def set_up_test_arrays(self, length=100, rank=3):
''' Helper for set up arrays to test math'''
MA1 = MatrixArray(length=length, rank=rank)
MA1['A', 'A'] = np.ones(length) * 2.0
MA1['B', 'B'] = np.ones(length)
MA1['C', 'C'] = np.ones(length) * 3.0
MA1['B', 'C'] = np.ones(length) * 3.0
MA2 = MatrixArray(length=length, rank=rank)
MA2['A', 'A'] = np.arange(length)
MA2['B', 'B'] = np.ones(length) * 2.0
MA2['C', 'C'] = np.ones(length) * -3.0
array1 = np.zeros((length, rank, rank))
array1[:, 0, 0] = np.ones(length) * 2.0
array1[:, 1, 1] = np.ones(length)
array1[:, 2, 2] = np.ones(length) * 3.0
array1[:, 1, 2] = np.ones(length) * 3.0
array1[:, 2, 1] = np.ones(length) * 3.0
array2 = np.zeros((length, rank, rank))
array2[:, 0, 0] = np.arange(length)
array2[:, 1, 1] = np.ones(length) * 2.0
array2[:, 2, 2] = np.ones(length) * -3.0
return (MA1, MA2), (array1, array2)
def __init__(self, types):
r'''Constructor
Arguments
---------
types: list
List of types of sites
Attributes
----------
density: :class:`pyPRISM.core.ValueTable`
Table of site number density values
total: float
Total number density
site: :class:`pyPRISM.core.MatrixArray`
Site density for each pair.
pair: :class:`pyPRISM.core.MatrixArray`
Pair site density for each pair.
'''
self.types = types
self.density = ValueTable(types=types, name='density')
self.total = 0.
self.pair = MatrixArray(length=1,
rank=len(types),
types=types,
space=Space.NonSpatial)
self.site = MatrixArray(length=1,
rank=len(types),
types=types,
space=Space.NonSpatial)
def test_MatrixArray_export(self):
types = ['A', 'B', 'C']
length = 1024
rank = len(types)
values1 = np.ones(length)
values2 = np.ones(length) * 5.0
values3 = np.ones(length) * 2.1234
MA1 = MatrixArray(length=length, rank=rank, space=Space.Fourier)
MA1['A', 'A'] = values2
MA1['A', 'B'] = values1
MA1['A', 'C'] = values1
MA1['B', 'B'] = values3
MA1['B', 'C'] = values3
MA1['C', 'C'] = values3
ntypes = len(types)
PT = PairTable(types, 'density')
PT[['A'], ['B', 'C']] = values1
PT[['A'], ['A']] = values2
PT.setUnset(values3)
MA2 = PT.exportToMatrixArray(space=Space.Fourier)
np.testing.assert_array_almost_equal(MA1.data, MA2.data)
self.assertEqual(MA1.space, MA2.space)
def exportToMatrixArray(self, space=Space.Real):
'''Convenience function for converting a table of arrays to a MatrixArray
.. warning::
This only works if the PairTable contains numerical data that is
all of the same shape that can be cast into a np.ndarray like
object.
'''
lengths = []
for i, t, val in self.iterpairs():
if val is None:
raise ValueError(
'Can\'t export not-fully specified Table {}'.format(
self.name))
lengths.append(len(val))
if not len(set(lengths)) <= 1:
raise ValueError(
'Arrays in Table are not all the same length. Aborting export.'
)
length = lengths[0]
rank = len(self.types)
MA = MatrixArray(length=length,
rank=rank,
space=space,
types=self.types)
for i, (t1, t2), val in self.iterpairs():
MA[t1, t2] = val
return MA
def test_assign(self):
'''Can we create and assign values?'''
length = 100
rank = 8
MA = MatrixArray(length=length, rank=rank)
# Make sure the array starts as all zeros
array = np.zeros((length, rank, rank))
np.testing.assert_array_almost_equal(MA.data, array)
# Test assignment (especially off diagonal)
array = np.zeros((length, rank, rank))
MA['B', 'B'] = np.ones(length)
MA['B', 'C'] = np.ones(length) * 3.0
array[:, 1, 1] = np.ones(length)
array[:, 1, 2] = np.ones(length) * 3.0
array[:, 2, 1] = np.ones(length) * 3.0
np.testing.assert_array_almost_equal(MA.data, array)
def test_MatrixArray_loop(self):
'''Can we transform an entire MatrixArray?'''
