def test_rtcc_he_cc_pvdz():
"""He cc-pVDZ"""
psi4.set_memory('2 GiB')
psi4.core.set_output_file('output.dat', False)
psi4.set_options({'basis': 'cc-pVDZ',
'scf_type': 'pk',
'mp2_type': 'conv',
'freeze_core': 'false',
'e_convergence': 1e-13,
'd_convergence': 1e-13,
'r_convergence': 1e-13,
'diis': 1})
mol = psi4.geometry(moldict["He"])
rhf_e, rhf_wfn = psi4.energy('SCF', return_wfn=True)
e_conv = 1e-13
r_conv = 1e-13
cc = pycc.ccwfn(rhf_wfn)
ecc = cc.solve_cc(e_conv, r_conv)
hbar = pycc.cchbar(cc)
cclambda = pycc.cclambda(cc, hbar)
lecc = cclambda.solve_lambda(e_conv, r_conv)
ccdensity = pycc.ccdensity(cc, cclambda)
# Sine squared pulse (a.u.)
F_str = 1.0
omega = 2.87
tprime = 5.0
V = sine_square_laser(F_str, omega, tprime)
# RT-CC Setup
t0 = 0
tf = 1.0
h = 0.01
rtcc = pycc.rtcc(cc, cclambda, ccdensity, V)
y0 = rtcc.collect_amps(cc.t1, cc.t2, cclambda.l1, cclambda.l2).astype('complex128')
ODE = ode(rtcc.f).set_integrator('vode',atol=1e-13,rtol=1e-13)
ODE.set_initial_value(y0, t0)
t1, t2, l1, l2 = rtcc.extract_amps(y0)
mu0_x, mu0_y, mu0_z = rtcc.dipole(t1, t2, l1, l2)
ecc0 = rtcc.lagrangian(t0, t1, t2, l1, l2)
mu_z_ref = 0.008400738202694 # a.u.
while ODE.successful() and ODE.t < tf:
y = ODE.integrate(ODE.t+h)
t = ODE.t
t1, t2, l1, l2 = rtcc.extract_amps(y)
mu_x, mu_y, mu_z = rtcc.dipole(t1, t2, l1, l2)
ecc = rtcc.lagrangian(t, t1, t2, l1, l2)
print(mu_z)
assert (abs(mu_z_ref - mu_z.real) < 1e-10)
def test_rtpao(datadir):
"""H2O RT-PAO"""
psi4.set_memory('2 GiB')
psi4.core.set_output_file('output.dat', False)
psi4.set_options({'basis': 'cc-pVDZ',
'scf_type': 'pk',
'mp2_type': 'conv',
'freeze_core': 'false',
'e_convergence': 1e-13,
'd_convergence': 1e-13,
'r_convergence': 1e-13,
'diis': 1,
'local_convergence': 1.e-13})
mol = psi4.geometry(moldict["H2O"]+"\nnoreorient\nnocom")
ref_dir = str(datadir.join(f"wfn.npy"))
rhf_wfn = psi4.core.Wavefunction.from_file(ref_dir)
maxiter = 75
e_conv = 1e-13
r_conv = 1e-13
max_diis = 8
cc = pycc.ccwfn(rhf_wfn, local='PAO', local_cutoff=1e-2)
ecc = cc.solve_cc(e_conv, r_conv, maxiter, max_diis)
hbar = pycc.cchbar(cc)
cclambda = pycc.cclambda(cc, hbar)
lecc = cclambda.solve_lambda(e_conv, r_conv)
ccdensity = pycc.ccdensity(cc, cclambda)
# Narrow Gaussian pulse
F_str = 0.001
omega = 0
sigma = 0.01
center = 0.05
V = gaussian_laser(F_str, omega, sigma, center=center)
# RT-CC Setup
t0 = 0
tf = 0.5
h = 0.02
rtcc = pycc.rtcc(cc, cclambda, ccdensity, V)
y0 = rtcc.collect_amps(cc.t1, cc.t2, cclambda.l1, cclambda.l2).astype('complex128')
ODE = rk4(h)
# Propagate
ret = rtcc.propagate(ODE, y0, tf, ti=t0, ref=False)
# check
ref = {'ecc': (-84.21540972040579+2.9584453421137937e-16j),
