L-PDFT Nuclear Gradients (pyscf#43)

* add lpdft grad * some basic skeleton stuff * modify lpdft to cache CI vectors etc and grad/mcpdft for gfock sym build * might have get_wfn_response completed * fixed? maybe the get_ci_adiabats finally? * added some tests for wfn_response, not getting correct CI terms I know since they are not zero for fully variational case.. * fixed CI projection issue * won't try and test wfn_response...moving on to ham_response * need to add the EX component to derivative I think * got to evaluating eot, vot, and fot * need to fix vot contraction * moved xc_response to function * might have everything???? * trying to test h2 with no parameters * fix coulomb and weight derivaive contribution * agggggg off by a little * maybe progress made? * IT WORKS!!!!! Signed-off-by: Matthew Hennefarth <[email protected]> * error with core orbitals or something * merge * adding tests * test but also fix lpdft log printing * maybe some printing, but still have CI issues for lagrange... * no update, just checking tests * confused still * might hvae fixed itgit status * add tests * remove df test and uncomment slow stuff * add git tag info for tests * add scanner test * add some details for multi_state_mix...but leaving for now.. * add doc strings to some functions * fix lint * fix lint * fix lint * remove print from test * fix np warning * try and fix test * clean imports for lpdft * explicitily add _e_states * update lpdft grad test, add mo hhe * add hhe ci only * add final test for hhe * add lih ci only * modify a comment... * fixed for mo? * add all lda tests * add ftpbe test * slight improvement, but think I can do better * made it faster finally * fix lint * add pdft_feff test for delta * add examples * update readme * update to include slow tests * add space * remove space * add lpdft doi --------- Signed-off-by: Matthew Hennefarth <[email protected]>
NingZhang1 · Mar 26, 2024 · f817911 · f817911
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diff --git a/doc/mcpdft/README.md b/doc/mcpdft/README.md
@@ -1,19 +1,20 @@
-Multi-configuration pair-density functional theory module for PySCF
-=========================
+# Multi-configuration pair-density functional theory module for PySCF
 
-2022-11-27
+2024-01-26
 
-* Version 1.0
+- Version 1.0
 
-Install
--------
-* Install to python site-packages folder
-```
+## Install
+
+- Install to python site-packages folder
+
+```sh
 pip install git+https://github.com/pyscf/pyscf-forge
 ```
 
-* Install in a custom folder for development
-```
+- Install in a custom folder for development
+
+```sh
 git clone https://github.com/pyscf/pyscf-forge /home/abc/local/path
 
 # Set pyscf extended module path
@@ -27,64 +28,67 @@ cmake ..
 make
 ```
 
