Forensic Chemistry 2 (2016) 2228

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Forensic Chemistry
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Full length articles

Visible and UV resonance Raman spectroscopy of the peroxide-based

explosive HMTD and its photoproducts
Brian S. Leigh , Keith L. Monson 1, Judy E. Kim
Department of Chemistry and Biochemistry, University of California at San Diego, 9500 Gilman Drive, La Jolla, CA 92093, United States

a r t i c l e

i n f o

Article history:
Received 8 June 2016
Received in revised form 25 July 2016
Accepted 11 August 2016
Available online 21 August 2016
Keywords:
Raman
Peroxide explosives
Vibrational spectroscopy
Photodegradation

a b s t r a c t
Hexamethylene triperoxide diamine (HMTD) is a peroxide-based explosive that is easily manufactured
from household chemicals. This high-energy molecule is challenging to detect because it lacks the characteristic NO2 functional group that is the primary target of modern detection devices. One tool that is
well-suited for detection and characterization of HMTD and other peroxide explosives is Raman spectroscopy. Off-resonance Raman spectra with 514.5 nm excitation of HMTD and its 13C and 15N isotopologues are presented here. These experimental results are compared to calculations to reveal the
vibrational structure and normal mode assignments of this strained molecule. Intense peaks that reflect
global torsional motion appear in the low-frequency region (<700 cm
1), and the dominant peroxide OO
stretch appears at 773 cm
1. UV resonance Raman (UVRR) spectra with 228 nm excitation show signatures of the photodegradation products of HMTD. These photoproducts, including those of the isotopologues, are identified via mass spectrometry and vibrational analysis. We hypothesize that upon
absorption of UV light, one or more OO bond is cleaved, resulting in the release of formaldehyde and
O2. Subsequent reactions create an imide product that has a strong band in the UVRR spectrum centered
at 1736 cm
1. These results highlight the benefits of off- and on-resonance Raman spectroscopy as detection tools for HMTD and its photoproducts.
Published by Elsevier B.V.

1. Introduction
The detection of explosives is an ongoing priority and challenge
for national security. The most common method of detection in
civilian areas is ion mobility spectrometry in which a swab of the
unknown sample is collected, the chemical constituents are vaporized, ionized, and separated based on their mobility in the gas
phase [1,2]. This technique is coupled to mass spectrometry, and
an NO2 signature alerts to the possible presence of explosives.
Common nitro-based explosives can be detected relatively easily
whereas peroxide-based molecules are more challenging because
these materials decompose to form products such as CO2, CO,
and HCN that are not associated with common explosives [3].
Additionally, successful detection of HMTD may require complexation with inorganic partners (e.g. Cl
), or use of advanced instru-

Corresponding authors at: Defense Forensic Science Center, Forest Park, GA

30297, United States (B.S. Leigh); University of California at San Diego, United States
(J.E. Kim).
E-mail addresses: bleigh@ucsd.edu (B.S. Leigh), judyk@ucsd.edu (J.E. Kim).
1
Counterterrorism and Forensic Science Research Unit, FBI Academy, 2501
Investigation Parkway, Quantico, VA 22135, United States.
http://dx.doi.org/10.1016/j.forc.2016.08.002
2468-1709/Published by Elsevier B.V.

mentation that may not be easily accessible [2]. For these and
other reasons, peroxide explosives can be challenging to detect in
a commercial setting.
HMTD, or hexamethylene triperoxide diamine, is of particular
interest. This explosive can be made with household chemicals,
and untrained civilians have prepared and illegally stored large
quantities of it [4]. HMTD is a high-energy molecule comprised
of three peroxide moieties. It has the explosive power of 60% TNT
(trinitrotoluene), and is a primary explosive [5]. The structure is
highly strained, with both nitrogen atoms in a trigonal planar
structure (Fig. 1 inset) [6,7], and is found in enantiomeric conformers [8]. The detonation of HMTD may not be driven as strongly by
an enthalpic driving force as other high explosives and instead,
there may be a significant entropic component that has been calculated for another tri-peroxide explosive triacetone triperoxide
(TATP) [9].
One technique that offers advantages for detection of HMTD
and other peroxide explosives is Raman spectroscopy. This vibrational method provides molecular fingerprints because it inherently reports on bond connectivity and structure [10].
Additionally, Raman spectroscopy has been utilized in the field
for stand-off detection because it is a scattering technique [1,11].

