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J Chem Theory Comput. Author manuscript; available in PMC 2020 September 17.
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Published in final edited form as:

J Chem Theory Comput. 2017 July 11; 13(7): 3185–3197. doi:10.1021/acs.jctc.7b00174.
PSI4 1.1: An Open-Source Electronic Structure Program

Emphasizing Automation, Advanced Libraries, and
Interoperability
Robert M Parrish1, Lori A Burns1, Daniel G A Smith1, Andrew C Simmonett2, A Eugene
DePrince 3rd3, Edward G Hohenstein4, Uğur Bozkaya5, Alexander Yu Sokolov6, Roberto Di
Remigio7, Ryan M Richard1, Jérôme F. Gonthier1, Andrew M James8, Harley R
McAlexander8, Ashutosh Kumar8, Masaaki Saitow9, Xiao Wang8, Benjamin P Pritchard1,
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Prakash Verma10, Henry F Schaefer 3rd11, Konrad Patkowski12, Rollin A King13, Edward F
Valeev8, Francesco A Evangelista10, Justin M Turney11, T Daniel Crawford8, C David
Sherrill1
1Center for Computational Molecular Science and Technology, School of Chemistry and
Biochemistry, School of Computational Science and Engineering, Georgia Institute of Technology,
Atlanta, Georgia 30332-0400, United States.
2National
Institutes of Health, National Heart, Lung and Blood Institute, Laboratory of
Computational Biology, 5635 Fishers Lane, T-900 Suite, Rockville, Maryland 20852, United
States.
3Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida
32306-4390, United States.
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4Department of Chemistry and Biochemistry, The City College of New York, New York, New York
10031, United States.
5Department of Chemistry, Hacettepe University, Ankara 06800, Turkey.
6Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena,
California 91125, United States.
7Department of Chemistry, Centre for Theoretical and Computational Chemistry, UiT, The Arctic
University of Norway, N-9037 Tromsø, Norway.
8Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
9Department of Chemistry and Research Center for Smart Molecules, Rikkyo University, 3-34-1
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Nishi-ikebukuro, Toshima-ku, Tokyo 171-8501, Japan.

10Department of Chemistry, Emory University, Atlanta, Georgia 30322, United States.
11Center for Computational Quantum Chemistry, University of Georgia, Athens, Georgia 30602,
United States.
12Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, United
States.
13Department of Chemistry, Bethel University, St. Paul, Minnesota 55112, United States.
Parrish et al. Page 2
Abstract
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PSI4 is an ab initio electronic structure program providing methods such as Hartree-Fock, density
functional theory, configuration interaction, and coupled-cluster theory. The 1.1 release represents
a major update meant to automate complex tasks, such as geometry optimization using complete-
basis-set extrapolation or focal-point methods. Conversion of the top-level code to a Python
module means that PSI4 can now be used in complex workflows alongside other Python tools.
Several new features have been added with the aid of libraries providing easy access to techniques
such as density fitting, Cholesky decomposition, and Laplace denominators. The build system has
been completely rewritten to simplify interoperability with independent, reusable software
components for quantum chemistry. Finally, a wide range of new theoretical methods and analyses
have been added to the code base, including functional-group and open-shell symmetry adapted
perturbation theory (F-SAPT and O-SAPT), density-fitted coupled cluster with frozen natural
orbitals [DF-FNO-CCSD(T)], orbital-optimized perturbation and coupled-cluster methods (e.g.,
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OO-MP2 and OO-CCSD), density-fitted multiconfigurational self-consistent field (DF-MCSCF),

density cumulant functional theory (DCT), algebraic-diagrammatic construction [ADC(2)] excited
states, improvements to the geometry optimizer, and the “X2C” approach to relativistic
corrections, among many other improvements.
Graphical Abstract
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1 Introduction
Quantum chemical computations have become an indispensable part of molecular science.
They can provide accurate molecular geometries, reaction mechanisms and energetics, and
simulated spectra. Quantum chemistry also yields parameters needed to develop force-field
models, and as such serves to anchor multiscale modeling efforts. Advances in electronic
structure theory and in computer hardware have meant that quantum chemistry is now
capable of giving very accurate results for systems with about three dozen atoms or less and
reasonably accurate results for hundreds of atoms.
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Unfortunately, electronic structure methods are inherently complicated, and the computer
programs to implement them are quite lengthy. Fully featured quantum chemistry program
packages can easily reach more than one million lines of source code. Additionally, it takes
significant effort to optimize these codes so that they run as quickly as possible (an
important consideration, given that computations are very time-consuming for larger
molecules and/or more accurate models). Thus, most of the popular quantum chemistry
programs have been developed over many years through the combined efforts of numerous
programmers and often several research groups. This model of large, complex codes
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developed by multiple programmers over many years presents a tremendous challenge to

keeping up with the rapid pace of recent innovations in computer hardware, including the
increasing number of central processing unit (CPU) cores per node, the ubiquity of graphics
processing units (GPUs), and emerging hardware like Intel’s Xeon Phi. It also presents a
challenge to the rapid deployment of new techniques from electronic structure theory,
because typically a desirable new feature is re-implemented for each quantum chemistry
package.
We believe that this current development model is unsustainable and that the future of
quantum chemistry software development lies in a more modular approach, in which small,
independent teams develop reusable software components that can be incorporated directly
into multiple quantum chemistry packages, for example, as a library or standalone program
that has no dependency on any particular quantum chemistry program.1 For example,
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libraries like LIBINT,2 LIBEFP,3,4 CHEMPS2,5–7 SIMINT,8,9 LIBXC,10,11 DKH,12,13 and

PCMSOLVER14,15 are written so that they can be called from multiple quantum chemistry
programs, and programs like DFTD316 and MRCC17,18 have been developed so that they are
straightforward to interface to other packages. Several analysis and visualization tools (e.g.,
WebMO,19 Molden,20,21 and VMD22,23) have been written to analyze wavefunctions with
data written in common formats. Over the past few years, we have substantially restructured
and extended key portions of the PSI4 quantum chemistry package to facilitate
interoperability with such reusable software components (or even with other large quantum
chemistry programs).
Our build system, driver, and binary distribution system have been redesigned to make it
easier for PSI4 to call independent software components. At the same time, we have also
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made PSI4 callable as a Python library, so that it can be incorporated into complex
workflows driven by custom Python scripts or interfaced with other scientific Python
projects, of which there has been an explosion in the past few years. Wrapping much of the
C++ functionality of PSI4 by Python has not only enabled interoperability, but it has also led
to more rapid prototyping and development of complex functionality. Interoperability has
also been enhanced by the addition of functions to write out data in common file formats
used by quantum chemistry analysis tools, e.g., Molden format for molecular orbitals and
formatted checkpoint files.
By moving our development system to a publicly viewable GitHub24 repository and by

incorporating social coding practices, we have made it easier for independent developers to
interface their work to PSI4. Completely independently of the PSI4 developers, interfaces to
PSI4 have been developed for a number of projects, including GeomeTRIC,25,26 a geometry
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optimization code that includes the translation-rotation-internal coordinate (TRIC) system;