-Features
--------
-* Multi-configuration pair-density functional theory (MC-PDFT) total electronic
+## Features
+
+- Multi-configuration pair-density functional theory (MC-PDFT) total electronic
   energy calculations for wave functions of various types.
-    - CASCI
-    - CASSCF
-    - State-averaged CASSCF (including "mixed" solver with different spins
-      and/or point groups)
-    - Extended multi-state MC-PDFT (XMS-PDFT): [*Faraday Discuss* **2020**, 224, 348-372]
-    - Compressed multi-state MC-PDFT (CMS-PDFT): [*JCTC* **2020**, *16*, 7444]
-    - Linearized PDFT (L-PDFT): [*JCTC* **2023**, *19*, 3172]
-* On-the-fly generation of on-top density functionals from underlying KS-DFT
+  - CASCI
+  - CASSCF
+  - State-averaged CASSCF (including "mixed" solver with different spins
+    and/or point groups)
+  - Extended multi-state MC-PDFT (XMS-PDFT): [*Faraday Discuss* **2020**, 224, 348-372]
+  - Compressed multi-state MC-PDFT (CMS-PDFT): [*JCTC* **2020**, *16*, 7444]
+  - Linearized PDFT (L-PDFT): [*JCTC* **2023**, *19*, 3172]
+- On-the-fly generation of on-top density functionals from underlying KS-DFT
   'LDA' or 'GGA' exchange-correlation functionals as defined in Libxc.
-    - Translated functionals: [*JCTC* **2014**, *10*, 3669]
-    - Fully-translated functionals: [*JCTC* **2015**, *11*, 4077]
-    - Global hybrid functionals: [*JPCL* **2020**, *11*, 10158] and
-      [*JCTC* **2020**, *16*, 2274]
-    - Notes:
-        1. Translation of 'meta' KS-DFT functionals which depend on the
-           kinetic energy density and/or Laplacian is not supported.
-        2. Range-separated hybrid on-top functionals are not supported.
-        3. Translation of functionals defined as global hybrids at the Libxc or
-           PySCF level is not supported, except for 'tPBE0' and 'ftPBE0'.
-           Other global hybrid functionals are specified using PySCF's [custom
-           functional parser]; see [examples/mcpdft/02-hybrid_functionals.py].
-* Additional properties
-    - Decomposition of total electronic energy into core, Coulomb, on-top
-      components
-    - Analytical nuclear gradients (non-hybrid functionals only) for:
-        1. Single-state CASSCF wave function: [*JCTC* **2018**, *14*, 126]
-        2. State-averaged CASSCF wave functions: [*JCP* **2020**, *153*, 014106]
-        3. CMS-PDFT: [*Mol Phys* **2022**, 120]
-    - Permanent electric dipole moment (non-hybrid functionals only) for:
-        1. Single-state CASSCF wave function: [*JCTC* **2021**, *17*, 7586]
-        2. State-averaged CASSCF wave functions
-        3. CMS-PDFT
-    - Transition electric dipole moment (non-hybrid functionals only) for:
-        1. CMS-PDFT
-    - Derivative couplings for:
-        1. CMS-PDFT [*JPC A* **2024**]
-* Multi-configuration density-coherence functional theory (MC-DCFT)
+  - Translated functionals: [*JCTC* **2014**, *10*, 3669]
+  - Fully-translated functionals: [*JCTC* **2015**, *11*, 4077]
+  - Global hybrid functionals: [*JPCL* **2020**, *11*, 10158] and
+    [*JCTC* **2020**, *16*, 2274]
+  - Notes:
+    1. Translation of 'meta' KS-DFT functionals which depend on the
+       kinetic energy density and/or Laplacian is not supported.
+    1. Range-separated hybrid on-top functionals are not supported.
+    1. Translation of functionals defined as global hybrids at the Libxc or
+       PySCF level is not supported, except for 'tPBE0' and 'ftPBE0'.
+       Other global hybrid functionals are specified using PySCF's [custom
+       functional parser][custom functional parser]; see [examples/mcpdft/02-hybrid_functionals.py].
+- Additional properties
+  - Decomposition of total electronic energy into core, Coulomb, on-top
+    components
+  - Analytical nuclear gradients (non-hybrid functionals only) for:
+    1. Single-state CASSCF wave function: [*JCTC* **2018**, *14*, 126]
+    1. State-averaged CASSCF wave functions: [*JCP* **2020**, *153*, 014106]
+    1. CMS-PDFT: [*Mol Phys* **2022**, 120]
+    1. L-PDFT: [*JCTC* **2024**]
+  - Permanent electric dipole moment (non-hybrid functionals only) for:
+    1. Single-state CASSCF wave function: [*JCTC* **2021**, *17*, 7586]
+    1. State-averaged CASSCF wave functions
+    1. CMS-PDFT
+  - Transition electric dipole moment (non-hybrid functionals only) for:
+    1. CMS-PDFT
+  - Derivative couplings for:
+    1. CMS-PDFT [*JPC A* **2024**]
+- Multi-configuration density-coherence functional theory (MC-DCFT)
   total energy: [*JCTC* **2021**, *17*, 2775]
 
-[comment]: <> (Reference hyperlinks)
-[*JCTC* **2020**, *16*, 7444]: http://dx.doi.org/10.1021/acs.jctc.0c00908
-[*JCTC* **2014**, *10*, 3669]: http://dx.doi.org/10.1021/ct500483t
-[*JCTC* **2015**, *11*, 4077]: http://dx.doi.org/10.1021/acs.jctc.5b00609
-[*JPCL* **2020**, *11*, 10158]: http://dx.doi.org/10.1021/acs.jpclett.0c02956
-[*JCTC* **2020**, *16*, 2274]: http://dx.doi.org/10.1021/acs.jctc.9b01178
-[*JCTC* **2018**, *14*, 126]: http://dx.doi.org/10.1021/acs.jctc.7b00967
-[*JCP* **2020**, *153*, 014106]: http://dx.doi.org/10.1063/5.0007040
-[*JCTC* **2021**, *17*, 7586]: http://dx.doi.org/10.1021/acs.jctc.1c00915
-[*JCTC* **2021**, *17*, 2775]: http://dx.doi.org/10.1021/acs.jctc.0c01346
-[*Mol Phys* **2022**, 120]: http://dx.doi.org/10.1080/00268976.2022.2110534
-[*Faraday Discuss* **2020**, 224, 348-372]: http://dx.doi.org/10.1039/D0FD00037J
-[*JCTC* **2023**, *19*, 3172]: https://dx.doi.org/10.1021/acs.jctc.3c00207
+[*arxiv* 2401.12933]: https://dx.doi.org/10.48550/arXiv.2401.12933
+[*faraday discuss* **2020**, 224, 348-372]: http://dx.doi.org/10.1039/D0FD00037J
+[*jcp* **2020**, *153*, 014106]: http://dx.doi.org/10.1063/5.0007040
+[*jctc* **2014**, *10*, 3669]: http://dx.doi.org/10.1021/ct500483t
+[*jctc* **2015**, *11*, 4077]: http://dx.doi.org/10.1021/acs.jctc.5b00609
+[*jctc* **2018**, *14*, 126]: http://dx.doi.org/10.1021/acs.jctc.7b00967
+[*jctc* **2020**, *16*, 2274]: http://dx.doi.org/10.1021/acs.jctc.9b01178
+[*jctc* **2020**, *16*, 7444]: http://dx.doi.org/10.1021/acs.jctc.0c00908
+[*jctc* **2021**, *17*, 2775]: http://dx.doi.org/10.1021/acs.jctc.0c01346
+[*jctc* **2021**, *17*, 7586]: http://dx.doi.org/10.1021/acs.jctc.1c00915
+[*jctc* **2023**, *19*, 3172]: https://dx.doi.org/10.1021/acs.jctc.3c00207
+[*jpcl* **2020**, *11*, 10158]: http://dx.doi.org/10.1021/acs.jpclett.0c02956
+[*mol phys* **2022**, 120]: http://dx.doi.org/10.1080/00268976.2022.2110534
+[*JCTC* **2024**]: https://dx.doi.org/10.1021/acs.jctc.4c00095
 [*JPC A* **2024**]: https://dx.doi.org/10.1021/acs.jpca.3c07048
 