B.S. Leigh et al. / Forensic Chemistry 2 (2016) 2228

23

15
N-HMTD was synthesized and confirmed following the same steps as for HMTD
and 13C-HMTD, but 2.5 mL of 6N 98%-enriched 15N ammonium hydroxide
(SigmaAldrich) was used [17].

2.2. Spectroscopy and calculations

Fig. 1. Absorption spectrum of HMTD. Molar absorptivity data from reference [24].
Insets show molecular connectivity (left), and minimized structure from DFT
calculation (right).

Variations of Raman spectroscopy have been applied to common

explosives, such as near-infrared excitation and surface-enhanced
Raman spectroscopy [1015]. One method that to our knowledge
has not been utilized for peroxide explosives, but offers excellent
advantages, is UV resonance Raman spectroscopy (UVRR). With
UV excitation, the scattering is more efficient because of the m4
dependence, and resonance enhancement is expected for the peroxides. UV excitation also avoids molecular fluorescence, and
allows Raman spectroscopy to be performed in ambient light
[16]. However, because UV light is absorbed by the explosive, there
is a possibility of a photochemical reaction upon photon absorption. Here, we present a UVRR and off-resonance Raman analysis
of HMTD to determine the vibrational signatures of this explosive
as well as its UV photoproducts. By coupling the Raman experiments with mass spectrometry and calculations, we are able to
propose a photodegradation pathway.
2. Materials and methods
2.1. Sample preparation
Synthesis of 3,4,8,9,12,13-hexaoxa-1,6-diazabicyclo[4.4.4]tetradecane (often
referred to as hexamethylene triperoxide diamine, HMTD) was performed on a
small scale, and with minor modifications of a published protocol [7,8,17]. Briefly,
0.46 g of hexamethylenetetramine (Alfa Aesar, Ward Hill MA) was placed in a
5 mL beaker. 2.21 mL of cold 30% hydrogen peroxide (Fisher Scientific, Pittsburgh
PA) was added to the beaker while stirring. The beaker was then placed on ice
and continually stirred while 0.65 g of anhydrous citric acid (Fisher Scientific)
was added over 10 min. The solution was stirred on ice for 3 h. The solution was
covered, left at room temperature without stirring, and a white slurry formed overnight. White crystals were collected by vacuum filtration, and washed with deionized Milli-Q water (18.2 MO cm) and dry methanol. The sample was dried for 12 h
in a vacuum desiccator. The NMR, Raman, and mass spectra of the white powder
matched those reported previously [10,1820]. Isotopically-labeled 13C-HMTD
was synthesized with isotopically enriched hexamethylenetetramine that was prepared as described by Oxley and coworkers [17]. Briefly, 0.5 g of 99% 13C
paraformaldehyde (SigmaAldrich, St. Louis MO) and 0.6 mL of Milli-Q water were
placed in a scintillation vial with a stir bar. The headspace was purged with nitrogen
gas as the vial was brought to 75 C, and held at this temperature until the solution
was clear. This heating process converted the paraformaldehyde into formaldehyde.
The solution was then cooled to 45 C and 2.5 mL of 28% ammonium hydroxide
(SigmaAldrich) was added drop-wise followed by 1 mL of Milli-Q water. The temperature of the solution was increased to 80 C over two hours, and then allowed to
cool. The resulting white slurry was dried via rotary evaporation using three 10 mL
anhydrous methanol (SigmaAldrich) washes. The isolated white powder was used
as the starting material in the reaction with hydrogen peroxide and citric acid to
form 13C-HMTD. The compound was analyzed via Raman spectroscopy and mass
analysis, and was confirmed to be fully 13C substituted. The isotopologue