JANPA, a Java-based implementation of the Natural Population Analysis (NPA)27 method;
28,29 an implementation30 of the restrained electrostatic potential (RESP) method for fitting
atomic charges;31 and htmd, a force-field parameterization tool.32
We have used object-oriented design to make certain key functionalities available through a
generic application program interface (API), while allowing optimizations or adaptations to
various hardware to be done “under the hood” without necessitating changes to the top-level
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code that implements a particular quantum chemistry method. For example, this allows us to
transparently switch among different libraries to compute electron repulsion integrals,
depending on which is optimal for a particular type of hardware. Finally, we have also added
libraries to enable techniques that are becoming more important in modern quantum
chemistry, such as density fitting33–41 and Cholesky decomposition.42–46
Here we summarize our efforts to modularize and extend PSI4 along these lines. We also
report on additional new capabilities of the package. This article, and its author list, reflects
primarily the changes since the previous PSI4 publication,47 written at the stage of an alpha
release. The PSI4 1.1 release carries over much of the design, code, and capabilities of that
earlier version of PSI4 and also retains some code and capabilities from PSI3.48
2 Python Interface
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In the alpha release of PSI4 in 2012,47 we introduced a Python front-end to what had
previously been an exclusively C/C++ program. All computationally intensive modules
remain written in C++ for efficiency reasons, but user input parsing and simple, high-level
functions that help drive the program are written in Python.
2.1 Using Python to Parse User-Friendly Input and Automate Multi-Step Computations
One of the design goals of PSI4 is to make the program as easy to use as possible, for both
beginners and expert users. For beginners, a minimal input suffices for basic computations.
Indeed, one does not even need to specify atomic coordinates — for common molecules,
these can be obtained from the PubChem database (for nodes with internet connectivity).49
An input file to optimize the geometry of the benzene molecule using Hartree-Fock self-
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consistent-field (SCF) with the STO-3G basis50 is as simple as this:
molecule benzene{
pubchem:benzene
}
set basis sto-3g
optimize(“scf”)
For a graphical user interface (GUI), the popular WebMO program19 is capable of drawing
molecules, generating text input files, managing a job queue, and visualizing orbitals and
other results.
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Although many solutions would have sufficed to parse input files like the example above, we
also wished to allow much more complex input files by advanced users, who might want to
perform multi-step computations, execute loops to build a potential energy surface, create
tables and export data structures of results, or interface with other Python projects, all in the
input file. In this, we were inspired by the MOLPRO program,51 which enables looping and
post-processing operations.
Our approach is to use the Python language itself for input, yet allow free-form specification
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of common quantum chemical input (e.g., molecules, options, custom basis sets) by
intercepting and parsing them into proper Python commands. In this way, basic users submit
minimal input files without any required knowledge of Python, while the inclined can draw
upon the full scientific Python ecosystem. This combination of simple quantum chemistry
directives and user-specified Python code forms a domain-specific language, “Psithon,” that
has shown itself an effective balance between power and ease-of-use since its introduction in
alpha PSI4. Advanced users of quantum chemistry programs commonly write workflow-
automating helper scripts to aggregate computations, drive supporting executables, or extract
key quantities. With PSI4 such functionality can be expressed directly in an input file with
conventional Python or, if a given functionality is popular, absorbed into the PSI4 driver.
2.1.1 Specifying Levels of Theory, Basis Set Extrapolations, Corrections for

Basis Set Superposition Errors, and Many-Body Expansions of Clusters—In
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the 1.1 release, PSI4 has been significantly overhauled to make many common operations,
which would normally be done by custom user scripts, as easy as specifying a single input
string. For example, the common notation of computational chemistry that separates method
and basis with a slash can be used, e.g., optimize(“SCF/STO-3G”). This idea can be
extended to complete-basis-set (CBS) extrapolations, which can be expressed as
energy(“SCF/cc-pV[D,T,Q]Z”) to perform an exponential extrapolation of the SCF energy
using the cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets.52 A two-point extrapolation of the
correlation energy can be specified in a similar way, e.g., energy(“MP2/aug-cc-pV[T,Q]Z”)
for second-order Møller-Plesset perturbation theory (MP2) in augmented basis sets.52,53
Depending on the method (SCF or post-SCF) and number of ζ-levels specified,
extrapolation formulae are selected automatically among 2- and 3-point Helgaker schemes
for SCF energies54 and 2-point Helgaker for correlation energies.55 Alternate or user-defined
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(by writing a Python function) extrapolation equations may be specified through additional
keywords. For example, opt(“MP2/aug-cc-pV[T,Q]Z + D:CCSD(T)/cc-pV[D,T]Z”,
corl_scheme=myxtpl_2) performs a focal point optimization with the coupled-cluster delta
correction employing a custom formula for its 2-point extrapolation atop MP2 using the
default 2-point Helgaker formula. Importantly, the 1.1 release also generalizes these
extrapolations to work also for geometry optimizations and vibrational frequencies, e.g.,
frequencies(“MP2/cc-pV[D,T]Z”) for an MP2 extrapolated vibrational frequency
computation.
In a similar way, corrections for basis set superposition errors (BSSE) can also be specified
very simply: energy(“MP2/aug-cc-pV[T,Q]Z”, bsse_type=“cp”) for an MP2 extrapolated
Boys-Bernardi counterpoise correction.56 For a molecular cluster, the Valiron-Mayer
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functional counterpoise (VMFC) correction57 is also available. Molecular clusters can also
be analyzed in an N-body fashion in terms of dimers, trimers, etc. This is fully automated by
PSI4’s Python driver and can be called by altering the bsse_type argument to the usual
energy() function. Grep-able, tabulated, and programmatically accessible quantities for each
requested fragment and basis set partitioning combination are made available, and multiple
BSSE treatments can be computed concurrently.
Handling such complex operations with such minimal user input is the role of the Python
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driver portion of PSI4. It contains generic functions like energy(), optimize(), and
frequencies(), which take a quantum chemistry method as an argument, then set appropriate
options based on user specifications and best practices for the method. The driver then
decides what C++ modules need to be called, and in what order. Results are passed back
from the C++ modules to the Python driver so that they can undergo various types of post-
processing (e.g., converting to other units, combining with results from other programs,
exporting as data structures, etc.). For composite and otherwise complex methods, the main
driver functions are often recursively called.
2.1.2 Passing Wavefunction Information—As the input to PSI4 computations is a

single Python script, information may be passed through objects in main memory. The 1.1
release greatly improves information passing over the alpha release by allowing
wavefunction objects to be passed between modules. For example, one could use density
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functional theory (DFT) orbitals as guess orbitals for a complete-active-space self-

consistent-field (CASSCF) procedure:
scf_e, scf_wfn = energy(“bp86”, return_wfn=True)