 [comment]: <> (Code hyperlinks)
 [examples/mcpdft/02-hybrid_functionals.py]: examples/mcpdft/02-hybrid_functionals.py
 [custom functional parser]: https://github.com/pyscf/pyscf/blob/master/examples/dft/24-custom_xc_functional.py
+[examples/mcpdft/02-hybrid_functionals.py]: examples/mcpdft/02-hybrid_functionals.py
diff --git a/examples/grad/02-multi_state_mcpdft_grad.py b/examples/grad/02-multi_state_mcpdft_grad.py
@@ -7,23 +7,35 @@
 from pyscf import gto, scf, mcpdft
 
 mol = gto.M(
-    atom = [
-        ['Li', ( 0., 0.    , 0.   )],
-        ['H', ( 0., 0., 1.7)]
-    ], basis = 'sto-3g',
-    symmetry = 0 # symmetry enforcement is not recommended for MS-PDFT
-    )
+    atom=[
+        ['Li', (0., 0., 0.)],
+        ['H', (0., 0., 1.7)]
+    ], basis='sto-3g',
+    symmetry=0  # symmetry enforcement is not recommended for MS-PDFT
+)
 
 mf = scf.RHF(mol)
 mf.kernel()
 
 mc = mcpdft.CASSCF(mf, 'tpbe', 2, 2)
-mc.fix_spin_(ss=0) # often necessary!
-mc = mc.multi_state ([.5,.5]).run ()
+mc.fix_spin_(ss=0)  # often necessary!
 
-mc_grad = mc.nuc_grad_method ()
-de0 = mc_grad.kernel (state=0)
-de1 = mc_grad.kernel (state=1)
-print ("Gradient of ground state:\n",de0)
-print ("Gradient of first singlet excited state:\n",de1)
+# For CMS-PDFT Gradients
+cms = mc.multi_state([.5, .5], method='cms').run()
 
+mc_grad = cms.nuc_grad_method()
+de0 = mc_grad.kernel(state=0)
+de1 = mc_grad.kernel(state=1)
+print("CMS-PDFT Gradients")
+print("Gradient of ground state:\n", de0)
+print("Gradient of first singlet excited state:\n", de1)
+
+# For L-PDFT Gradients
+lpdft = mc.multi_state([0.5, 0.5], method='lin').run()
+
+mc_grad = lpdft.nuc_grad_method()
+de0 = mc_grad.kernel(state=0)
+de1 = mc_grad.kernel(state=1)
+print("L-PDFT Gradients")
+print("Gradient of ground state:\n", de0)
+print("Gradient of first singlet excited state:\n", de1)
diff --git a/pyscf/df/grad/mcpdft.py b/pyscf/df/grad/mcpdft.py
@@ -13,7 +13,7 @@
 # See the License for the specific language governing permissions and
 # limitations under the License.
 #
-from pyscf import lib, mcpdft
+from pyscf import lib
 from pyscf.grad import mcpdft as mcpdft_grad
 from pyscf.df.grad import sacasscf as dfsacasscf_grad
 from pyscf.df.grad import rhf as dfrhf_grad

diff --git a/pyscf/df/grad/mspdft.py b/pyscf/df/grad/mspdft.py
@@ -13,12 +13,10 @@
 # See the License for the specific language governing permissions and
 # limitations under the License.
 #
-from pyscf import lib, mcpdft
-from pyscf.grad import casscf as casscf_grad
+from pyscf import lib
 from pyscf.grad import sacasscf as sacasscf_grad
 from pyscf.grad import mspdft as mspdft_grad
 from pyscf.grad import mcpdft as mcpdft_grad
-from pyscf.df.grad import mcpdft as dfmcdpft_grad
 from pyscf.df.grad import casscf as dfcasscf_grad
 from pyscf.df.grad import sacasscf as dfsacasscf_grad
 from pyscf.df.grad import rhf as dfrhf_grad