Mass spectra were collected with a Thermo Finnigan MAT 900XL Magnetic
Sector Mass Spectrometer. Samples were analyzed using electron impact and direct
sample injection. HMTD samples were dissolved in acetonitrile (SigmaAldrich) at a
concentration of 1 mg/mL, and further diluted 10 with acetonitrile prior to injection. Dissolution of the HMTD in acetonitrile was accomplished more efficiently
(in seconds) by bath sonication, rather than by mechanical stirring (minutes), and
neither method was found to degrade the sample.
Visible Raman spectra were collected with a home-built Raman microscope system that has been described previously [21]. The excitation source was a Coherent
Innova 70C Ar+/Kr+ laser. The 514.5 nm beam was steered into a side-port of a Zeiss
upright microscope (Axio Imager.A1m) that was fitted with beamsplitters to direct
the excitation to a 50 objective. At the sample, the diameter of the laser spot was
approximately 1 lm, and the incident power was 1 mW for all experiments. Scattered light was directed into a Horiba iHR320 spectrograph equipped with a
1200 groove/mm holographic grating blazed at 500 nm. The entrance slit width
was 50 lm, corresponding to a spectral bandpass of 4 cm
1. The dispersed light
was imaged onto a CCD (JY Horiba Synapse). A narrow-band notch filter (Ondax
SureBlock) or edge filter (Semrock) were used to reject Rayleigh scattering; the
Ondax filter allowed collection of low frequency and simultaneous Stokes/antiStokes spectra. Each spectrum represents an accumulation time of 5 min. Raman
shifts were determined using ethanol and 1:1 acetonitrile:toluene as calibration
standards, and the accuracy was 1 cm
1 in the low- and intermediate-frequency
window, and 2 cm
1 in the high-frequency window.
The ultraviolet resonance Raman (UVRR) system has been described previously
[22]. Briefly, the 1 W red output from a 1 kHz Photonics Industries Ti:Sapphire
laser was frequency-doubled in a crystal of lithium triborate (LBO), and the resulting near-UV output was doubled in b-barium borate (BBO) to obtain the 228 nm
excitation wavelength. The UV beam was focused onto the sample. HMTD was
loaded in a spinning cell to minimize sample degradation. The power incident on
the sample ranged from 40 lW to 1 mW, and the spot size was approximately
230  75 lm. The back-scattered photons were collected with a UV achromatic
lens, focused into a prism prefilter with a slit opening of 110 lm (11 cm
1 bandpass), dispersed with a Spex 500M spectrograph, and imaged onto a Princeton
Instruments Pixis CCD. Each UVRR spectrum represents an accumulation time of
15-min unless noted otherwise. Raman shifts were determined using ethanol and
a 1:1 acetonitrile:toluene solution as calibration standards, and accurate to within
2 cm
1. All Raman spectra were analyzed using Igor Pro (Wavemetrics, Lake
Oswego OR).
UV photolysis experiments were performed using the 228 nm laser line from
the UVRR system. The 1 mW beam was defocused to fully illuminate the
5  1 cm cross-sectional area of a spectrosil cuvette (NSG Precision Cells, Farmingdale NY) that was filled with a 1 mg/mL solution of HMTD in acetonitrile. Samples
were irradiated from one second up to one hour with constant stirring.
Calculations were performed with Gaussian 09. Different DFT exchangecorrelation functionals (B3LYP, BLYP, M06-2x,) were tried with a variety of basis sets
(6-311G and cc-pVDZ). The match to the experimental frequencies of the three isotopologues was obtained using B3LYP in combination with the cc-pVDZ basis set, as
described below. No scaling factor was applied. The calculated normal modes were
analyzed with Vibalizer [23]. Matching vibrations among the set of isotopologues
were identified based on the similarity of the displacements; for a given vibration,
the similarity score was 95% or better for the three isotopologues. The isotope shift
for each normal mode, defined as the difference in frequency between isotopicallylabeled HMTD and unlabeled HMTD (e.g. m(13C HMTD) m(HMTD)), was tabulated.
The calculated Raman vibrational frequencies and isotopic shifts were compared
with values from the experimental spectra, and bands were assigned. Table S1 in
Supporting information lists the isotope shifts, as well as the difference between
calculated and experimental isotope shifts.