length = 1024
rank = 3
dr = 0.1
d = Domain(length=length, dr=dr)
array1 = np.sin(np.arange(0, 10 * np.pi, 0.01))[:length]
array2 = 5 * np.sin(np.arange(0, 10 * np.pi, 0.01))[:length]
array3 = np.cos(np.arange(0, 10 * np.pi, 0.01))[:length]
array4 = np.cos(np.arange(0, 10 * np.pi, 0.01))[:length] + np.sin(
np.arange(0, 10 * np.pi, 0.01))[:length]
MA = MatrixArray(length=length, rank=rank)
MA['A', 'A'] = array1
MA['B', 'B'] = array2
MA['B', 'C'] = array3
MA['C', 'C'] = array4
d.MatrixArray_to_fourier(MA)
np.testing.assert_array_almost_equal(MA['A', 'A'],
d.to_fourier(array1))
np.testing.assert_array_almost_equal(MA['B', 'B'],
d.to_fourier(array2))
np.testing.assert_array_almost_equal(MA['B', 'C'],
d.to_fourier(array3))
np.testing.assert_array_almost_equal(MA['C', 'B'],
d.to_fourier(array3))
np.testing.assert_array_almost_equal(MA['C', 'C'],
d.to_fourier(array4))
# This should recover the original values of the MatrixArray
d.MatrixArray_to_real(MA)
np.testing.assert_array_almost_equal(MA['A', 'A'], array1)
np.testing.assert_array_almost_equal(MA['B', 'B'], array2)
np.testing.assert_array_almost_equal(MA['B', 'C'], array3)
np.testing.assert_array_almost_equal(MA['C', 'B'], array3)
np.testing.assert_array_almost_equal(MA['C', 'C'], array4)
def __init__(self, sys):
self.sys = deepcopy(sys)
# Need to set the potential for each closure object
for (i, j), (t1, t2), U in self.sys.potential.iterpairs():
if isinstance(self.sys.closure[t1, t2], AtomicClosure):
#only set sigma if not set directly in potential
if U.sigma is None:
U.sigma = self.sys.diameter[t1, t2]
self.sys.closure[t1, t2].sigma = self.sys.diameter[t1, t2]
self.sys.closure[t1, t2].potential = U.calculate(
self.sys.domain.r) / self.sys.kT
elif isinstance(self.sys.closure[t1, t2], MolecularClosure):
raise NotImplementedError(
'Molecular closures are not fully implemented in this release.'
)
#only set sigma if not set directly in potential
if U.sigma is None:
U.sigma = self.sys.diameter[t1, t2]
self.sys.closure[t1, t2].sigma = self.sys.diameter[t1, t2]
self.sys.closure[t1, t2].potential = U.calculate_attractive(
self.sys.domain.r) / self.sys.kT
#cost function input and output
self.x = np.zeros(sys.rank * sys.rank * sys.domain.length)
self.y = np.zeros(sys.rank * sys.rank * sys.domain.length)
# The omega objects must be converted to a MatrixArray of the actual correlation
# function values rather than a table of OmegaObjects.
applyFunc = lambda x: x.calculate(sys.domain.k)
self.omega = self.sys.omega.apply(
applyFunc, inplace=False).exportToMatrixArray(space=Space.Fourier)
self.omega *= sys.density.site #omega should always be scaled by site density
# Spaces are set based on when they are used in self.cost(...). In some cases,
# this is redundant because these array's will be overwritten with copies and
# then their space will be inferred from their parent MatrixArrays
self.directCorr = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Real,
types=sys.types)
self.totalCorr = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Fourier,
types=sys.types)
self.GammaIn = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Real,
types=sys.types)
self.GammaOut = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Real,
types=sys.types)
self.OC = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Fourier,
types=sys.types)
self.I = IdentityMatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Fourier,
types=sys.types)
class PRISM:
r'''Primary container for a storing a PRISM calculation
Each pyPRISM.PRISM object serves as an encapsulation of a fully specified
PRISM problem including all inputs needed for the calculation and the
function to be numerically minimized.
Attributes
----------
domain: pyPRISM.Domain
The Domain object fully specifies the Real- and Fourier- space solution
grids.
directCorr: pyPRISM.MatrixArray
The direct correlation function for all pairs of site types
omega: pyPRISM.MatrixArray
The intra-molecular correlation function for all pairs of site types
closure: pyPRISM.core.PairTable of pyPRISM.closure.Closure
Table of closure objects used to generate the direct correlation
functions (directCorr)
pairCorr: pyPRISM.MatrixArray
The *inter*-molecular pair correlation functions for all pairs of
site types. Also commonly refered to as the radial distribution functions.
totalCorr: pyPRISM.MatrixArray
The *inter*-molecular total correlation function is simply the pair
correlation function y-shifted by 1.0 i.e. totalCorr = pairCorr - 1.0
potential: pyPRISM.MatrixArray
Interaction potentials for all pairs of sites
GammaIn,GammaOut: pyPRISM.MatrixArray
Primary inputs and outputs of the PRISM cost function. Gamma is defined as
"totalCorr - directCorr" (in Fourier space) and results from a change
of variables used to remove divergences in the closure relations.