'mu_x': (-4.987717148832141e-05-2.5885460555301484e-12j),
'mu_y': (-4.707786986481166e-05-1.5660290548026362e-11j),
'mu_z': (-0.0783037960868978-1.168135844689433e-11j)}
for prop in ret['0.50']:
assert (abs(ret['0.50'][prop] - ref[prop]) < 1e-8)
def test_rtpno(datadir):
"""H2O RT-LPNO"""
psi4.set_memory('2 GiB')
psi4.core.set_output_file('output.dat', False)
psi4.set_options({'basis': 'cc-pVDZ',
'scf_type': 'pk',
'mp2_type': 'conv',
'freeze_core': 'false',
'e_convergence': 1e-13,
'd_convergence': 1e-13,
'r_convergence': 1e-13,
'diis': 1,
'local_convergence': 1.e-13})
mol = psi4.geometry(moldict["H2O"]+"\nnoreorient\nnocom")
ref_dir = str(datadir.join(f"wfn.npy"))
rhf_wfn = psi4.core.Wavefunction.from_file(ref_dir)
maxiter = 75
e_conv = 1e-13
r_conv = 1e-13
max_diis = 8
cc = pycc.ccwfn(rhf_wfn, local='LPNO', local_cutoff=1e-5)
ecc = cc.solve_cc(e_conv, r_conv, maxiter, max_diis)
hbar = pycc.cchbar(cc)
cclambda = pycc.cclambda(cc, hbar)
lecc = cclambda.solve_lambda(e_conv, r_conv)
ccdensity = pycc.ccdensity(cc, cclambda)
# Narrow Gaussian pulse
F_str = 0.001
omega = 0
sigma = 0.01
center = 0.05
V = gaussian_laser(F_str, omega, sigma, center=center)
# RT-CC Setup
t0 = 0
tf = 0.5
h = 0.02
rtcc = pycc.rtcc(cc, cclambda, ccdensity, V)
y0 = rtcc.collect_amps(cc.t1, cc.t2, cclambda.l1, cclambda.l2).astype('complex128')
ODE = rk4(h)
# Propagate
ret = rtcc.propagate(ODE, y0, tf, ti=t0, ref=False)
# check
ref = {'ecc': (-84.21331867940133+4.925945912792495e-17j),
'mu_x': (-5.106207671158796e-05+3.641896436116718e-12j),
'mu_y': (-5.001503722097678e-05-1.7436592314191415e-12j),
'mu_z': (-0.06905411053873889-9.328439713393588e-12j)}
for prop in ret['0.50']:
assert (abs(ret['0.50'][prop] - ref[prop]) < 1e-8)
def test_dipole_h2_2_cc_pvdz():
"""He cc-pVDZ"""
psi4.set_memory('2 GiB')
psi4.core.set_output_file('output.dat', False)
psi4.set_options({
'basis': 'cc-pVDZ',
'scf_type': 'pk',
'mp2_type': 'conv',
'freeze_core': 'false',
'e_convergence': 1e-13,
'd_convergence': 1e-13,
'r_convergence': 1e-13,
'diis': 1
})
mol = psi4.geometry(moldict["(H2)_2"])
rhf_e, rhf_wfn = psi4.energy('SCF', return_wfn=True)
e_conv = 1e-13
r_conv = 1e-13
cc = pycc.ccwfn(rhf_wfn)
ecc = cc.solve_cc(e_conv, r_conv)
hbar = pycc.cchbar(cc)
cclambda = pycc.cclambda(cc, hbar)
lecc = cclambda.solve_lambda(e_conv, r_conv)
ccdensity = pycc.ccdensity(cc, cclambda)
# no laser
rtcc = pycc.rtcc(cc, cclambda, ccdensity, None, magnetic=True)
y0 = rtcc.collect_amps(cc.t1, cc.t2, cclambda.l1,
cclambda.l2).astype('complex128')
t1, t2, l1, l2 = rtcc.extract_amps(y0)
ref = [0, 0, 0.005371586416860086] # au
mu_x, mu_y, mu_z = rtcc.dipole(t1, t2, l1, l2)
