Energetic Materials Frontiers 2 (2021) 292–305

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Energetic Materials Frontiers

journal homepage: www.keaipublishing.com/en/journals/energetic-materials-frontiers

A review of quantum chemical methods for treating energetic molecules

Shi-tai Guo a, b, Jian Liu b, Wen Qian b, Wei-hua Zhu a, Chao-yang Zhang b, c, *
a
School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China
b
Institute of Chemical Materials, China Academy of Engineering Physics (CAEP), Mianyang, 621999, China
c
Beijing Computational Science Research Center, Beijing, 100048, China

A R T I C L E I N F O A B S T R A C T

Keywords: As a necessary tool for understanding, prediction, and design (especially on a microscopic scale), Quantum
Quantum chemical methods chemical (QC) methods have a profound impact on the field of energetic materials (EMs). This study focuses upon
Energetic molecules the QC methods applicable to energetic molecules and their related applications. They generally include the
Density functional theory
Hartree-Fock method, semi-empirical QC methods, density functional theory (DFT), and high-accuracy ab initio
Thermodynamic property
Machine learning
methods. This study includes a detailed discussion about the application scope and accuracy of the descriptions of
the geometric structure, electronic structure, thermodynamic property, and reactivity of energetic molecules.
Additionally, this study stresses machine learning combined with DFT calculations that becomes increasingly
popular as an important way to establish models for accurate property predictions. This work is expected to be
instructive and constructive for the use of QC methods in EM study.

1. Introduction
Energetic materials (EMs) are substances that can rapidly release a
large quantity of heat and gas by self-decay and thus can be extensively
applied for both civilian and military purposes. Typically, EMs refer to
propellants, explosives, and pyrotechnics.1,2 Energetic compounds are
intrinsic for EMs since their molecular structures and molecular packing
structures can keep invariable under a wide range of pressure and tem-
perature compared with the variable structures in mixed formulations.3,4
For EMs, energy and safety are the two most important properties and
attract the most attention because energy determines the effectiveness of
the application while safety guarantees the application. Unfortunately,
they are intrinsically in conflict with each other on the molecule level,
which is the so-called energy-safety contradiction. In fact, an applied EM
has already reached a balance between energy and safety or is a conse-
quence of the contradiction compromised.5,6 As the bricks for building
EMs, various energetic molecules are generally the starting point of re-
searches.1,2 Although energetic molecules are far from the applied forms
such as materials and devices, lots of relationships based on them still
favor material design and preparation.7
As done in other fields, theoretical modeling and calculation play a
vital role in understanding, designing, and predicting EMs. With the
rapid development of computer technology and algorithms, modeling
and calculation is being increasingly important in creating new materials
as they can deal with lots of issues, such as structural prediction and
optimization, property prediction, mechanism understanding, and tech-
nique optimization. They have covered the scales of atoms/molecules,
crystals, and mixed formulations. Besides, nowadays, calculation, espe-
cially high-throughput calculation, is one of the main forces promoting
data-driven progress. Regarding the EMs that are generally full of risks
and work under high-temperature and high-pressure conditions, it is
preferred to use theoretical modeling and calculations to remedy the
shortcomings of experiments, such as the difficult detections under ex-
tremes of fast reactions, high pressure, and high temperature. Hence, the
combination of theoretical modeling, calculations, and energetic mole-
cules significantly promotes the development of EMs.
As an important division of theoretical modeling and calculation
methods, quantum chemistry (QC) methods have evolved fast, setting a
basis for a larger range of predictions with high reliability.8 They present
many dazzling choices and thus it's time to summarize these methods and
make the right ones for special cases. The applications of QC and mo-
lecular dynamics simulation (MD) methods in EMs were previously
reviewed from the aspects of thermodynamic properties, detonation
properties, decomposition mechanism, sensitivity, intermolecular in-
teractions, compatibility, solid-interface properties, and properties under
extreme conditions.9 Recently, He et al.10 reviewed the calculation
methods of key parameters of EMs (density, heat of formation, heat of
detonation, detonation velocity, detonation pressure, and impact

* Corresponding author. Institute of Chemical Materials, China Academy of Engineering Physics (CAEP), Mianyang, 621999, China.
E-mail address: chaoyangzhang@caep.cn (C.-y. Zhang).