OC,IOC,I,etc: pyPRISM.MatrixArray
Various MatrixArrays used as intermediates in the PRISM functional.
These arrays are pre-allocated and stored for efficiency.
x,y: float np.ndarray
Current inputs and outputs of the cost function
pairDensityMatrix: float np.ndarray
Rank by rank array of pair densities between sites. See :class:`pyPRISM.core.Density`
siteDensityMatrix: float np.ndarray
Rank by rank array of site densities. See :class:`pyPRISM.core.Density`
Methods
-------
cost:
Primary cost function used to define the criteria of a "converged"
PRISM solution. The numerical solver will be given this function
and will attempt to find the inputs (self.x) that make the outputs
(self.y) as close to zero as possible.
'''
def __init__(self, sys):
self.sys = deepcopy(sys)
# Need to set the potential for each closure object
for (i, j), (t1, t2), U in self.sys.potential.iterpairs():
if isinstance(self.sys.closure[t1, t2], AtomicClosure):
#only set sigma if not set directly in potential
if U.sigma is None:
U.sigma = self.sys.diameter[t1, t2]
self.sys.closure[t1, t2].sigma = self.sys.diameter[t1, t2]
self.sys.closure[t1, t2].potential = U.calculate(
self.sys.domain.r) / self.sys.kT
elif isinstance(self.sys.closure[t1, t2], MolecularClosure):
raise NotImplementedError(
'Molecular closures are not fully implemented in this release.'
)
#only set sigma if not set directly in potential
if U.sigma is None:
U.sigma = self.sys.diameter[t1, t2]
self.sys.closure[t1, t2].sigma = self.sys.diameter[t1, t2]
self.sys.closure[t1, t2].potential = U.calculate_attractive(
self.sys.domain.r) / self.sys.kT
#cost function input and output
self.x = np.zeros(sys.rank * sys.rank * sys.domain.length)
self.y = np.zeros(sys.rank * sys.rank * sys.domain.length)
# The omega objects must be converted to a MatrixArray of the actual correlation
# function values rather than a table of OmegaObjects.
applyFunc = lambda x: x.calculate(sys.domain.k)
self.omega = self.sys.omega.apply(
applyFunc, inplace=False).exportToMatrixArray(space=Space.Fourier)
self.omega *= sys.density.site #omega should always be scaled by site density
# Spaces are set based on when they are used in self.cost(...). In some cases,
# this is redundant because these array's will be overwritten with copies and
# then their space will be inferred from their parent MatrixArrays
self.directCorr = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Real,
types=sys.types)
self.totalCorr = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Fourier,
types=sys.types)
self.GammaIn = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Real,
types=sys.types)
self.GammaOut = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Real,
types=sys.types)
self.OC = MatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Fourier,
types=sys.types)
self.I = IdentityMatrixArray(length=sys.domain.length,
rank=sys.rank,
space=Space.Fourier,
types=sys.types)
def __repr__(self):
return '<PRISM length:{} rank:{}>'.format(self.sys.domain.length,
self.sys.rank)
def cost(self, x):
r'''Cost function
There are likely several cost functions that could be imagined using
the PRISM equations. In this case we formulate a self-consistent
formulation where we expect the input of the PRISM equations to be
identical to the output.
.. image:: ../../img/numerical_method.svg
:width: 300px
The goal of the solve method is to numerically optimize the input (:math:`r \gamma_{in}`)
so that the output (:math:`r(\gamma_{in}-\gamma_{out})`) is minimized to zero.
'''
self.x = x #store input
# The np.copy is important otherwise x saves state between calls to
# this function.
self.GammaIn.data = np.copy(
x.reshape((-1, self.sys.rank, self.sys.rank)))
self.GammaIn /= self.sys.domain.long_r
# directCorr is calculated directly in Real space but immediately
# inverted to Fourier space. We must reset this from the last call.
self.directCorr.space = Space.Real
for (i, j), (t1, t2), closure in self.sys.closure.iterpairs():
if isinstance(closure, AtomicClosure):
self.directCorr[t1, t2] = closure.calculate(
self.sys.domain.r, self.GammaIn[t1, t2])
elif isinstance(closure, MolecularClosure):
raise NotImplementedError(
'Molecular closures are untested and not fully implemented.'