opdm = rtcc.ccdensity.compute_onepdm(t1, t2, l1, l2, withref=True)
assert (abs(ref[0] - mu_x) < 1E-10)
assert (abs(ref[1] - mu_y) < 1E-10)
assert (abs(ref[2] - mu_z) < 1E-10)
ref = [0, 0, -2.3037968376087573E-5]
m_x, m_y, m_z = rtcc.dipole(t1, t2, l1, l2, magnetic=True)
assert (abs(ref[0] * 1.0j - m_x) < 1E-10)
assert (abs(ref[1] * 1.0j - m_y) < 1E-10)
assert (abs(ref[2] * 1.0j - m_z) < 1E-10)
def test_rtcc_water_cc_pvdz():
"""H2O cc-pVDZ"""
psi4.set_memory('2 GiB')
psi4.core.set_output_file('output.dat', False)
psi4.set_options({
'basis': 'cc-pVDZ',
'scf_type': 'pk',
'mp2_type': 'conv',
'freeze_core': 'false',
'e_convergence': 1e-13,
'd_convergence': 1e-13,
'r_convergence': 1e-13,
'diis': 1
})
mol = psi4.geometry(moldict["H2O"])
rhf_e, rhf_wfn = psi4.energy('SCF', return_wfn=True)
e_conv = 1e-13
r_conv = 1e-13
cc = pycc.ccwfn(rhf_wfn)
ecc = cc.solve_cc(e_conv, r_conv)
hbar = pycc.cchbar(cc)
cclambda = pycc.cclambda(cc, hbar)
lecc = cclambda.solve_lambda(e_conv, r_conv)
ccdensity = pycc.ccdensity(cc, cclambda)
# Gaussian pulse (a.u.)
F_str = 0.01
omega = 0
sigma = 0.01
center = 0.05
V = gaussian_laser(F_str, omega, sigma, center)
# RT-CC Setup
t0 = 0
tf = 0.1
h = 0.01
t = t0
rtcc = pycc.rtcc(cc, cclambda, ccdensity, V)
y0 = rtcc.collect_amps(cc.t1, cc.t2, cclambda.l1,
cclambda.l2).astype('complex128')
y = y0
ODE = rk4(h)
t1, t2, l1, l2 = rtcc.extract_amps(y0)
mu0_x, mu0_y, mu0_z = rtcc.dipole(t1, t2, l1, l2)
ecc0 = rtcc.lagrangian(t0, t1, t2, l1, l2)
# For saving data at each time step.
"""
dip_x = []
dip_y = []
dip_z = []
time_points = []
dip_x.append(mu0_x)
dip_y.append(mu0_y)
dip_z.append(mu0_z)
time_points.append(t)
"""
while t < tf:
y = ODE(rtcc.f, t, y)
t += h
t1, t2, l1, l2 = rtcc.extract_amps(y)
mu_x, mu_y, mu_z = rtcc.dipole(t1, t2, l1, l2)
ecc = rtcc.lagrangian(t, t1, t2, l1, l2)
"""
dip_x.append(mu_x)
dip_y.append(mu_y)
dip_z.append(mu_z)
time_points.append(t)
"""
print(mu_z)
mu_z_ref = -0.34894577
assert (abs(mu_z_ref - mu_z.real) < 1e-4)
def test_rtcc_water_cc_pvdz():
"""H2O cc-pVDZ"""
psi4.set_memory('2 GiB')
psi4.core.set_output_file('output.dat', False)
psi4.set_options({
'basis': 'cc-pVDZ',
'scf_type': 'pk',
'mp2_type': 'conv',
'freeze_core': 'false',
'e_convergence': 1e-13,
'd_convergence': 1e-13,
'r_convergence': 1e-13,
'diis': 1
})
mol = psi4.geometry(moldict["H2O"])
rhf_e, rhf_wfn = psi4.energy('SCF', return_wfn=True)
e_conv = 1e-13
r_conv = 1e-13
cc = pycc.ccwfn(rhf_wfn)
ecc = cc.solve_cc(e_conv, r_conv)
hbar = pycc.cchbar(cc)
cclambda = pycc.cclambda(cc, hbar)
lecc = cclambda.solve_lambda(e_conv, r_conv)
ccdensity = pycc.ccdensity(cc, cclambda)
