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! matrix_tmp2 = W cos(t)
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call dgemm('N','N',n,n,n,1.d0,eigvectors,size(eigvectors,1), &
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eigvalues_mat,size(eigvalues_mat,1),0.d0,matrix_tmp1,size(matrix_tmp1,1))
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! matrix_tmp2 = W cos(t) W^T
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call dgemm('N','T',n,n,n,-1.d0,matrix_tmp1,size(matrix_tmp1,1), &
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eigvectors,size(eigvectors,1),0.d0,matrix_tmp2,size(matrix_tmp2,1))
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exp_X = matrix_tmp2
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! matrix_tmp2 = W t^-1 sin(t) W^T X
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do i = 1,n
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if(dabs(eigvalues(i)).gt.1.d-4)then
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eigvalues_mat(i,i) = dsin(eigvalues(i))/eigvalues(i)
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else ! Taylor development of sin(x)/x near x=0 = 1 - x^2/6
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eigvalues_mat(i,i) = 1.d0 - eigvalues(i)*eigvalues(i)*c_1_3*0.5d0
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endif
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enddo
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! matrix_tmp1 = W t^-1 sin(t)
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call dgemm('N','N',n,n,n,1.d0,eigvectors,size(eigvectors,1), &
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eigvalues_mat,size(eigvalues_mat,1),0.d0,matrix_tmp1,size(matrix_tmp1,1))
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! matrix_tmp2 = W t^-1 sin(t) W^T
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call dgemm('N','T',n,n,n,-1.d0,matrix_tmp1,size(matrix_tmp1,1), &
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eigvectors,size(eigvectors,1),0.d0,matrix_tmp2,size(matrix_tmp2,1))
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! exp_X += matrix_tmp2 X
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call dgemm('N','N',n,n,n,1.d0,matrix_tmp2,size(matrix_tmp2,1), &
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X,size(X,1),1.d0,exp_X,size(exp_X,1))
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end
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subroutine exp_matrix_taylor(X,n,exp_X,converged)
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implicit none
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BEGIN_DOC
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! exponential of a general real matrix X using the Taylor expansion of exp(X)
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!
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! returns the logical converged which checks the convergence
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END_DOC
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double precision, intent(in) :: X(n,n)
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integer, intent(in):: n
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double precision, intent(out):: exp_X(n,n)
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logical :: converged
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double precision :: f
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integer :: i,iter
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double precision, allocatable :: Tpotmat(:,:),Tpotmat2(:,:)
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allocate(Tpotmat(n,n),Tpotmat2(n,n))
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BEGIN_DOC
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! exponential of X using Taylor expansion
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END_DOC
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Tpotmat(:,:)=0.D0
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exp_X(:,:) =0.D0
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do i=1,n
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Tpotmat(i,i)=1.D0
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exp_X(i,i) =1.d0
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end do
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iter=0
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converged=.false.
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do while (.not.converged)
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iter+=1
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f = 1.d0 / dble(iter)
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Tpotmat2(:,:) = Tpotmat(:,:) * f
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call dgemm('N','N', n,n,n,1.d0, &
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Tpotmat2, size(Tpotmat2,1), &
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X, size(X,1), 0.d0, &
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Tpotmat, size(Tpotmat,1))
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exp_X(:,:) = exp_X(:,:) + Tpotmat(:,:)
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converged = ( sum(abs(Tpotmat(:,:))) < 1.d-6).or.(iter>30)
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end do
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if(.not.converged)then
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print*,'Warning !! exp_matrix_taylor did not converge !'
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endif
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end
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subroutine get_A_squared(A,n,A2)
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implicit none
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BEGIN_DOC
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! A2 = A A where A is n x n matrix. Use the dgemm routine
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END_DOC
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double precision, intent(in) :: A(n,n)
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integer, intent(in) :: n
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double precision, intent(out):: A2(n,n)
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call dgemm('N','N',n,n,n,1.d0,A,size(A,1),A,size(A,1),0.d0,A2,size(A2,1))
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end
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