energy(“casscf”, ref_wfn=scf_wfn)
Additionally, one can obtain any method’s wavefunction and pass it to generic objects that
can write out or manipulate data: molden(), which writes Molden files; cubeprop(), which
writes densities and electrostatic potentials on a grid; and OEprop(), which computes
arbitrary one-electron properties. For example, writing the optimized-orbital MP2 orbitals in
Molden format can be accomplished by the following:
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omp2_e, omp2_wfn = energy(“omp2”, return_wfn=True)

molden(omp2_wfn, “omp2_orbitals.molden”)
2.2 Rapid Prototyping

Much of the C++ infrastructure of PSI4 has been made accessible at the Python layer. This
provides opportunities for rapid prototyping of quantum chemical procedures in Python,
while leveraging the existing, efficient C++ infrastructure. Indeed, for some procedures it is
even possible to write the final, production-level version of the code by organizing C++ calls
completely in Python. Interoperability between C++ and Python was previously
accomplished using Boost Python,58 but in the 1.1 release we have removed Boost due to its
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large size and build difficulties; we now use the header-only pybind11 library.59
PSI4 modules such as the “JK” object that generates Coulomb and exchange matrices are
readily available through Python:
# Create a JK object in the primary basis set

jk = psi4.core.JK.build(primary_basis)
# Provide an occupied orbital matrix for the density matrix:

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# D = C_left * C_right(T); by default C_right = C_left

jk.add_C_left(Cocc)
# Note that there are many possible sources for Cocc, e.g. sphericalized
atomic
# orbitals, a converged SCF, etc., and these details are up to the user
# Perform the computation and get the J and K matrices
jk.compute()
J = jk.J()
K = jk.K()
As JK builds are the bottleneck in SCF computations, a Python-based SCF algorithm can
have nearly identical execution time to that of full C++ code. This is one of many cases
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where the most computationally intensive parts of calculations can be handled by a PSI4
library, resulting in top-level code that is easy to write, easy to understand, and
computationally efficient.
The PSI4NUMPY project60 aims to enable the creation of clear, readable code for
development or pedagogical purposes by combining the extensive Python accessibility of
PSI4 with the popular Numerical Python (NumPy)61 library for high-level array
manipulation and access to the BLAS library. The latest version of PSI4 adopts code from
that project60 allowing PSI4 data and NumPy objects to be seamlessly interconverted. For
example,
np_array = numpy.zeros((5, 5))

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psi4_matrix = psi4.Matrix.from_array(np_array)
new_np_array = numpy.array(psi4_matrix)
2.3 Opportunities for Education in Electronic Structure Theory

Writing quantum chemistry code in this manner allows for the decoupling of learning
quantum chemistry from having to simultaneously learn a low-level programming language.
As low-level languages typically have much steeper learning curves than high-level
languages like Python, this can be quite advantageous. We have leveraged the Python
accessibility of much of the PSI4 infrastructure to develop guided projects for students to
write their own Hartree-Fock code; several students in Georgia Tech’s Computational
Chemistry course have done this as a class project. One of us (D.G.A.S.) offered an
introduction to electronic structure theory and programming in the summer of 2016 for
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summer students and new graduate students, utilizing PSI4 and PSI4NUMPY.
2.4 Psi4 as a Python Module

Finally, the most recent improvement in PSI4 is its ability to be loaded into a Python script as
a regular Python module. This ability has also opened up numerous opportunities to
integrate PSI4 with other powerful Python modules and related tools. For example, we have
been working on integrating PSI4 with the popular OpenMM package for molecular
mechanics. As both of these programs have Python front-ends, passing data between
programs is straightforward. PSI4 can also be run interactively through Jupyter notebooks,62
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which are like Mathematica notebooks for Python; intermediate results can be graphed and
analyzed with standard Python tools. We believe Jupyter notebooks hold promise as “lab
notebooks” (or supplementary information) for computational research, as well as for guided
computational chemistry laboratory exercises.
3 Interfaces to External Projects

The current model of quantum chemistry software development is one in which each
quantum chemistry package is a large “silo” of code standing independently of all the others.
While it is convenient for the user to have a package that contains many different features, it
is wasteful for different teams of developers to duplicate the effort of adding new features. It
would be better for specialists in a particular method to develop a reusable component that
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could be adopted by multiple programs. PSI4 strives to minimize the barrier to

interoperability with these add-ons by keeping their build and maintenance back-ends
separate from PSI4, yet maintaining a monolithic front-end for users. Since the beta versions
of PSI4, all projects not written by PSI4 core developers for PSI4 have been removed from the
code repository; the source instead resides in the author’s primary (upstream) repository
where possible. In their place are single “External Project” files that, when activated by
ENABLE_<AddOn> options, queue up the task of building that library from external source
code using an internal configuration or common set of build parameters and shared
dependencies. This “superbuild” framework is driven by the popular CMake tools.63 The
External Project scheme ensures that the footprint of each interfaced project within the PSI4
codebase consists of one build file and typically half-a-dozen lines of linking and include
directives. For greatest flexibility, all quantum chemistry dependencies and add-ons that
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require linking or internal code activation can be built from source (downloaded from
GitHub or research websites) during the PSI4 build. Or, existing pre-built libraries can be
detected and seamlessly linked in to the final PSI4 library and plugin system. Wherever
rational, shared and archive (static) libraries are equally supported. Whenever possible, the
changes to an external project’s build system required by PSI4 have been accepted upstream
to the main project. These typically consist of a few short files that should prove useful to
non-PSI4 users of the add-ons also.
Forming a clear delineation between PSI4 code and external projects simplifies build
maintenance but also permits better management and reuse of libraries so that core
developers and users alike can access a full-featured PSI4 compilation without hassle.
Invaluable in this endeavor is Anaconda,64 a distribution of Python (and its associated
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package manager, conda) that focuses on the scientific community and the cross-platform
accessibility of Python and Python/C++/Fortran binaries. Conda tools facilitate the
construction of relocatable (installable into any directory) and generic (executable on almost
any OS distribution) binary packages, which are hosted at https://anaconda.org/psi4 for Mac
and Linux (and, through Ubuntu Terminal, recent versions of Microsoft Windows). To make
binaries as foolproof as possible, while also maintaining the efficiency so vital to quantum
chemistry computations, a number of techniques are employed, including static linking of
high-quality math libraries, static linking of system libraries wherever possible,65 resolving
symbols to a widely available version of glibc, and turning off processor-specific

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optimizations (users wishing to obtain the full performance of processor-specific

optimizations, which vary from negligible to considerable, can activate these by building the
project from scratch). Conda packages are built for PSI4 itself and each of its add-ons. Each
can be downloaded individually or an environment specification can install a complete set.
For the PSI4 developer, pointing CMake to that install location allows all the add-on and
dependency libraries to be detected and linked into PSI4 itself, drastically reducing the
compile time and resulting in a full-featured PSI4 build. For someone who wishes to use the
PSI4 libraries to develop quantum chemistry code as quickly as possible, C++ and Python
PSI4 plugins can be developed from conda packages and conda compilers, without a local
development environment. For the user, the PSI4 conda package, some half-a-dozen add-on
packages, and still more non-quantum-chemistry dependencies are bundled up along with
the conda package manager into a standalone installer, available from http://psicode.org/
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downloads.html, that unpacks into a Miniconda + PSI4 + AddOns release distribution.
For External Projects the PSI4 project will (1) leave control of their code under their
purview; (2) maintain any interfacing code needed; (3) regularly run integration tests
between PSI4 and their code; (4) build a mostly statically linked conda package so that any
of their users can obtain a pre-built binary distribution through conda install addon --channel
psi4; (5) provide a development sandbox for their code through PSI4 plugins; and (6) provide
conda download counts independent of PSI4. This maintain-in-pieces build-as-whole model
is working for add-ons that are executables, libraries, and plugins from languages C, C++,
and Fortran (and could be extended to proprietary or restricted license add-ons), as seen in
Figure 1.
Cognizant that the expanding interconnectivity of quantum chemical software demonstrated