)
self.directCorr[t1, t2] = closure.calculate(
self.GammaIn[t1, t2], self.omega[t1, t1], self.omega[t2,
t2])
else:
raise ValueError('Closure type not recognized')
self.sys.domain.MatrixArray_to_fourier(self.directCorr)
self.OC = self.omega.dot(self.directCorr)
self.IOC = self.I - self.OC
self.IOC.invert(inplace=True)
self.totalCorr = self.IOC.dot(self.OC).dot(self.omega)
self.totalCorr /= self.sys.density.pair
self.GammaOut = self.totalCorr - self.directCorr
self.sys.domain.MatrixArray_to_real(self.GammaOut)
self.y = self.sys.domain.long_r * (self.GammaOut.data -
self.GammaIn.data)
return self.y.reshape((-1, ))
def solve(self, guess=None, method='krylov', options=None):
'''Attempt to numerically solve the PRISM equations
Using the supplied inputs (in the constructor), we attempt to numerically
solve the PRISM equations using the scheme laid out in :func:`cost`. If the
numerical solution process is successful, the attributes of this class
will contain the solved values for a given input i.e. self.totalCorr will
contain the numerically optimized (solved) total correlation functions.
This function also does basic checks to ensure that the results are
physical. At this point, this consists of checking to make sure that
the pair correlation functions are not negative. If this isn't true
a warning is issued to the user.
Parameters
----------
guess: np.ndarray, size (rank*rank*length)
The initial guess of :math:`\gamma` to the numerical solution process.
The numpy array should be of size rank x rank x length corresponding to
the a full flattened MatrixArray. If not specified, an initial guess
of all zeros is used.
method: string
Set the type of optimization scheme to use. The scipy documentation
for `scipy.optimize.root
<https://docs.scipy.org/doc/scipy/reference/generated/scipy.optimize.root.html>`__
details the possible values for this parameter.
options: dict
Dictionary of options specific to the chosen solver method. The
scipy documentation for `scipy.optimize.root
<https://docs.scipy.org/doc/scipy/reference/generated/scipy.optimize.root.html>`__
details the possible values for this parameter.
'''
if guess is None:
guess = np.zeros(self.sys.rank * self.sys.rank *
self.sys.domain.length)
if options is None:
options = {'disp': True}
self.minimize_result = root(self.cost,
guess,
method=method,
options=options)
if self.totalCorr.space == Space.Fourier:
self.sys.domain.MatrixArray_to_real(self.totalCorr)
tol = 1e-5
warnstr = 'Pair correlations are negative (value = {:3.2e}) for {}-{} pair!'
for i, (t1, t2), H in self.totalCorr.iterpairs():
if np.any(H < -(1.0 + tol)):
val = np.min(H)
warnings.warn(warnstr.format(val, t1, t2))
return self.minimize_result
def pmf(PRISM):
r'''Calculate the potentials of mean force
Parameters
----------
PRISM: pyPRISM.core.PRISM
A **solved** PRISM object.
Returns
-------
pmf: pyPRISM.core.MatrixArray
The full MatrixArray of potentials of mean force
**Mathematical Definition**
.. math::
w_{\alpha,\beta}(r) = -k_{B} T \ln(h_{\alpha,\beta}(r)+1.0)
**Variable Definitions**
- :math:`w_{\alpha,\beta}(r)`
Potential of mean force between site types :math:`\alpha` and
:math:`\beta` at a distance :math:`r`
- :math:`g_{\alpha,\beta}(r)`
Pair correlation function between site types :math:`\alpha` and
:math:`\beta` at a distance :math:`r`
- :math:`h_{\alpha,\beta}(r)`
Total correlation function between site types :math:`\alpha` and
:math:`\beta` at a distance :math:`r`
**Description**
A potential of mean force (PMF) between site types :math:`\alpha` and
:math:`\beta`, :math:`w_{\alpha,\beta}` represents the the ensemble
averaged free energy change needed to bring these two sites from
infinite separation to a distance :math:`r`. It can also be thought of
as a potential that would be needed to reproduce the underlying
:math:`g_{\alpha,\beta}(r)`.
.. warning::
Passing an unsolved PRISM object to this function will still produce
output based on the default values of the attributes of the PRISM
object.
Example
-------
.. code-block:: python
import pyPRISM
sys = pyPRISM.System(['A','B'])
# ** populate system variables **
PRISM = sys.createPRISM()
PRISM.solve()
pmf = pyPRISM.calculate.pmf(PRISM)
pmf_BB = pmf['B','B']
'''
rdf = pair_correlation(PRISM)
#let's ignore any warnings about negative values in the log function
with np.errstate(invalid='ignore'):
rdf = -1.0 * PRISM.sys.kT * np.log(rdf.data)
#length and rank will be inferred from data
pmf = MatrixArray(data=rdf,
space=Space.Real,
length=None,
rank=None,
types=PRISM.sys.types)
return pmf