3. Results
The absorption spectrum of HMTD (Fig. 1) matches that of a
recent report [24]. Visible Raman spectra of HMTD and its 15N
and 13C isotopologues are displayed in Fig. 2 (low frequency),
Fig. 3 (intermediate frequency), and Fig. 4 (high frequency). These
off-resonance Raman spectra show shifts in peak positions that
reflect the isotopic substitution. The full Raman spectral window
of 1003200 cm
1, low-frequency (50 cm
1) and anti-Stokes data,
and unnormalized Raman spectra (with estimate of number of
Raman photons) are included in Supporting information. Calculated and experimental spectra are also compared in Supporting
information.

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B.S. Leigh et al. / Forensic Chemistry 2 (2016) 2228

Fig. 2. Low-frequency region of Raman spectra of HMTD and isotopologues with

514.5 nm excitation. Spectra are normalized to the most intense peak at
169 cm
1, and offset for clarity.

Fig. 3. Intermediate-frequency region of Raman spectra of HMTD and isotopologues with 514.5 nm excitation. Spectra are normalized to the most intense peak at
773 cm
1, and offset for clarity.

The results from UV resonance Raman experiments are shown

in Figs. 5 and 6. Despite the use of a spinning cell, even the lowest
UV power (40 lW) yielded spectra that were largely those of photoproducts, rather than HMTD. At early times in the Raman acquisition, one band of HMTD is apparent at 773 cm
1. However, the
band diminishes with successive accumulations, and other bands
dominate after five minutes (Fig. 5). The signatures of the photoproducts for the three isotopologues are shown in Fig. 6.
The photolysis products were investigated by mass analysis.
Unphotolyzed HMTD and its 13C and 15N isotopologues produced
the mass fragmentation patterns shown in Fig. 7 (panels A, B,
and C). In addition to the parent peak above 200 m/z, seven other
fragments are apparent for each isotopologue. Upon photolysis
with 228 nm light, one of the fragment peaks near 73 m/z grows
in intensity, and additional peaks appear in the mass spectra:
114 and 146 m/z for HMTD; 116 and 148 m/z for 15N-HMTD; 119
and 151 for 13C-HMTD (Fig. 7, panels DF). The new bands were

Fig. 4. High-frequency region of Raman spectra of HMTD and isotopologues with

514.5 nm excitation. Experimental spectra (red, blue, green curves) are normalized
for equal amplitude of the 2930 cm
1 band, and offset for clarity. The spectra were
fitted with Lorentzian functions (solid black curves). The dashed black curves are
the sum of the Lorentzian fits.

Fig. 5. UVRR (228 nm excitation, 40 lW) spectra of HMTD and its photoproducts
collected in 1-min intervals over a cumulative exposure time of 5 min. The
indicated times reflect the Raman spectrum up to the first minute (1 min), up to
second minute (2 min), etc.

not apparent after 5 s of photolysis, were small after 30 min, and

significant after 1 h.
Calculations were pursued at different levels. Of the several
methods that were tried, a cc-pVDZ basis set combined with
B3LYP functional gave the best agreement between theory and
experiment.
4. Discussion
Raman spectroscopy is a powerful method for stand-off forensic
analysis of peroxide explosives. Here, we present a vibrational
analysis of HMTD. The combination of isotopic substitution and
normal mode analysis reveals the vibrational structure of HMTD,
and helps identify its photoproducts. The identification of photodegradation products of HMTD is important for the possible

B.S. Leigh et al. / Forensic Chemistry 2 (2016) 2228

25

application of UVRR as a method for standoff detection. Additionally, knowledge of the photoproducts may provide general insights
into the decomposition of this high explosive.
4.1. Normal mode analysis

Fig. 6. UVRR (228 nm excitation, 0.95 mW) spectra of HMTD and isotopologues;
labeled bands are those of photoproducts (see main text). Spectra are normalized to
the most intense peak at 1736 cm
1, and offset for clarity. *Raman signal from N2
and O2.