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by Figure 1 does not end with PSI4 (especially now that PSI4 is a library more than an
executable) and that PSI4 has benefited from the flexible licensing terms of our add-ons, the
license for PSI4 itself has been relaxed from the GNU General Public License version 2 or
later (GPL-2.0+) to the GNU Lesser General Public License version 3 (LGPL-3.0), thereby
permitting PSI4 to be incorporated downstream without downstream projects inheriting the
GPL. The required dependencies have been minimized so that it is possible to build a (non-
full-featured) PSI4 without any GPL involvement, and a conda package meeting those
restrictions is distributed.
The following is a list of external projects integrated with PSI4.
• DFTD3: This independent executable program by S. Grimme provides damped
dispersion corrections for use with density functional theory.16 The latest version
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incorporates modified damping parameters [-D3M and -D3M(BJ)] to better

model short-range contacts as described by Smith et al.66
• GCP: This “geometric counterpoise” executable by S. Grimme provides

approximate corrections for basis set superposition error based on the the
molecular geometry, allowing the implementation of the semiempirical methods
HF-3c and PBEh-3c.67,68
• PCMSOLVER: This library by Di Remigio, Frediani, and coworkers14,15

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implements the widely used polarizable continuum model (PCM) for solvation.
69–72 Within PCM, the mutual solute-solvent polarization is represented by an
apparent surface charge σ spread over the cavity boundary and computed as the
unique solution to the integral equation associated to the classical Poisson
problem,73 Tσ = − ℛφ, where the definition of the operators T and ℛ depends
on the molecular geometry and the Green’s function for the differential problem
at hand. This mathematical framework can be applied to complex environments,
such as homogeneous isotropic, ionic, and anisotropic liquids,73 and systems
with interfaces.74–77 In the model, a molecular cavity built from a set of
interlocking atom-centered spheres is partitioned into a mesh of (curvilinear or
planar) finite elements, to each of which is attached a finite basis set of
piecewise-regular polynomials that offer a natural discretization of the above
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equation into matrix form.
• LIBEFP: This library by Kaliman and Slipchenko3,4 implements the effective

fragment potential (EFP) method of Gordon and co-workers78,79 to provide ab
initio force fields.
• MRCC: The high-order coupled-cluster methods available in the multi-reference
coupled-cluster program of Kállay and co-workers17,18 are accessible from PSI4.
• DKH: This library by Wolf, Reiher, and Hess implements the Douglas-Kroll-Hess
relativistic corrections between 2nd and 4th order.12,13
• Integrals: PSI4 is unusual in that it supports multiple electron repulstion integral

(ERI) libraries. We continue to support the LIBINT library (version 1),2 originally
written for PSI3. However, an interface layer called libmints allows us to replace
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LIBINT with other integrals libraries, and we have written an interface to the ERD
library of Flocke and Lotrich.80 Very recently, we have also interfaced to the new
SIMINT library of Pritchard,8,9 optimized for architectures like the Intel Xeon Phi.
• CHEMPS2: This library5–7 presents a spin-adapted implementation of the density

matrix renormalization group (DMRG) approach,81,82 which is an effective way
to approximate complete active space configuration interaction (CAS CI) with
much larger active spaces (up to about 50 electrons in 50 orbitals for general
problems). DMRG-based complete active space self-consistent field (DMRG-
CASSCF)83 and CASSCF plus second-order perturbation theory (DMRG-
CASPT2)84 are available through CheMPS2.
• GDMA: PSI4 has been interfaced with the GDMA program of Stone,85 which
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provides distributed multipole analysis of wavefunctions to represent the

electrostatic field as a sum of contributions from point charges, dipoles, etc., at
atomic centers or other sites.
• V2RDM_CASSCF: This plugin86 (requiring PSI4) implements a semidefinite

programming algorithm for the variational optimization of the ground-state two-
electron reduced-density matrix (2RDM). This variational 2RDM (v2RDM)
approach is most useful as an alternative to CAS CI for describing the electronic
structure of an active space. Unlike CAS CI, v2RDM methods can be applied to
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large active spaces comprised of as many as 50 electrons in 50 orbitals. The

plugin also provides a v2RDM-driven CASSCF procedure that exploits density
fitting technology for the treatment of large numbers of external orbitals.87
• AMBIT: This library by Turney and co-workers88 provides tensors to represent

quantum chemistry quantities such as electron repulsion integrals or coupled-
cluster amplitudes.
• CFOUR:We have nearly completed a prototype interface that allows PSI4 to drive
computations performed by the CFOUR package for coupled-cluster theory.89
• FORTE: This plugin (requiring PSI4) by Li, Hannon, Schriber, Zhang, and
Evangelista90 implements a number of multireference quantum chemistry
methods, including approaches based on the driven similarity renormalization
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group (DSRG)91 with perturbative92,93 and nonperturbative truncation schemes.