https://doi.org/10.1016/j.enmf.2021.10.004
Received 2 September 2021; Received in revised form 24 October 2021; Accepted 27 October 2021
Available online 29 November 2021
2666-6472/© 2022 The Authors. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC BY-NC-ND
license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
S.-t. Guo et al.
Fig. 1. Objects in the molecular calculations of EMs. The gray, green, red, and blue balls represent the C, H, O, and N atoms, respectively.
sensitivity) in detail and compared the characteristics and application
scopes of these methods. Generally, the sensitivity of EMs is significantly
governed by molecular stability, including thermodynamic and kinetic
stability. Thermodynamic stability is the energy difference between a
reactant and a product. An increase in energy means thermodynamical
instability; and vice versa. Kinetic stability reflects the level of the po-
tential barrier from a reactant to a product. The higher the potential
barrier, the more kinetically stable the reactant. In this paper, the sta-
bility involved in the reactivity mainly refers to kinetic stability instead
of thermal stability. This review focuses on the QC methods that deal
with geometric and electronic structures, thermodynamic properties, and
the reactivity of energetic molecules.
Energetic molecules are generally composed of light elements, such as
C, H, O, and N, as well as halogen sometimes. On the molecular scale, the
QC methods treat isolated neutral molecules, ions, dimers, and polymers,
as illustrated in Fig. 1. There are many QC methods for dealing with
energetic molecules, such as the Hartree-Fock (HF) method, semi-
empirical methods, density functional theory (DFT), and high-level ab
initio methods. It is necessary to strike a good accuracy-cost balance when
dealing with various energetic molecules due to the usual contradiction
between high accuracy and high cost. Based on QC methods, many
microscopic properties of molecular structure can be predicted, such as
electron density, molecular orbital (MO), electrostatic potential (ESP),
heat of formation (HOF), and bond dissociation energy (BDE). Based on
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Energetic Materials Frontiers 2 (2021) 292–305
these microscopic properties and related theories, the macroscopic
properties of molecules can be deduced, such as detonation performances
and sensitivity (Fig. 2). These predicted properties can guide the design
of EMs.
To date, with the rapid development of the computer industry, high
throughput calculations have become feasible and have significantly
promoted material design.11 They are also an important part of the Ma-
terials Genome Initiative.12,13 Through high-throughput calculations, a
series of virtual materials (structures) can be constructed with predicted
properties. In this way, some materials with needed properties can be
screened out followed by further synthesis. This mode accelerates the
material evolution from discovery to application.14 As the first EMs
high-throughput computing interactive application system, EM-Studio
1.015 was successfully developed by the Institute of Chemical Mate-
rials, China Academy of Engineering Physics for the high-throughput
calculations of EMs.
After the introduction, the rest of this paper is organized as follows.
Section 2 consists of a brief introduction of main QC methods and the
evaluation of the dependence of system size and calculation cost and
accuracy. Section 3 focuses upon the applications of QC calculations in
energetic molecules. Section 4 introduces the application of machine
learning based on QC calculated data in EMs. Finally, some conclusions
are drawn. This review is expected to favor the right and efficient use of
the QC methods in energetic molecules, especially for a junior.
S.-t. Guo et al.
Fig. 2. Properties and performances derived from QC calculations. The inner
circles represent the calculated microscopic properties of molecular structure,
such as HOF, BDE, MO, ESP, and IR and NMR spectra. The outermost circle
represents macroscopic properties of molecules that can be deduced from
microscopic properties in conjunction with relevant theories, such as detonation
performance and sensitivity.
2. QC methods
QC stems from quantum mechanics. Recently, Bauer et al.16 reviewed
the algorithms of QC methods and raised some issues of chemistry and
material science, among which the core one is to solve the Schrodinger
equation to acquire the wave function of the system and all the properties
of chemical materials. As illustrated in Fig. 3a, QC methods mainly
contain four categories, namely HF method, semi-empirical methods,
DFT methods, and high-level ab initio methods, which have been
implemented using numerous software, such as Gaussian,17 VASP,18 and
Materials Studio.19
The HF method is a mean-field technique that aims to find the
dominant Slater determinant in the wave function of the system.20 This is
Fig. 3. QC methods and the relationship between cost and accuracy of each method. (a) QC methods for describing energetic molecules. (b) The dependence of system
size, computational cost, and computational accuracy of QC methods.
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achieved by optimizing the spatial form of the spin orbitals to minimize
the energy of the wave function. It is generally not used to calculate the
activation energy and bond dissociation energy, especially for systems
that are conjugated or contain lone pairs of electrons.
Semi-empirical QC methods are based on the Schrodinger equation.
They generally include CNDO,21 INDO,22 MNDO,23 a.m.1,24 p.m.3,25
p.m.6,26 and PM727 and can quickly deal with larger systems. These
methods are much faster than ab initio ones mainly because the number of
integrals is greatly reduced by making them approximate to experimental
results. AM1 and PM3 perform similarly and usually give quite good
geometries but less satisfactory HOF and other relative energies. PM6
and PM7 appear to be a major improvement over AM1 and PM3 and will
likely be the standard of general semi-empirical methods for some
years.26,27 Previous studies have shown that the PM3 method can provide
good HOF prediction for polynitrocubanes.28 Later, with the develop-
ment of methods such as PM6 and PM7, it has been found that these two
methods work much better on the HOF prediction of organic
compounds.29
High-accuracy ab initio methods consider more electron correlation,
as well as the repulsion among electrons. They commonly refer to MPn,
Gn, CI, CC, CCSD, CCSD(T), CBS, and CASSCF.30–33 These methods are
widely used to predict molecular geometries, energies, vibrational fre-
quencies, and spectra for theoretical and experimental purposes. For