# Gaussian pulse (a.u.)
F_str = 100
omega = 0
# The pulse is chosen to be thinner for less time steps with h_small(see below).
sigma = 0.0001
center = 0.0005
V = gaussian_laser(F_str, omega, sigma, center)
# Cutoff for the field to decide which step size is used
e_field = 1e-7
# RT-CC Setup
t0 = 0
tf = 0.1
h_small = 1e-5
h = 0.01
t = t0
rtcc = pycc.rtcc(cc, cclambda, ccdensity, V)
y0 = rtcc.collect_amps(cc.t1, cc.t2, cclambda.l1,
cclambda.l2).astype('complex128')
y = y0
ODE1 = rk4(h_small)
ODE2 = rk4(h)
t1, t2, l1, l2 = rtcc.extract_amps(y0)
mu0_x, mu0_y, mu0_z = rtcc.dipole(t1, t2, l1, l2)
ecc0 = rtcc.lagrangian(t0, t1, t2, l1, l2)
#mu_z_ref = 0.008400738202694 # a.u.
# For saving data at each time step.
"""
dip_x = []
dip_y = []
dip_z = []
time_points = []
dip_x.append(mu0_x)
dip_y.append(mu0_y)
dip_z.append(mu0_z)
time_points.append(t)
"""
while t < tf:
# When the field is on
if V(t) > e_field:
y = ODE1(rtcc.f, t, y)
h_i = h_small
# When the field is off
else:
y = ODE2(rtcc.f, t, y)
h_i = h
t += h_i
t1, t2, l1, l2 = rtcc.extract_amps(y)
mu_x, mu_y, mu_z = rtcc.dipole(t1, t2, l1, l2)
ecc = rtcc.lagrangian(t, t1, t2, l1, l2)
"""
dip_x.append(mu_x)
dip_y.append(mu_y)
dip_z.append(mu_z)
time_points.append(t)
"""
print(mu_z)
mu_z_ref = -0.34894577
assert (abs(mu_z_ref - mu_z.real) < 1e-1)
# narrow Gaussian pulse
F_str = 0.001
sigma = 0.01
center = 0.05
V = gaussian_laser(F_str, 0, sigma, center=center)
# RTCC
# use tf = 5 to generate checkpoint file
h = 0.1
ti = 0
if full:
tf = 10
else:
tf = 5
rtcc = pycc.rtcc(cc, cclambda, ccdensity, V, magnetic=True, kick='z')
y0 = rtcc.collect_amps(cc.t1, cc.t2, cclambda.l1,
cclambda.l2).astype('complex128')
ODE = rk2(h)
# if full: run entire propagation, save amps / props / rhf wfn
if full:
ret, ret_t = rtcc.propagate(ODE,
y0,
tf,
ti=ti,
ref=False,
chk=True,
tchk=1,
cfile="chk_full.pk",
ofile="output_full.pk",
def test_chk(datadir):
# run cc
psi4.set_memory('600MB')
psi4.core.set_output_file('output.dat', False)
psi4.set_options({'basis': 'cc-pVDZ',
'scf_type': 'pk',
'mp2_type': 'conv',
'freeze_core': 'false',
'e_convergence': 1e-8,
'd_convergence': 1e-8,
'r_convergence': 1e-8,
'diis': 8})
mol = psi4.geometry(moldict["H2"])
# pull ref wfn, psi4 is picky about strings
rhf_dir = str(datadir.join(f"ref_wfn.npy"))
rhf_wfn = psi4.core.Wavefunction.from_file(rhf_dir)
e_conv = 1e-8
r_conv = 1e-8
cc = pycc.ccwfn(rhf_wfn)
ecc = cc.solve_cc(e_conv, r_conv)
hbar = pycc.cchbar(cc)
cclambda = pycc.cclambda(cc, hbar)
lecc = cclambda.solve_lambda(e_conv, r_conv)
ccdensity = pycc.ccdensity(cc, cclambda)
# narrow Gaussian pulse
F_str = 0.001
sigma = 0.01
center = 0.05
V = gaussian_laser(F_str, 0, sigma, center=center)
# RTCC setup
h = 0.1
tf = 10
rtcc = pycc.rtcc(cc,cclambda,ccdensity,V,magnetic=True,kick='z')
