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Fix SMD hessian #534

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Fix SMD hessian #534

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1ee7f6d
Fix SMD hessian
sunqm Oct 8, 2025
ae3936f
lint
sunqm Oct 8, 2025
573e8d4
import error
sunqm Oct 9, 2025
74fadfd
Forcing an empty commit.
sunqm Oct 9, 2025
d00e414
Merge branch 'master' into smd-hess
sunqm Oct 13, 2025
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1 change: 0 additions & 1 deletion gpu4pyscf/solvent/hessian/pcm.py
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Original file line number Diff line number Diff line change
Expand Up @@ -1024,7 +1024,6 @@ def to_cpu(self):
return pcm.make_hess_object(hess_method)

def kernel(self, *args, dm=None, atmlst=None, **kwargs):
dm = kwargs.pop('dm', None)
if dm is None:
dm = self.base.make_rdm1()
if dm.ndim == 3:
Expand Down
73 changes: 14 additions & 59 deletions gpu4pyscf/solvent/hessian/smd.py
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Expand Up @@ -21,40 +21,36 @@
from pyscf import lib
from gpu4pyscf import scf
from gpu4pyscf.lib import logger
from gpu4pyscf.solvent import smd
from gpu4pyscf.solvent.grad import smd as smd_grad
from gpu4pyscf.solvent.hessian import pcm as pcm_hess
from gpu4pyscf.hessian.rhf import HessianBase, _ao2mo

def get_cds(smdobj):
mol = smdobj.mol
solvent = smdobj.solvent
mol = smdobj.mol.copy()
smdobj_tmp = smdobj.copy()
def smd_grad_scanner(mol):
smdobj_tmp = smd.SMD(mol)
smdobj_tmp.solvent = solvent
return smd.get_cds_legacy(smdobj_tmp)[1]
smdobj_tmp.reset(mol)
return smd_grad.get_cds(smdobj_tmp)

log = logger.new_logger(mol, mol.verbose)
t1 = log.init_timer()

coords = mol.atom_coords(unit='B')
coords_backup = coords.copy()
eps = 1e-4
natm = mol.natm
hess_cds = np.zeros([natm,natm,3,3])
for ia in range(mol.natm):
for j in range(3):
coords = mol.atom_coords(unit='B')
coords[ia,j] += eps
mol.set_geom_(coords, unit='B')
mol.build()
grad0_cds = smd_grad_scanner(mol)

coords[ia,j] -= 2.0*eps
mol.set_geom_(coords, unit='B')
mol.build()
grad1_cds = smd_grad_scanner(mol)

coords[ia,j] += eps
mol.set_geom_(coords, unit='B')
hess_cds[ia,:,j] = (grad0_cds - grad1_cds) / (2.0 * eps)
coords[ia,j] = coords_backup[ia,j]
t1 = log.timer_debug1('solvent energy', *t1)
return hess_cds # hartree

Expand Down Expand Up @@ -106,6 +102,9 @@ def kernel(self, *args, dm=None, atmlst=None, **kwargs):
dm = self.base.make_rdm1()
if dm.ndim == 3:
dm = dm[0] + dm[1]
if self.base.with_solvent.frozen_dm0_for_finite_difference_without_response is not None:
raise NotImplementedError("frozen_dm0_for_finite_difference_without_response not implemented for PCM Hessian")

with lib.temporary_env(self.base.with_solvent, equilibrium_solvation=True):
logger.debug(self, 'Compute hessian from solutes')
self.de_solute = super().kernel(*args, **kwargs)
Expand All @@ -115,53 +114,9 @@ def kernel(self, *args, dm=None, atmlst=None, **kwargs):
self.de = self.de_solute + self.de_solvent + self.de_cds
return self.de

def make_h1(self, mo_coeff, mo_occ, chkfile=None, atmlst=None, verbose=None):
if atmlst is None:
atmlst = range(self.mol.natm)
h1ao = super().make_h1(mo_coeff, mo_occ, atmlst=atmlst, verbose=verbose)
if isinstance(self.base, scf.hf.RHF):
dm = self.base.make_rdm1()
dv = pcm_hess.analytical_grad_vmat(self.base.with_solvent, dm, mo_coeff, mo_occ, atmlst=atmlst, verbose=verbose)
for i0, ia in enumerate(atmlst):
h1ao[i0] += dv[i0]
return h1ao
elif isinstance(self.base, scf.uhf.UHF):
h1aoa, h1aob = h1ao
solvent = self.base.with_solvent
dm = self.base.make_rdm1()
dm = dm[0] + dm[1]
dva = pcm_hess.analytical_grad_vmat(solvent, dm, mo_coeff[0], mo_occ[0], atmlst=atmlst, verbose=verbose)
dvb = pcm_hess.analytical_grad_vmat(solvent, dm, mo_coeff[1], mo_occ[1], atmlst=atmlst, verbose=verbose)
for i0, ia in enumerate(atmlst):
h1aoa[i0] += dva[i0]
h1aob[i0] += dvb[i0]
return h1aoa, h1aob
else:
raise NotImplementedError('Base object is not supported')