example, the calculated energy difference roots for the experimental
reaction equilibria and rate, and the calculated spectroscopy plays an
important role in identifying and understanding novel molecules. In
particular, the G4 method provides accurate and economical predictions
of thermodynamics,34,35 while the CBS-QB3 method is more suitable for
the calculation of activation energy.36
DFT is an indispensable theory in modern materials and molecular
chemistry modeling. The core of the theory is the Hohenberg-Kohn
theorem,37 which shows that all ground-state properties of an atom or
a molecule are determined by electron density. Nowadays, DFT has
become one of the most popular and successful quantum mechanical
approaches since it provides a good balance between chemical accuracy
and computational cost. As one of the most popular DFT methods, the
B3LYP functional tends to be replaced by new functionals such as those of
the M06 family since the latter provides better overall average perfor-
mance,38 as exhibited in energetic molecules.39–42 However, a common
DFT method is not suitable for all systems and all property predictions. In
general, a common DFT method shows a low calculation accuracy when
dealing with covalent bonding, hydrogen bonding, and van der Waals
interactions.
S.-t. Guo et al.
Fig. 4. Applications of the QC methods in dealing with energetic molecules.
In general, higher accuracy tends to be obtained at the cost of more
time consumed and is apt to be achieved in smaller systems.43 As shown
in Fig. 3b, from semi-empirical methods to HF method, DFT methods,
and high-level ab initio methods, the calculation accuracy generally in-
creases, while the time consumption significantly increases and the size
of applicable systems reduces. Therefore, the semi-empirical methods are
usually applied to deal with the energetic polymers with low degrees of
polymerization, the HF method is adopted to analyze the composition
and energy level of MOs, and the high-level ab initio methods are
employed to predict the energy of small-size systems. In contrast, the DFT
methods are applied the most widely in systems composed of less than
1000 atoms.
3. Applications
The QC methods have been widely adopted to deal with the issues of
energetic molecules, including geometric structure, electronic structure,
thermodynamics, and reactivity, as shown in Fig. 4.
3.1. Geometric structure
By the QC methods, an energetic molecule is generally optimized to a
conformation of local minima of total energy (internal energy). In com-
parison, the subsequent accurate predictions are put forward based on
the conformation of the global energy minimum instead of local energy
minima. Therefore, searching the conformation of the global energy
minimum is required. This can be implemented by adjusting the related
dihedral angles, ordering the total energy, and confirming the
energetically-preferred conformation. A commercially available
code—the Conformers Tool kit in Materials Studio software—can be used
to conduct the conformation searching. Geometrically, a bond length is
the equilibrium distance between two nuclei in a molecule, and a bond
angle reflects the molecular spatial structure. Different methods can
present different results of these geometric parameters. For example, the
predicted bond lengths of CH3–NH2, CH3–NO2, and NH2–NO2 on two
levels of B3LYP/6-311G** and CCSD/cc-pVDZ are 0.1468 Å, 0.1503 Å,
and 0.1396 Å, and 0.1470 Å, 0.1497 Å, and 0.1405 Å, respectively.44 By
comparison, CCSD/cc-pVDZ presents a better prediction since the cor-
responding observed bond lengths are 0.1474 Å, 0.1489 Å, and 0.1477 Å,
respectively. The determination of geometric structure facilitates un-
derstanding molecular geometry and establishing the relationships be-
tween the geometries and properties.
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3.2. Electronic structure calculation of energetic molecules
QC methods can reliably describe the properties of the electronic
structure of energetic molecules, which is beneficial to understanding
energetic molecules. As shown in Fig. 5, the electronic structure mainly
includes electron density, electrostatic potential, charge, bond order,
HOMO and LUMO, and excited state.45–49
(A) Electron density. Electron density can be directly measured and
provide a wealth of information on the electronic structure of mole-
cules.45 Usually, it can be confirmed from wave function using Bader's
theory of Atoms in Molecules (AIM),50 which is very useful to under-
standing the nature of chemical bonds, reactivity, and stability of mo-
lecular systems. Higher electron density suggests more electrons located,
stronger bonding, higher molecular stability, and lower impact sensi-
tivity.51 The electron density value determines the shape and volume of
the molecule. At present, the B3LYP/6-31G** method is usually adopted
to calculate electron density. This method is more economical than MP2
and CCSD(T)52 and its accuracy outperforms the semi-empirical
methods.53 Given this, Rice et al.54 estimated the packing densities of
180 CHNO compounds derived from the volumes enclosed by the iso-
surfaces of the electronic density of 0.001 a.u. and discovered that they
were in good agreement with experimental determination. Thereby,
detonation velocity and detonation pressure can be predicted with the
K-J equation.55 Furthermore, the deformation density map can also
reflect the related nature of electron density.56
(B) ESP. ESP is a measurable and fundamental physical property of
molecules since it provides information about the charge density distri-
bution and molecular reactivity.46 Furthermore, the relations between
ESP and impact sensitivity have been proposed.57,58 Briefly, more
negative ESP assembled represents higher electron density, stronger
bonding, and lower sensitivity. Specifically, Murray's hypothesis59 allows
the impact sensitivity to be estimated according to the degree of internal
charge separation and the presence of ESP maxima on the molecular
surface. Fig. 6 shows the ESP of the six energetic molecules. In each case,
positive ESP is mostly localized in the molecular center (corresponding to
the area of benzene ring) and partly on the molecular edge (corre-
sponding to the areas of H, NH2, and CH3), while the negative ESP lies on
the molecular edge corresponding to the areas of NO2. The arrangement
of alternate positive-negative ESP facilitates increasing molecular sta-
bility according to Klap€otke's proposal.60
(C) Charge. The knowledge of charge distribution of molecules is
essential to understanding molecular chemical reactivity and
S.-t. Guo et al. Energetic Materials Frontiers 2 (2021) 292–305