94 Forte also implements two new selected-CI approaches, the adaptive-95 and
projector-CI.96
4 Development Process
PSI4 has adopted tools standard in the industry such as GitHub for collaboration and version
control, Travis CI97 for continuous integration testing, and CodeCov98 for test coverage
metrics. This ensures the primary source code retains its reproducibility and all code
changes can be reviewed by the entire PSI4 community. New developers feel safe making
changes to the base code, as all changes will be publicly visible and reviewed by the core
team through the GitHub “pull request” mechanism, and the changes will also be tested
automatically by the Travis CI system. The public visibility of the GitHub project helps
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communication between developers, both within the core team and also with independent
developers who want their code to work with PSI4. Several improvements and bug fixes have
been contributed back to the PSI4 development team from the broader community.
5 Libraries
5.1 Density fitting
One of the major barriers to efficient electronic structure computations is the large number
of ERIs. For a set of one-particle spatial basis functions ϕp r 1 (e.g., Gaussian atomic
orbitals, molecular orbitals), the ERIs are defined as
pq ∣ rs ≡ ∬ d3r1d3r2ϕp r ϕq r
1
ϕ r ϕs r ,
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1 1 r12 r 2 2 (1)
ℝ6
where r 1 and r 2 denote the Cartesian coordinates of electrons 1 and 2, respectively, and r12
is the distance between electrons 1 and 2. Each ERI encapsulates the electrostatic interaction
between a particle in the “pair-space” basis function ρpq r 1 ≡ ϕp r 1 ϕq r 1 in coordinate 1
with another particle in pair-space basis function ρrs r 2 ≡ ϕr r 2 ϕs r 2 in coordinate 2.
Despite the existence of a rich literature on the efficient evaluation of the ERIs in Gaussian
orbitals,99–101 the order-4 ERI tensor is a major bottleneck in terms of generation, storage
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and utilization.
A particularly elegant approach to reducing the impact of the 4-index nature of the ERIs in
electronic structure theory begins from the observation that the quadratic-scaling pair-space
basis ρpq r 1 is highly numerically redundant, particularly in large molecular systems
and/or high-quality basis sets. Fortunately, the usual quadratic-scaling pair-space basis can
be accurately represented in a linear-scaling “auxiliary basis” χA r 1 , e.g.,
A A
ρpq r 1 ≈ ∑A dpq χA r 1 , where dpq is an order-3 fitting coefficient tensor. This is the crux of
the extremely successful Cholesky decomposition (CD)42–46 and density fitting (DF)33–41
approaches. In particular, we focus on the now-ubiquitous “Coulomb-metric” DF approach,
in which the ERI is approximated as
∑ −1
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C C
pq ∣ rs ≈ pq ∣ A A ∣ B B ∣ rs ≡ Bpq Brs . (2)
AB
In the last step, and below, we assume that repeated indices are summed over. The use of DF
reduces the storage burden of the ERI tensor from order-4 to order-3. In addition,
transforming the integrals from the atomic orbital to molecular orbital basis now becomes an
O n4 operation instead of an O n5 operation. Moreover, the subsequent utilization of the
ERI tensor in contractions with density matrices or wavefunction amplitudes is often
considerably more efficient than with conventional integrals, due to reduced storage cost and
the occasional opportunity to achieve formal scaling reduction by the “unpinning” of the pq
and rs indices in the DF representation (i.e., this sometimes allows more efficient ways to
order the steps in the tensor multiplications). Coulomb-metric DF is exceedingly accurate,
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with errors in relative properties of chemical interest (barrier heights, interaction energies,
etc.) generally lower than 0.05 kcal mol−1 when using standardized auxiliary fitting basis
sets.41
Coulomb-metric DF is utilized in many electronic structure methods in PSI4, as discussed

below. The use of DF to compress the molecular-orbital basis ERIs is so ubiquitous that we
have introduced a DFERI helper class to quickly construct the DF factorization for a given
set of orbital pair-spaces (including customized pair-spaces). An example of using the
Q Q
DFERI object to build the DF factorization of the hole-particle integrals ia ∣ jb ≈ Bia Bjb
(where i and j indicate hole orbitals and a and b indicate particle orbitals) is presented below,
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// Build a DFERI object with default options/orbital spaces

shared_ptr<DFERI> df = DFERI::build(primary,auxiliary,options);
// Request the decomposition (ia|jb) ~= B_iâQ B_jb^Q for MP2
df->add_pair_space(“MP2”, “ACTIVE_OCC”, “ACTIVE_VIR”);
// Compute the DF factorization
df->compute();
// Grab the DF tensor (on disk) for subsequent use
shared_ptr<Tensor> BiaQ = df->ints[“MP2”];
This helper class shields the user from the specifics of forming the DF integrals:
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parallelization over multiple cores, using Cauchy-Schwarz spatial sieving to remove

insignificant pq pairs in the AO basis DF integrals, applying the atomic orbital to molecular
orbital integral transform, locating the pseudoinverse of the fitting metric, and applying the
fitting metric. Additionally, if multiple pair-space tasks are requested, the generation of the
integrals, first-half integral transformation, and fitting metric inverse are coalesced to avoid
redundant effort. Thus, in just a few lines of client code, the user has access to DF
factorizations that are tractable on problems with up to ~ 6000 basis functions, and can then
focus on the application of these DF tensors to implement their desired method.
5.2 JK object
A fundamental (and often quite computationally expensive) operation in myriad electronic
structure methods is the construction of one-electron “Coulomb” (Jpq) or “exchange” (Kpq)
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matrices corresponding to a pre-specified generalized one-particle density matrix (Drs):
J pq ≡ ∑ pq ∣ rs Drs, (3)
rs
Kpq ≡ ∑ pr ∣ qs Drs . (4)

rs
SCF, coupled-perturbed Hartree-Fock, configuration interaction singles, and many terms in

symmetry-adapted perturbation theory and multiconfigurational self-consistent-field
(MCSCF) can be formulated in terms of these matrices. There are many approaches to
efficiently and/or exactly forming these matrices, including integral-direct, PK supermatrix,
102 or density fitting. To hide the details of these approaches from the user, we have
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introduced an abstract JK class, implemented by any one of a number of DirectJK, DFJK,

DiskJK, etc. classes. After construction, the user interacts with the JK object in an abstract
manner, requesting J and K matrices without needing to know the details of how they are
constructed. This means that any method coded in terms of the JK object automatically can
use DF, Direct, or any other integral technology from the outset. An example of computing J
and K matrices at the Python layer was presented above in Section 2.2.
The density matrices supplied to the JK object are actually specified in terms of their
underlying factorization in terms of occupied orbital coefficients. This factorization naturally
occurs in most places that J and K matrices appear (and can always be achieved by
supplying the density and identity matrices as the factor tensors, if needed). However,
endowing the JK object with knowledge of the factorization and symmetry of the density
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matrix often allows for significant performance gains, e.g., in DF Hartree-Fock.41
6 New Capabilities
6.1 Symmetry-Adapted Perturbation Theory (SAPT)
One of the specialties of PSI4 is a suite of symmetry-adapted perturbation theory
(SAPT)103–105 codes for the analysis of noncovalent interactions.106 Previously, we had
introduced efficient density-fitted and/or natural-orbital-accelerated implementations of
SAPT0,107,108 SAPT2+3,109,110 and SAPT2+3 with a coupled-cluster doubles treatment of

dispersion, SAPT2+3(CCD).111 These allow the use of DF-SAPT0 on systems with up to ~
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3500 basis functions and the use of DF-SAPT2+3(CCD) on systems with up to ~ 1200 basis
functions. Recently, we have extended the capabilities of the SAPT codes in PSI4 to broaden
their applicability beyond closed-shell dimers and to deepen the insight obtained. These
developments include the “functional group” SAPT (F-SAPT) decomposition,112,113 which
provides a partition of the SAPT0 energy at the chemical functional group level through
partial summations of the SAPT perturbation series in terms of pairs of nuclei and localized
electrons. F-SAPT0 has the same computational cost as a standard DF-SAPT0 analysis, but
provides deeper insight by quantifying the contribution of each pair of functional groups to
each intermolecular interaction energy term. For example, with F-SAPT we can partition the
interaction energy in a protein-ligand interaction into contributions between functional
groups on the ligand and individual side-chains in the active site.
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Another new development is “intramolecular” SAPT (I-SAPT),115 which uses Hartree-Fock-