def get_veff_resp_mo(self, mol, dms, mo_coeff, mo_occ, hermi=1):
v1vo = super().get_veff_resp_mo(mol, dms, mo_coeff, mo_occ, hermi=hermi)
if not self.base.with_solvent.equilibrium_solvation:
return v1vo
v_solvent = self.base.with_solvent._B_dot_x(dms)

if isinstance(self.base, scf.uhf.UHF):
n_dm = dms.shape[1]
mocca = mo_coeff[0][:,mo_occ[0]>0]
moccb = mo_coeff[1][:,mo_occ[1]>0]
moa, mob = mo_coeff
nmoa = moa.shape[1]
nocca = mocca.shape[1]
v1vo_sol = v_solvent[0] + v_solvent[1]
v1vo[:,:nmoa*nocca] += _ao2mo(v1vo_sol, mocca, moa).reshape(n_dm,-1)
v1vo[:,nmoa*nocca:] += _ao2mo(v1vo_sol, moccb, mob).reshape(n_dm,-1)
elif isinstance(self.base, scf.hf.RHF):
n_dm = dms.shape[0]
mocc = mo_coeff[:,mo_occ>0]
v1vo += _ao2mo(v_solvent, mocc, mo_coeff).reshape(n_dm,-1)
else:
raise NotImplementedError('Base object is not supported')
return v1vo
make_h1 = pcm_hess.WithSolventHess.make_h1

get_veff_resp_mo = pcm_hess.WithSolventHess.get_veff_resp_mo

def _finalize(self):
# disable _finalize. It is called in grad_method.kernel method
Expand Down
54 changes: 54 additions & 0 deletions gpu4pyscf/solvent/tests/test_smd_hessian.py
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Original file line number Diff line number Diff line change
Expand Up @@ -270,6 +270,60 @@ def test_to_cpu(self):
hess_cpu = hessobj.kernel()
assert numpy.linalg.norm(hess_cpu - hess_gpu) < 1e-5

def test_cds(self):
from gpu4pyscf.solvent.hessian.smd import get_cds as get_cds_hess
from gpu4pyscf.solvent.grad.smd import get_cds as get_cds_grad
mol = gto.M(atom='''
C 0.000000 0.000000 -0.542500
H 0.000000 0.935307 -1.082500
H 0.000000 -0.935307 -1.082500''')
mf = mol.RHF().SMD()
# [n, n25, alpha, beta, gamma, epsilon, phi, psi]
mf.with_solvent.solvent_descriptors = [1.3843, 1.3766, 0.0, 0.45, 35.06, 13.45, 0.0, 0.0]
dat = get_cds_hess(mf.with_solvent)

mol.set_geom_('''
C 0.000000 0.000000 -0.543500
H 0.000000 0.935307 -1.082500
H 0.000000 -0.935307 -1.082500''')
mf = mol.RHF().SMD()
mf.with_solvent.solvent_descriptors = [1.3843, 1.3766, 0.0, 0.45, 35.06, 13.45, 0.0, 0.0]
g1 = get_cds_grad(mf.with_solvent)
mol.set_geom_('''
C 0.000000 0.000000 -0.541500
H 0.000000 0.935307 -1.082500
H 0.000000 -0.935307 -1.082500''')
mf = mol.RHF().SMD()
mf.with_solvent.solvent_descriptors = [1.3843, 1.3766, 0.0, 0.45, 35.06, 13.45, 0.0, 0.0]
g2 = get_cds_grad(mf.with_solvent)
assert abs(dat[0,:,2] - ((g2 - g1) / 2e-3 * lib.param.BOHR)).max() < 1e-5

def test_hess(self):
mol = gto.M(atom='''
C 0.000000 0.000000 -0.542500
H 0.000000 0.935307 -1.082500
H 0.000000 -0.935307 -1.082500
''')
mf = mol.RHF().to_gpu().density_fit().SMD()
mf.with_solvent.solvent_descriptors = [1.3843, 1.3766, 0.0, 0.45, 35.06, 13.45, 0.0, 0.0]
hess = mf.run().Hessian().kernel()

mol.set_geom_('''
C 0.000000 0.000000 -0.543500
H 0.000000 0.935307 -1.082500
H 0.000000 -0.935307 -1.082500''')
mf = mol.RHF().to_gpu().density_fit().SMD()
mf.with_solvent.solvent_descriptors = [1.3843, 1.3766, 0.0, 0.45, 35.06, 13.45, 0.0, 0.0]
g1 = mf.run().Gradients().kernel()
mol.set_geom_('''
C 0.000000 0.000000 -0.541500
H 0.000000 0.935307 -1.082500
H 0.000000 -0.935307 -1.082500''')
mf = mol.RHF().to_gpu().density_fit().SMD()
mf.with_solvent.solvent_descriptors = [1.3843, 1.3766, 0.0, 0.45, 35.06, 13.45, 0.0, 0.0]
g2 = mf.run().Gradients().kernel()
assert abs(hess[0,:,2] - ((g2 - g1) / 2e-3 * lib.param.BOHR)).max() < 1e-5

if __name__ == "__main__":
print("Full Tests for Hessian of SMD")
unittest.main()
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