Fig. 5. Electronic structures and properties of energetic molecules.

electrostatic interactions,47 which can be determined through molecular stability and further order sensitivity. A few years ago, Zhang et al.61,62
charge density analysis using either experimental or theoretical methods. presented the nitro group charge (Qnitro) method to assess impact sensi-
The charge of assigned atoms or groups (atomic/group charge) involved tivity of nitro compounds by means of BLYP/DNP-optimized geometries
in trigger linkages has been employed as an indicator to denote molecular and Mulliken charge, establishing the Qnitro - impact sensitivity

Fig. 6. ESP of the six nitrobenzene molecules at a density of 0.001 a.u. derived from the theoretical calculation on the level of B3LYP/6-31G**. The orange and blue
values indicate the maximum and minimum ESP points on each surface, respectively.

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Fig. 7. (a) High-resolution REMPI spectra of NO product from excited state decomposition of RDX. (The rotational and vibration temperatures of NO are 20 K and
1800 K, respectively). Reprinted with the permission from ref. 67. Copyright 2010 American Chemical Society. (b) R2PI spectra of the vibronic transitions of the NO
product from the excited electronic state decomposition of DNP. The black line is the experimental data and the red one is the theoretical simulation for NO transition
at the rotational temperature of 25 K. Reprinted with the permission from ref. 68. Copyright 2014 American Institute of Physics. (c) HOMO and LUMO level evolution
of NM. (d) and (e) HOMO, LUMO, and the evolution of nearby energy levels of RDX. (f) HOMO and LUMO level evolution of TATB. The green and red solid lines
represent the highest occupied orbital and lowest unoccupied orbital, respectively, corresponding to the energy level of the excited hole and excited electron. The gray
solid line represents other nearby energy levels. Reprinted with the permission from ref. 69. Copyright 2021 Chinese Physical Society.

correlation as follows: the more negative the Qnitro, the more decreased
the electron-attraction ability and the less the impact sensitivity. Simi-
larly, the charge of N3 groups (QN3) can also be used to grade the impact
sensitivity for a group of azides.
(D) MO. The highest occupied molecular orbital (HOMO) and the
lowest unoccupied molecular orbital (LUMO) are the key orbitals in a
molecular as frontier MOs. They mean the abilities to denote and accept
electrons, respectively, and their difference (ΔELUMO-HOMO) is the energy
gap. They serve as important parameters showing the chemical reactivity
and kinetic stability of a molecular.48,49 Generally, the higher the
ΔELUMO-HOMO, the more difficult the electron excitation and the higher
the insensitivity against photic stimulation.63,64 For example, the
ΔELUMO-HOMO of RDX and HMX molecules are 5.634 eV and 5.304 eV,
respectively, suggesting high photic insensitivity. In addition, bond order
(BO) and conjugation determined by MO can also be related to sensi-
tivity. For example, Xiao et al. employed BO to correlate with impact
sensitivity of energetic molecules grouped since higher BO corresponds
to lower impact sensitivity.65
(E) Excited state. The high temperature generated by the decom-
position of energetic materials will lead to the occurrence of excited-state
reactions, which even occupy a dominant position. Some new experi-
mental phenomena have been revealed as excited-state reaction pro-
cesses. For example, NO is the only small-molecule product observed in
RDX excited by 226–258 nm photons.66 The REMPI spectrum of the NO

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Fig. 8. HOF prediction using various QC methods. (a) Methods for calculating HOF. (b) The HOF and nitro derivatives of methane calculated using semiempirical QC
methods and comparison with experimental data. Reprinted with the permission from ref. 74. Copyright 2007 American Chemical Society. (c) Calculation of the HOFs
of 1,2,4,5-tetrazine derivatives by different QC methods. (d) RMS and MAD of calculated HOF at various levels. (e) MUE, MSE, and maximum absolute deviations (|Φ
max|) for individual compound methods, and combinations thereof, upon comparison with the ATcT. Reprinted with the permission from ref. 79. Copyright 2015
American Chemical Society.