in-Hartree-Fock embedding116 to produce a SAPT0-type interaction energy analysis for two
moieties interacting within the presence of a third body, which might be covalently bound to
one or both of the moieties in question. I-SAPT thus yields insight into intramolecular
noncovalent interactions, previously inaccessible to SAPT. An example of the combined
deployment of F-SAPT and I-SAPT is depicted in Figure 2 above. The last new extension of
SAPT methods in PSI4 is an efficient implementation of open-shell SAPT0.117 The
corresponding equations were only recently published,118,119 and we present the first
publicly available fully density-fitted implementation SAPT0 using unrestricted Hartree-
Fock references, allowing computations on high-spin radical dimers of unprecedented sizes.
The SAPT0 codes, and their F-SAPT, I-SAPT, and open-shell extensions, make substantial
use of the JK object and other libraries described in Section 5, which greatly accelerated the
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implementation of these methods. Moreover, the use of these common library primitives
serve to “standardize” the tractability limits of all of the SAPT0-type methods, meaning that
they all are deployable to the same ~ 3500 basis function scale.
6.2 Density-Fitted and Cholesky Decomposition Coupled-Cluster Theory, with Frozen

Natural Orbitals
One of the major additions to PSI4 since the alpha release is coupled-cluster theory utilizing
density-fitting or Cholesky decomposition approximations for the ERIs, as provided by the
libraries described in section 5.1. The DF/CD approximations substantially reduce the input/
output time associated with processing the ERIs. However, the rate-determining step in
coupled-cluster singles and doubles (CCSD)120 remains the same, scaling as O o2v4 , where
o and v are the number of occupied and virtual orbitals, respectively. Indeed, this rate-
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determining step, the so-called particle-particle ladder term, becomes actually more
computationally costly in the DF/CD formalism, as one has to create the all-virtual ERIs
from the 3-index quantities in a step that scales as O Naux v4 , where Naux is the size of the
auxiliary index (the number of auxiliary basis functions in the DF approach, or the number
of Cholesky vectors in the CD approach). While technically only a fifth-power term, it is a
very expensive one, since Naux and v are both large compared to o.
We addressed this issue by using a synergistic approximation, frozen natural orbitals

(FNOs).121–124 These orbitals are better suited to truncating the virtual orbital subspace; one
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can delete a significant fraction of the most weakly occupied natural orbitals with only a
minor impact on the total energy. Indeed, in our tests of intermolecular interaction energies
in the S22 test set,125 we performed computations with coupled-cluster through perturbative
triples [CCSD(T)] in which we deleted FNO virtual orbitals with occupation numbers less
than 10−5. In an aug-cc-pVDZ basis set,52,53 the mean absolute error for this approximation
was only 0.012 kcal/mol when MP2 is used to approximately correct for the deleted FNO
virtual orbitals.126 The errors due to density fitting are an order of magnitude smaller than
this, about 0.001–0.002 kcal/mol when using the standard double-ζ density fitting auxiliary
basis sets.127 On the other hand, the combined DF/CD and FNO approximations can lead to
substantial speedups in some cases, particularly for intermolecular interactions when
counterpoise corrections are applied, because most of the “ghost” functions are weakly
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occupied and can be effectively truncated by the FNO procedure. To compute the relatively
small and subtle three-body contribution to the interaction energy of the benzene trimer, we
used a very conservative 10−7 cutoff on the FNOs, and nevertheless the overall counterpoise-
corrected DF-FNO-CCSD(T)/aug-cc-pVDZ computation ran four times faster than the
corresponding conventional CCSD(T) computation.127 This allowed us to perform a large
number of such computations, which resulted in the first definitive resolution of the three-
body contribution to the lattice energy of crystalline benzene.128 Additional speedups of
about 3x are possible using our version of the code optimized for GPUs.129 The
MOLCAS130 and Q-Chem131 programs have also implemented coupled-cluster codes using
DF and/or CD approximations combined with FNOs or similar orbitals.132,133
6.3 Perturbation theory and coupled-cluster gradients

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Analytic gradients have been implemented for MP2 and third-order Møller-Plesset
perturbation theory (MP3), using restricted Hartree-Fock (RHF) or unrestricted Hartree-
Fock (UHF) orbitals, with conventional integrals or with density fitting. From these codes, it
was straightforward134 to also implement “MP2.5,” which is a simple average of MP2 and
MP3.135 This method has been found134–136 to give rather accurate results for non-covalent
interaction energies at a substantially reduced cost compared to CCSD(T).
We have also recently added analytic gradients for CCSD and CCSD(T) with RHF or UHF
orbitals. In addition, we published the analytic gradients of density-fitted CCSD.137 The
density fitting approximation, while speeding up the computation of certain terms, has very
little effect on geometries or vibrational frequencies.137,138
6.4 Optimized-Orbital Methods

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In wavefunction methods, one typically uses canonical Hartree-Fock orbitals. However, it is

also possible to use orbitals that minimize the energy of the targeted post-Hartree-Fock
wavefunction; MCSCF would be a popular example. Minimizing the energy of other kinds
of wavefunctions with respect to orbital rotations is not nearly as well explored, but it has
been reported in the past for MP2139–142 and coupled-cluster doubles (CCD).120,143–145 The
use of optimized orbitals simplifies computation of response properties and means that
orbital response terms are already accounted for in analytic gradients. Additionally,
optimized-orbital (OO) CCD was found,144 like Brueckner CCD, to provide much better
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vibrational frequencies for systems exhibiting artifactual spatial symmetry-breaking like

NO3 and O+
4.
146,147
PSI4 provides extensive support for optimized-orbital wavefunction methods, including an

improved Newton-Raphson algorithm for the orbital optimization.148 Optimized-orbital
versions of MP2,148 MP3,149 MP2.5,150 linearized CCD,151 and CCD148 are implemented,
as well as standard or asymmetric (T) triples corrections152,153 to the latter.154 In addition,
analytic energy gradients are available for OO-MP2,150 OO-MP3,155 OO-linearized CCD,
151 and OO-MP2.5.134 Density-fitted versions of the energies and gradients are also
available for MP2,156 MP3,157 MP2.5,157 and linearized CCD.158 For a set of weakly
interacting dimers, orbital optimization was found to maintain the good performance of
Hartree-Fock-based MP2.5 for closed-shell systems, but for open-shell systems, orbital
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optimization decreased errors by a factor of 5 (leading to results better than the more
expensive CCSD method).134
6.5 Density-Fitted Multi-Configurational Self-Consistent-Field

In PSI4 1.1 the MCSCF module has been completely rewritten using an approach similar to
the atomic-orbital formulation.159 This method is able to reduce the most computationally
expensive pieces of MCSCF to J and K builds. There are several pieces of the pure atomic-
orbital formulation that do not scale well to large active spaces, and these pieces can be
supplied either by density-fitting techniques160 or transforming exact ERIs.
For flexibility, all methods of the MCSCF wavefunction object have been exported to Python
so that advanced MCSCF methods can be easily built.
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cas_e, cas_wfn = energy(“CASSCF”, return_wfn=True)