# pull chk files for 0-5.1au
chk_file = datadir.join(f"chk_5.pk")
with open(chk_file,'rb') as cf:
chk = pk.load(cf)
# propagate to 10au
ODE = rk2(h)
y0 = chk['y']
ti = chk['time']
ofile = datadir.join(f"output.pk")
tfile = datadir.join(f"t_out.pk")
ret, ret_t = rtcc.propagate(ODE, y0, tf, ti=ti, ref=False, chk=True, tchk=1,
ofile=ofile, tfile=tfile, k=2)
# reference is "full" propagation (0-10au)
refp_file = datadir.join(f"output_full.pk")
with open(refp_file,'rb') as pf:
ref_p = pk.load(pf)
reft_file = datadir.join(f"t_out_full.pk")
with open(reft_file,'rb') as ampf:
ref_t = pk.load(ampf)
# check properties
pchk = ['ecc','mu_x','mu_y','mu_z','m_x','m_y','m_z']
for k in ref_p.keys():
for p in pchk:
assert np.allclose(ret[k][p],ref_p[k][p])
# check amplitudes
tchk = ['t1','t2','l1','l2']
for k in ref_t.keys():
for t in tchk:
assert np.allclose(ret_t[k][t],ref_t[k][t])
def test_dipole_h2_2_field():
"""H2 dimer"""
psi4.set_memory('2 GiB')
psi4.core.set_output_file('output.dat', False)
psi4.set_options({
'basis': '6-31G',
'scf_type': 'pk',
'mp2_type': 'conv',
'freeze_core': 'false',
'e_convergence': 1e-13,
'd_convergence': 1e-13,
'r_convergence': 1e-13,
'diis': 1
})
mol = psi4.geometry(moldict["(H2)_2"])
rhf_e, rhf_wfn = psi4.energy('SCF', return_wfn=True)
e_conv = 1e-13
r_conv = 1e-13
cc = pycc.ccwfn(rhf_wfn)
ecc = cc.solve_cc(e_conv, r_conv)
hbar = pycc.cchbar(cc)
cclambda = pycc.cclambda(cc, hbar)
lecc = cclambda.solve_lambda(e_conv, r_conv)
ccdensity = pycc.ccdensity(cc, cclambda)
# narrow Gaussian pulse
F_str = 0.01
sigma = 0.01
center = 0.05
V = gaussian_laser(F_str, 0, sigma, center=center)
rtcc = pycc.rtcc(cc, cclambda, ccdensity, V, magnetic=True)
mints = psi4.core.MintsHelper(cc.ref.basisset())
dipole_ints = mints.ao_dipole()
m_ints = mints.ao_angular_momentum()
C = np.asarray(cc.ref.Ca_subset("AO", "ACTIVE"))
ref_mu = []
ref_m = []
for axis in range(3):
ref_mu.append(C.T @ np.asarray(dipole_ints[axis]) @ C)
ref_m.append(C.T @ (np.asarray(m_ints[axis]) * -0.5) @ C)
assert np.allclose(ref_mu[axis], rtcc.mu[axis])
assert np.allclose(ref_m[axis] * 1.0j, rtcc.m[axis])
ref_mu_tot = sum(ref_mu) / np.sqrt(3.0)
assert np.allclose(ref_mu_tot, rtcc.mu_tot)
rtcc = pycc.rtcc(cc, cclambda, ccdensity, V, magnetic=True, kick="Y")
mints = psi4.core.MintsHelper(cc.ref.basisset())
dipole_ints = mints.ao_dipole()
m_ints = mints.ao_angular_momentum()
C = np.asarray(cc.ref.Ca_subset("AO", "ACTIVE"))
ref_mu = []
ref_m = []
for axis in range(3):
ref_mu.append(C.T @ np.asarray(dipole_ints[axis]) @ C)
ref_m.append(C.T @ (np.asarray(m_ints[axis]) * -0.5) @ C)
assert np.allclose(ref_mu[axis], rtcc.mu[axis])
assert np.allclose(ref_m[axis] * 1.0j, rtcc.m[axis])
assert np.allclose(ref_mu[1], rtcc.mu_tot)