produced was calculated at the CASSCF(12,8)/6-31G* level, yielding the
rotation and vibration temperatures of 20 and 1800 K, respectively
(Fig. 7a).67 The excited RDX is rapidly transformed into the ground state
through the intersection of the potential energy surface and decomposes
along a ground state potential energy surface. HMX and CL-20 also have
excited decomposition processes similar to RDX. In addition，Fig. 7b
shows the spectra of three different rovibronic transitions of the NO
molecule generated from the ground state to the first excited electronic
state of DNP on the CASSCF(12,8)/6-31þG* level. All spectra have
similar rotational patterns but different vibrational intensity of each
vibronic band.68 Recently, Zhao et al. used time-dependent DFT and
molecular dynamics methods to study the optically excited dissociation
process of NM, RDX, and TATB molecules.69 The evolution of the orbital
energy levels of three energetic molecules over time after light excitation
are shown in Fig. 7c–f. It can be found that the increase in the initial
temperature broadened the molecular energy level and changed the
position of the energy level to different degrees. As time proceeded, the
excited electron energy level continued to decrease and the excited hole
energy level continued to rise, which was accompanied by oscillations of
different frequencies. In addition, the energy level near the excited
electron in the RDX molecule exhibited an upward trend, while the en-
ergy level near the excited hole showed a downward trend. In short, the
study on the excited state of energetic molecules can provide an effective
theoretical means for certainly revealing the detonation process.
In general, these parameters can reflect the reactivity and stability of
molecules to a certain extent, but they differ. For example, ESP is a
property that can be evaluated by measurement or quantum mechanical
theory and is typically used to analyze the electron density distribution in
a molecule. The charge is mainly analyzed from the perspective of atom/
functional groups (such as Qnitro and QN3) to reflect the attraction of
electrons. Specifically, the more negative the charge, the more stable the
molecules. The energy gap represents the ability of electrons to transit
from the occupied orbital to a vacant orbital. These parameters are of
great significance for the analysis of the electronic structure and prop-
erties of molecules.
3.3. Thermodynamic properties
(A) HOF. HOF is fundamental to calculating reaction heat, and thus
the accurate prediction of HOF is crucial to obtaining reliable thermo-
dynamic indexes of an energetic compound. In principle, the HOF of an
energetic molecule can be exactly predicted. However, this is only
practical to a small number of small molecules. Based on QC calculations,
the HOF of energetic molecules can be achieved using three schemes:
atomization,70 atomic equivalent,71 and isodesmic reaction72 (Fig. 8a).
As for the atomization scheme, the HOF is predicted based on the at-
omization reaction heat and the known HOF of isolated atoms. The
atomic equivalent scheme is intrinsically similar to the atomization
scheme, with only a difference in the concept of equivalent. The pre-
diction accuracy of the atomization scheme and the atomic equivalent
scheme is significantly dependent on the accuracy of QC methods used.
In comparison, the isodesmic reaction scheme is much less dependent on
the QC methods. This method presents the HOF of a target molecule as
the accurate HOF of the references according to Hess's law.73 In an iso-
desmic reaction, the numbers of electron pairs and chemical bonds are
conserved, and the molecular skeleton and small substitutes keep un-
changed to reduce the impacts of the systemic errors induced in QC
calculations.