# Compute the sigma vector for the current MCSCF state
inp_vec = cas_wfn.reference_civector()
out_vec = cas_wfn.new_civector()
cas_wfn.sigma(inp_vec, out_vec)
# Build an arbitrary two-particle density matrix between two vectors
tpdm = cas_wfn.tpdm(inp_vec, out_vec)
Using these flexible objects allows for the rapid exploration of various post-MCSCF
theories. For example, SAPT based on CASSCF wavefunctions is being developed in such a
manner.
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6.6 Density Cumulant Functional Theory

PSI4 is the only quantum chemistry program that features a publicly available
implementation of density cumulant functional theory (DCT). Rather than describing
electron correlation using a many-electron wavefunction, as in conventional ab initio
theories, DCT uses the cumulant of the two-electron reduced density matrix.161 By
parametrizing the cumulant via a set of approximate constraints (also known as N-
representability conditions), DCT provides a way to directly obtain electronic density

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matrices and energies without explicitly constructing the electronic wave function, thus
making the computation of molecular properties (e.g., equilibrium structures, dipole
moments, vibrational spectra) very efficient. Among other attractive features of DCT are
size-extensivity, orbital relaxation, and the ability to efficiently incorporate high-order
electron correlation effects. The earlier version of PSI4 presented the first implementation162
of the original DCT formulation that used a simple set of approximate N-representability
conditions (the DC-06 method).161 In the PSI4 1.1 release, several new DCT methods have
been implemented, including an improved description of the one-particle density matrix
(DC-12),163 orbital-optimized DCT formulations (ODC-06 and ODC-12),164 and more
sophisticated N-representability conditions and three-particle correlation effects [ODC-13
and ODC-13(λ3)].165 These new methods have a similar computational cost as the original
DC-06 method, but exhibit much higher accuracy, especially for systems with unpaired
electrons and significant multi-reference effects.166,167 The new DCT code also features
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analytic gradients for the DC-06, ODC-06, and ODC-12 methods.164,168 Very recently, we
introduced density fitting and spin-adaptation, which significantly reduce the cost of the
two-electron integral transformation for the orbital-optimized DCT methods (e.g., ODC-12).
169 Using this new DF-based implementation, it is now possible to perform DCT
computations with all electrons correlated for systems with more than 1000 basis functions.
6.7 Algebraic-Diagrammatic Construction Excitation Energies

The latest version of PSI4 includes code to compute electronic excitation energies using the
second-order algebraic-diagrammatic construction scheme [ADC(2)].170 This can be
thought of as an excited state generalization of MP2. The code accounts for point-group
symmetry through the libdpd library, and it also includes a “partially renormalized” variant,
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PR-ADC(2), meant to confer resistance against quasi-degeneracy, described in Ref. 171. It

can perform routine computations on systems with ~ 1000 basis functions.
6.8 Geometry Optimizer

By default, the geometry optimizer uses redundant internal coordinates, but the ability to
alternatively use Cartesian or delocalized internal coordinates has been added since the alpha
release. The default optimization step is now the iterative, restricted one172 arising from the
rational function optimization method.173 Cartesian Hessians from any source, and the
Hessian guess from Lindh et al.174 may now be used.
There is improved support for constrained optimizations, including the ability to freeze
selected internal and Cartesian coordinates, and to optimize toward a structure with a desired
coordinate value using extra forces. The user can also turn on a “dynamic-level” algorithm
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that incrementally tries more robust optimization methods for difficult systems when poor
steps occur. This approach was critical in obtaining optimized geometries in a study of
highly-strained alkoxy-substituted 1,8-bis((propyloxyphenyl) ethynyl) naphthalenes.175
6.9 X2C Relativistic Corrections

One-component scalar theories offer an economical and convenient way to include
approximate relativistic effects in electronic structure computations both at the self-
consistent-field level (Hartree-Fock, DFT) and in electron correlation methods. PSI4

implements the spin-free one-electron version of the exact-two-component approach,176–185
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abbreviated as X2C. An X2C computation starts with the diagonalization of the one-electron
Dirac Hamiltonian using a kinetically balanced basis set. Next, a Foldy-Wouthuysen
transformation186 is performed, which yields an effective one-electron Hamiltonian matrix
(hX2C), which is the sum of one-electron modified kinetic and potential energy matrices.
The choice of basis for X2C computations requires some considerations. In general,
contracted basis sets do not offer a balanced description of the large and small components
of the wave function, so it is generally recommended to evaluate the X2C Hamiltonian via a
decontraction/recontraction procedure. The default procedure used in PSI4 consists in
solving the Dirac Hamiltonian in a decontracted atomic orbital basis followed by projection
of the solutions onto the contracted basis. Alternatively, the user may perform a computation
in a fully decontracted basis.
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One of the major advantages of spin-free scalar relativistic approaches like X2C is that they
can be easily interfaced with non-relativistic electronic structure methods by replacing the
one-electron Hamiltonian matrix with the quantity hX2C. All other quantities that enter these
theories (two-electron integrals, exchange-correlation functionals, etc.) are evaluated using
standard non-relativistic equations. The cost of X2C computation has a scaling proportional
to the cube of the number of basis functions (the number of primitive basis functions, in the
case of decontraction/recontraction procedure) and is generally negligible. An example
application of the X2C capabilities of PSI4 is a recently developed X2C/orthogonality-
constrained DFT187 approach to predict near edge X-ray absorption spectra.188 The use of
scalar relativistic Hamiltonians was found to be essential, since already for second-row
elements the correction to nonrelativistic excitation energies is as large as 8 eV.
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7 Community and Outreach

Finally, the PSI4 team and our collaborators have fostered the growth of a user community.
We have spent significant effort in writing and maintaining a clear user manual,189 which
presents not only the features and input file syntax, but also discussions on simplifying and
automating more complex computations. The manual is formatted using Sphinx,190 which
facilitates heavy use of cross-referencing for user convenience. To ensure that
documentation on API and user options is kept up-to-date, we automatically generate this
information directly from the source code. New users can consult a number of tutorial
videos posted on YouTube191 and post questions at our user forum.192 News about PSI4, and
downloads, are posted on our website.193
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Not only do we wish to help experienced users learn about how to use PSI4, but we also want
to leverage PSI4 to teach undergraduates and graduate students about computational
chemistry. We have formed the PSI4Education group to develop and distribute a set of
computational chemistry laboratory exercises using freely available software, including PSI4.
Our webpage provides the labs developed to date,194 and a book chapter describes the
project as a whole.195 We use the popular WebMO graphical front-end,19 which is interfaced
to PSI4. A Psi4Education workshop was held at the Biennial Conference on Chemical
Education demonstrating these lab exercises in 2014. In 2016, a joint workshop on quantum
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chemistry and molecular mechanics simulations at the Florida American Chemical Society
meeting introduced attendees to PSI4 integrated with plotting capabilities in Jupyter
notebooks. We plan to continue developing additional lab exercises as part of this effort. In
addition, as mentioned above in Section 2.3, advanced exercises in electronic structure
theory for upper-level undergraduates and beginning graduate students, developed using our
user-friendly Python front-end and the NumPy linear algebra library, are available through
the Psi4NumPy project.60
8 Conclusions
The hybrid C++/Python programming model seems successful in our experience so far. C++
allows fast, efficient code for lower-level, computationally intensive tasks. For the driver and
other higher-level portions of the code, Python seems to offer a lower barrier to entry for
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new programmers, and it can facilitate rapid prototyping thanks to the interface with NumPy.
Moreover, the large number of active scientific computing projects in Python is likely to aid
interoperability of PSI4 with other projects, which is one of our major goals. To that end, the
1.1 release uses a new build and distribution system to make it easy to connect PSI4 with
independently-developed, reusable software components. Finally, we have developed a new
set of libraries providing efficient generation of generalized Coulomb and exchange
matrices, density-fitted electron repulsion integrals, and related quantities. These libraries
have greatly simplified and sped up our development of numerous new features over the past
few years.
Acknowledgements
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We are grateful to the contributors of all earlier versions of the PSI program. Brandon Bakr provided Figure 2, and
Michael Zott provided a figure element for the TOC. Several of the co-authors have been supported in their
development of PSI4 and affiliated projects by the U.S. National Science Foundation, through grants ACI-1147843,
CHE-1300497, CHE-1351978, CHE-1361178, ACI-1449723, ACI-1450169, ACI-1465149, CHE-1566192, and
ACI-1609842; by the U.S. Department of Energy through grants DE-SC0015512 and DE-SC0016004; and by the
U.S. Department of Defense through a HPCMP Applications Software Initiative (HASI) grant. U. B. acknowledges
support from the Scientific and Technological Research Council of Turkey (Grant No. TUBITAK-114Z786) and the
European Cooperation in Science and Technology (Grant No. CM1405). R. D. R. acknowledges support from the
Research Council of Norway through a Centre of Excellence Grant (Grant No. 179568/V30). J. F. G. acknowledges
the postdoctoral fellowship No P2ELP2_155351 from the Swiss NSF. The authors thank Prof. Stefan Grimme for
consultations in validating HF-3c and PBEh-3c.
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Figure 1:
PSI4 creates an ecosystem for code, not a silo. Software packages required to build, required
to run, or optionally provide additional capabilities to PSI4 are shown. All are available as
conda packages from the default or psi4 channels (excepting pybind11, which is built
internally, MRCC, AMBIT, and FORTE).
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Figure 2:
Example F-SAPT analysis of non-covalent stabilization of a transition state in the reaction
of benzaldehyde with an enamine intermediate (see Ref. 114). Color coding shows the
electrostatic interaction between the phenyl group of benzaldehyde with the three functional
groups of the enamine intermediate. A red group is attracted to the other monomer, whereas
a blue group is repelled by the other monomer; C-H/π contacts contribute to the favorable
red/red interaction between the cyclohexenyl and phenyl groups.
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PSI4 1.1: An Open-Source Electronic Structure Program

Nishi-ikebukuro, Toshima-ku, Tokyo 171-8501, Japan.

OO-MP2 and OO-CCSD), density-fitted multiconfigurational self-consistent field (DF-MCSCF),

developed by multiple programmers over many years presents a tremendous challenge to

libraries like LIBINT,2 LIBEFP,3,4 CHEMPS2,5–7 SIMINT,8,9 LIBXC,10,11 DKH,12,13 and

By moving our development system to a publicly viewable GitHub24 repository and by

optimization code that includes the translation-rotation-internal coordinate (TRIC) system;

atomic charges;31 and htmd, a force-field parameterization tool.32

consistent-field (SCF) with the STO-3G basis50 is as simple as this:

2.1.1 Specifying Levels of Theory, Basis Set Extrapolations, Corrections for

2.1.2 Passing Wavefunction Information—As the input to PSI4 computations is a

functional theory (DFT) orbitals as guess orbitals for a complete-active-space self-

scf_e, scf_wfn = energy(“bp86”, return_wfn=True)

omp2_e, omp2_wfn = energy(“omp2”, return_wfn=True)

2.2 Rapid Prototyping

# Create a JK object in the primary basis set

# Provide an occupied orbital matrix for the density matrix:

# D = C_left * C_right(T); by default C_right = C_left

np_array = numpy.zeros((5, 5))

2.3 Opportunities for Education in Electronic Structure Theory

2.4 Psi4 as a Python Module

3 Interfaces to External Projects

could be adopted by multiple programs. PSI4 strives to minimize the barrier to

symbols to a widely available version of glibc, and turning off processor-specific

optimizations (users wishing to obtain the full performance of processor-specific

downloads.html, that unpacks into a Miniconda + PSI4 + AddOns release distribution.

Cognizant that the expanding interconnectivity of quantum chemical software demonstrated

The following is a list of external projects integrated with PSI4.

• DFTD3: This independent executable program by S. Grimme provides damped

incorporates modified damping parameters [-D3M and -D3M(BJ)] to better

• GCP: This “geometric counterpoise” executable by S. Grimme provides

• PCMSOLVER: This library by Di Remigio, Frediani, and coworkers14,15

equation into matrix form.

• LIBEFP: This library by Kaliman and Slipchenko3,4 implements the effective

• Integrals: PSI4 is unusual in that it supports multiple electron repulstion integral

• CHEMPS2: This library5–7 presents a spin-adapted implementation of the density

provides distributed multipole analysis of wavefunctions to represent the

• V2RDM_CASSCF: This plugin86 (requiring PSI4) implements a semidefinite

large active spaces comprised of as many as 50 electrons in 50 orbitals. The

• AMBIT: This library by Turney and co-workers88 provides tensors to represent

group (DSRG)91 with perturbative92,93 and nonperturbative truncation schemes.

Coulomb-metric DF is utilized in many electronic structure methods in PSI4, as discussed

// Build a DFERI object with default options/orbital spaces

parallelization over multiple cores, using Cauchy-Schwarz spatial sieving to remove

matrices corresponding to a pre-specified generalized one-particle density matrix (Drs):

Kpq ≡ ∑ pr ∣ qs Drs . (4)

SCF, coupled-perturbed Hartree-Fock, configuration interaction singles, and many terms in

introduced an abstract JK class, implemented by any one of a number of DirectJK, DFJK,

matrix often allows for significant performance gains, e.g., in DF Hartree-Fock.41

SAPT0,107,108 SAPT2+3,109,110 and SAPT2+3 with a coupled-cluster doubles treatment of

Another new development is “intramolecular” SAPT (I-SAPT),115 which uses Hartree-Fock-

6.2 Density-Fitted and Cholesky Decomposition Coupled-Cluster Theory, with Frozen

We addressed this issue by using a synergistic approximation, frozen natural orbitals

6.3 Perturbation theory and coupled-cluster gradients

6.4 Optimized-Orbital Methods

In wavefunction methods, one typically uses canonical Hartree-Fock orbitals. However, it is

vibrational frequencies for systems exhibiting artifactual spatial symmetry-breaking like