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Fig. 9. Comparison of ΔEint of various stacking modes. Reprinted with the permission from ref. 82. Copyright 2019 Royal Society of Chemistry.
It has been clarified that the prediction accuracy of HOF significantly
depends on the aforementioned schemes and QC methods. Fig. 8b com-
pares the calculated the HOF and nitro derivatives of methane using
three semi-empirical methods with experimentally determined results
and shows that PM3 yields the highest accuracy, followed by AM1 and
MNDO.74 Therefore, PM3 can be recommended for larger systems in the
case that both DFT and high-level ab initio methods are infeasible. The
calculated HOF of 1,2,4,5-tetrazine derivatives75 using various QC
methods was compared with experimentally determined results, as
shown in Fig. 8c. This confirms the highest reliability of the two DFT
methods (B3LYP/6-311G** and B3P86/6-311G**) and the
MP2/6-311G** method. The HF method shows no confirmed advantage
in terms of calculation accuracy, and it even presents less accurate pre-
dictions compared with the semi-empirical methods. According to the
testing results of the root mean square errors (RMSs) and mean absolute
errors (MAD) of HOF calculated using various DFT methods (6-311þG**
basis set) relative to the benchmark results of G4 calculation,76 the
hybrid meta-generalized gradient approximation (meta-GGA) shows the
highest accuracy, followed by hybrid GGA and common GGA methods
(Fig. 8d). Similarly, the HOF of 38 molecules were studied using some
composite methods and combinations of composite methods and the
results were compared with the recommended values of Active Ther-
mochemical Tables (ATcT),77,78 as shown in Fig. 8e. Based on the
comparative analysis of mean unsigned errors (MUEs) and mean signed
errors (MSEs), the accuracy of the five methods is in the order of G4 > G3
> W1BD > CBS-APNO > CBS-QB3.79 The deviation can be improved to
some extent by the combined methods, which requires a certain calcu-
lation cost, however. Therefore, G4 and G3 methods should be preferred
for the selection of composite methods.
(B) Intermolecular interaction energy. Extending individual mol-
ecules to molecular stacking involving multiple molecules is the devel-
opment tendency of the molecular design of EMs since the prediction
results it presents are much closer to practical materials. Therein, inter-
molecular interactions are the core. As the simplest prototype, dimer-
ization energy is usually employed to understand molecular stacking and
construct molecular force field.80 For example, the dimer interactions of
FOX-7 verified that the intralayered interactions in crystal packing
belong to hydrogen bonding (HB), while the interlayered ones belong to
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weak van der Waals forces.42 Similar case also occurs in NTO.81 The
results show that the intermolecular interactions govern the molecular
arrangement in crystal.
Recently, a series of dimers was created by taking some optimized
monomers as rigid bodies to describe the relative positions between the
two monomers involved in each dimer.82 The stacking pattern of dimers
can be divided into coplanar, parallel, V- or T-shaped, and crossing
modes, and four energetic analogs, namely TATB, TNB, DATB, and TNA,
were adopted as the monomers. To determine the energetically preferred
one, the maximum interaction energy (ΔEint) of each monomer in each
stacking mode was calculated at the level of PBE0/6-311þG** þD3 for
comparison. As shown in Fig. 9, the parallel stacking mode is the most
energetically favorable for all four types of dimers, followed by the
T-shaped, coplanar, and crossing stacking modes. Thus, it is supposed
that the parallel stacking mode dominates the molecular stacking. This
result agrees with experimental observations. Since the ΔEint in the
parallel stacking mode is controlled by dispersion, whose strength is
positively correlated with molecular size, the ΔEint increases as molecular
size increases, i.e., in the order of TNB ＜ TNA ＜ DATB ＜ TATB.
(C) Vibration absorption spectrum. Infrared and Raman spectros-
copies are important tools for characterizing chemical bonds and func-
tional groups and facilitate understanding various vibration modes of
energetic molecules and other microscopic mechanisms.83,84 QC calcu-
lations have been widely adopted to assist in spectral analysis.85
Recently, the spectroscopic properties of DATB have been studied,86 and
the dynamic stability under environmental conditions has been
confirmed.87 As shown in Fig. 10a and b, the low-frequency region
mainly belongs to the lattice vibration of nitro groups, while the
high-frequency vibration is attributable to amino groups, with peaks
associated with various functional groups. Compared with experimental
observations, it can be found that there are 22 and 20 peaks in the
measured region of Raman spectra and infrared spectra, respectively.
Compared with the experimental results,88 the main difference exists due
to the poor description of the asymmetric stretching of functional groups.
Similarly, two vibrational spectra of TNT were explored with the aid of
the DFT calculations (Fig. 10c), for which the basis set was 6-311þG**.
The results yielded by the O3LYP method were much closer to experi-
mental results.89 This shows that the spectral characteristics of energetic
S.-t. Guo et al. Energetic Materials Frontiers 2 (2021) 292–305

Fig. 10. Spectra of some energetic molecules. The calculated infrared (a) and Raman (b) spectra of DATB. Reprinted with the permission from ref. 86. Copyright 2019
Springer. (c) Comparison of the calculated and experimental Raman spectra of TNT. Reprinted with the permission from ref. 89. Copyright 2017 Elsevier.

molecules can be obtained by using suitable QC methods as an important
tool to assign spectra.
3.4. Reactivity
(A) BDE. Acceptable stability or sensitivity is necessary for guaran-
teeing the safety of the lifetime of EMs. BDE is a basic indicator showing
molecular stability. A small BDE indicates a weak trigger bond, low
molecular stability, and high reactivity.90 NO2 is usually the readiest
breaking group in energetic nitro molecules. That is, the –NO2 group is
usually linked by the weakest bond in an entire nitro molecule. There-
fore, the strength of the weakest bond plays a very important role in
determining the stability and sensitivity of EMs.91
DFT methods with high efficiency and high accuracy are generally
employed to predict BDE. For example, as shown in Fig. 11a, the BDE of
R–N3/NH2/NO2 molecules (R ¼ methyl, phenyl, and trinitromethyl) was
evaluated using several DFT methods, for which the basis set was all 6-
31þG*. As a result, the M06 functionals presented the highest accuracy,
followed by MPWB1K, BB1K, B3P86, and other functionals.92 Also, the
accuracy was ascertained by comparing predicted results with experi-
mental results.93–95 For some given energetic molecules, the B3P86
functional presented the prediction results that were the closest to the
experimental determination (Fig. 11b). According to these combined
with the higher accuracy of B3P86 (Fig. 11a), B3P86 can be deduced as
the preferred functional for BDE predictions.
(B) Energy barrier. Transition state (TS) is the structure corre-
sponding to a point with a local maximum on a potential energy surface
and connects reactants and products. The potential energy difference
between the reactant and the TS is defined as the reaction barrier, which
is an important factor governing reaction kinetic. Hydrogen-transfer (HT)
reactions have received much attention in the field of EMs. For example,
the HT in heated LLM-105 and TKX-50 (Fig. 12a), as well as other
possible initial steps, were explored by means of MD simulations.96,97
Regarding LLM-105, the energy barriers of the four possible initial steps
were separately calculated on the level of B3LYP/6–311þþG**, and it
was found that the intramolecular HT was the most energetically favor-
able (Fig. 12b) due to the highest reaction frequency observed in the MD
simulations. It shows that the HT initiated the LLM-105 decay. Mean-
while, a detailed intrinsic reaction coordinate (IRC) search of the HT in
LLM-105 (Fig. 12c) confirmed two steps involved and a shallow barrier of
2.1 kJ mol1 required to return from the hydrogen transferred product to
the original molecule, indicating the high reversibility of HT. This
reversible HT is thought to contribute to the low mechanical sensitivity of
LLM-105 as a new mechanism.96

Fig. 11. Comparison of the accuracy of various DFT methods. (a) Mean unsigned errors (MUEs) of the 13 DFT functionals for calculating the BDE of C–N. (b)
Calculated and experimental BDE of several energetic molecules.

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Fig. 12. Energy barriers for some reactions. (a) Molecular structures of LLM-105 and TKX-50. (b) Energy barriers for the four initial steps of the LLM-105 decom-
position. (c) Potential energy surface of the HT of heated LLM-105. Reprinted with the permission from ref. 96. Copyright 2018 American Chemical Society. (d)
Potential energy surface of NH3OHþþ Hþ → NH3OH2þ þ þ
2 → NH3 þ H2O , and bond lengths (in blue) and atomic NBO charge (in red) of all species. Reprinted with the
permission from ref. 97. Copyright 2017 American Chemical Society. (e) and (f) Comparison in energy between NO2 partition and intramolecular HT for impact-
insensitive energetic molecules and sensitive molecules, respectively. Reprinted with the permission from ref. 99. Copyright 2019 Royal Society of Chemistry.

Another case is the intermolecular HT in heated TKX-50. Unlike the
neutral H transferred in HMX,98 that in TKX-50 is proton (Fig. 12d).97 It
was found that the proton transferred products of NHþ þ
3 and H2O are
1
much energetically allowed, with a heat release of 543.5 kJ mol and a
very shallow barrier (9.2 kJ mol1) required to overcome. Besides, cur-
rent systematic work showed that strong intramolecular HBs are bene-
ficial to intramolecular HT when heating. For instance, an intramolecular
HT occurs more likely with a lower energy barrier compared with an NO2
partition in intramolecular HB-containing molecules (Fig. 12e). In
contrast, it is difficult for an intramolecular HT to occur in those without
the intramolecular HBs, and the NO2 partition govern the primary steps
of decomposition (Fig. 12f).99
(C) Synthesis mechanism. Revealing synthesis mechanisms facili-
tates designing more suitable techniques used to efficiently prepare new
energetic molecules. Recently, pentazole and 1,2,3-triazole rings have
received increasing attention for their potential as EMs.100–103 The
cyclo-N5 has been successfully isolated from the 3,5-dimethyl-4-oxido-
phenylentazole (OPP) anion with ferrous bisglycinate ([Fe(Gly)2]) and
m-chloroperben-zonic acid (m-CPBA), with a low yield.104 Thereafter, Liu
et al. proposed a solution to increase the yield of cyclo-N5 by analyzing
the complete reaction pathways of arylpentazene conformers and a series
of substituted derivatives,105 and explored the reaction mechanisms, and
the details are as follows.106 According to the comparison between Hu
and Lu's proposals, iron (IV)-oxo is more efficient and is able to proceed
at room temperature. The reactivity of the Fe– – O moiety can be tuned
through ligand binding, and thus other heme or nonheme iron (IV)-oxo
complexes may also be effective for the C–N bond activation of aryl-
pentazole. In addition, Sakai reaction is an important approach to syn-
thesizing 1,2,3-triazole by adding α, α-dichlorotosylhydrazones and
amines.107 The reactivity of α,α-dichlorotosylhydrazones with various
amines may undergo different pathways in the process of ring formation,
which was confirmed by the B3LYP-D3/6-31G* calculations.108
3.5. Application of machine learning based on QC calculations
Over the past decade, machine learning (ML) has been rapidly
developed and extensively used in materials discovery.109–112 Compared
with traditional calculation methods, ML is data-driven and can easily
handle complex datasets and thus can provide accurate predictions and
facilitate deciphering new knowledge. Moreover, it plays a significant

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Fig. 13. Comparison between ML predicted and DFT calculated results. (a)–(d) Aiming to predict the BDE of organic carbonyls: predictions by (a) neural network
(NN) and (b) random forest (RF) based on bond lengths and angles, and by (c) NN and (d) RF based on Coulomb forces. Reprinted with the permission from ref. 119.
Copyright 2020 American Chemical Society. Total energy (e) and energy gap (f) for various energetic molecules predicted by CNN calculations based on electron
density. Reprinted with the permission from ref. 120. Copyright 2020 American Chemical Society.
role in predicting the structure and properties of EMs.113,114 Till date,
there are many ML methods, such as neural network (NN), random forest
(RF) methods, k-nearest neighbor, support vector machine, naive bayes,
convolutional neural networks (CNN), and extreme gradient
boosting.115–117 ML methods can be used to study energetic molecules.
Therefore, the related properties such as BDE, orbital energy, detonation
properties, and sensitivity can be evaluated by selecting different de-
scriptors including molecular skeletons, oxygen balance, molecular
weight, pack coefficient, density, types and numbers of HB, space group,
and types and numbers of functional groups and gas products. Based on
the ML methods, Huang et al.118 investigated the detonation properties of
high-energy-density materials in detail using different descriptors and
provided the optimal range of key characteristics and a basis for the
design of new energetic materials.
Fig. 13 a-d compares the NN and RF fitted BDE of organic carbonyls
with those calculated using the B3LYP-D3/6-31G** method,119 in which
molecular geometric parameters such as bond length and bond angle
(LA) and Coulomb force (CF) are selected as feature descriptors to predict
BDE. As for the comparison results, the Pearson correlation coefficient (r)
between the DFT-calculated values and the NN (NN_LA) fitted values of
the test set is 0.932, with a mean relative error (MRE) of 1.62% (50.96 kJ
mol1) (Fig. 13a). The comparable metrics (r ¼ 0.931, MRE ¼ 1.62%)
obtained using the RF (RF_LA) method are nearly identical to those
determined using the NN method. Similarly, the Pearson correlation
coefficients between DFT-calculated values and those fitted by either the
NN (NN_CF) and RF (RF_CF) methods over the test set are 0.933 and
0.931 (Fig. 13c and d), respectively, with MREs of 1.68% (53.22 kJ
mol1) and 1.57% (49.20 kJ mol1), respectively. The results show that
the BDE can be effectively and accurately predicted by means of ML. In
addition, ML can provide guidance for studying the BDE of other mole-
cules and evaluating molecular stability and can be applied to the study
of total energy and orbital energy. Fig. 13e and f shows the comparison
between CNN fitted and B3LYP/6-31G** predicted total energy and
energy gap between the frontier orbitals, respectively, with R2 of up to
0.981.120 All these show the feasibility of ML in dealing with energetic
molecules.
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Energetic Materials Frontiers 2 (2021) 292–305
Overall, QC methods are suitable to determine the geometric struc-
ture, electronic structure, thermodynamic properties, and reactivity of an
energetic molecule. Generally, a more accurate method can provide more
satisfying prediction results. Nevertheless, much attention should be paid
to the trade-off between efficiency and cost. For special groups of ener-
getic molecules, different QC methods are still required for different
calculation objects. For example, the B3LYP method is adequate in
dealing with the symmetric and electronic structures, the M05-2X, M06-
2X, and other high-level methods are suitable to predict thermodynamic
properties, while the B3P86 functional is generally good at predicting
BDE. In machine learning, the related properties of energetic molecules
can be elevated using different descriptors, thus speeding up the design of
energetic molecules.
4. Conclusions
The study summarizes the QC methods that can be used to describe
energetic molecules and the selection of these methods for specific pur-
poses. Generally, higher prediction accuracy requires more calculation
cost and is more suitable for smaller systems. In addition, this study
discusses the applications of the QC methods in the geometric structure,
electronic structure, thermodynamic properties, and reactivity of ener-
getic molecules in detail. Therefore, this study will provide guidance on
selecting suitable methods for given purposes. Besides, it has been
confirmed that ML combined with DFT calculations is a feasible method
for energetic molecules and it could serve as the main trend for molecular
prediction.
Declaration of interests
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
S.-t. Guo et al. Energetic Materials Frontiers 2 (2021) 292–305

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Energetic Materials Frontiers 2 (2021) 292–305
Shitai Guo received his Master degree from Wuhan University
of Science and Technology in 2020. Currently, he is pursuing his
Ph.D. degree in Nanjing University of Science and Technology
and is receiving dual culture at the Institute of Chemical Ma-
terials, China Academy of Engineering Physics (CAEP). His
research interest is computational energetic materials. Email: 22
81763751@qq.com.
Chaoyang Zhang is a professor and a Ph.D. supervisor at the
Institute of Chemical Materials, CAEP. He received his Ph.D.
degree of physical chemistry from Fudan University. Now, he is
a member of Combustion Chemistry Division of Chinese
Chemical Society (CCS), a member of Materials & Devices under
Extremes Division of Chinese Materials Research Society
(CMRS), and a member of Scholar Committee of State Labora-
tory of Explosives & Combustion. Currently, he is part-time
professor of Beijing Computation Science Research Center,
University of Science and Technology of China, Chongqing
University, and Southwest University of Science and Technol-
ogy. He has published more than 100 papers on JACS, JPC,
PCCP, CGD, CEC, and JCC. He was awarded Yu-Min Mathe-
matical Prize and Deng-Jiaxian Youth Science and Technology
Prize for his scientific research on energetic materials. Email: ch
aoyangzhang@caep.cn.