Off-resonance Raman spectra (Figs. 24) show that isotopic

substitution of 15N or 13C causes shifts in the band positions, as
expected. The largest shift is 21 cm
1. Experimental peak positions
and isotopic shifts are compared to calculations, and summarized
in Table S1 of the Supporting information. The agreement between
experiment and calculation is excellent, and the largest discrepancy between observed and computed isotopic shifts is only
7 cm
1. The agreement provides strong support for the calculated
normal modes.
The close match between computed and experimental vibrational frequencies was not necessarily expected compared to DFT
computations of other ground-state molecules. HMTD and other
high-energy, strained molecules can be a challenge for computations, including normal mode analysis [25]. The minimized structure in Fig. 1 illustrates the unusual bond angles of this molecule.
In addition to strain, crystal packing forces could affect the experimental frequencies, but are not addressed in our calculations. For
example, these effects could account for the poor match between
experimental and calculated frequencies of the peroxide OO
stretch (see Supporting information).

Fig. 7. Mass spectra of HMTD and isotopologues. Left panels show the fragmentation pattern for (A) 13C HMTD, (B) 15N HMTD, and (C) unlabeled HMTD. Right panels show the
fragmentation pattern after 1-h of UV photolysis for (D) 13C HMTD, (E) 15N HMTD, and (F) unlabeled HMTD.

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B.S. Leigh et al. / Forensic Chemistry 2 (2016) 2228

The low-wavenumber region of the spectrum (Fig. 2) is dominated by global, torsional modes. Some peaks are down-shifted
for both the 15N and 13C substitution, while other peaks are
affected only by 13C substitution. For example, the 573 cm
1 peak
remains relatively constant in the 15N derivative (572 cm
1), but
downshifts to 564 cm
1 in the 13C derivative. This peak corresponds to a mode in which the carbon atoms are displaced towards
the center of the molecule (see Supporting information for normal
mode descriptions), thus only 13C substitution is expected to show
a downshift. In contrast, the 583 cm
1 mode of HMTD is downshifted for both the 15N and 13C derivatives. The 583 cm
1 normal
mode reflects breathing motion along the NN axis, and involves
both nitrogen and carbon displacements. The 415 cm
1 band is
attributed to opposing rotations of the two N(CH2)3 groups, simultaneous with expansion/compression along the long axis. The
297 cm
1 mode is comprised of torsional motions of the oxygen
atoms and accompanying displacements of hydrogen. The nitrogen
and carbon atoms of the N(CH2)3 cap do not contribute significantly to this motion, consistent with its constant frequency upon
13
C or 15N substitution. Finally, the two peaks at 169 and
200 cm
1 correspond to global torsional motion, and show modest isotope shifts of 3 or 2 cm
1 upon isotopic substitution. It is
perhaps unexpected that the 200 cm
1 mode upshifts in the 15N
derivative. Upshifts for an isotopologue with heavier atoms have
been reported for other systems [26,27], and reflect small changes
in the composition of the normal mode. To summarize, the prominent bands below 700 cm
1 reflect motions of HMTD with displacement of many atoms.
The intermediate spectral window of 7001500 cm
1 (Fig. 3) is
rich with Raman bands. The most prominent of these, centered at
773 cm
1, is assigned to the characteristic OO stretch. The band
downshifts 6 cm
1 upon incorporation of 13C, because the motion
of carbon is coupled to oxygen in this normal mode. The 15N
derivative shows a small upshift, which has been described for
other systems [26,27]. The majority of bands with frequencies in
the range 9001300 range show significant (>10 cm
1) downshift
upon 13C substitution because these modes have significant carbon
and oxygen displacements. For example, the 910 cm
1 mode is
comprised of CO stretches, and the 951 cm
1 mode reflects an
asymmetric COO stretch. The 977 cm
1 mode involves CH2 rock
combined with CO and OO displacement. In contrast, the cluster
of bands from 1300 to 1500 cm
1 exhibit only modest isotope
shifts. This region is dominated by normal modes that involve
the CH bending modes of the methylene groups, and C and N atoms
are relatively static. For example, bands with frequencies 1318,
1398, and 1421 cm
1 are assigned to CH2 twist, wag/scissor, and
scissor, respectively.
The high-wavenumber region between 2800 and 3050 cm
1
(Fig. 4) reflects CH stretches and therefore, the position of the
peaks are insensitive to 15N incorporation. The 2917 and
2930 cm
1 modes are symmetric CH stretches, and the 2963
and 2976 cm
1 modes are asymmetric CH stretches. Full graphical representations of these displacements are available in Supporting information.

that are the direct result of at least one OO bond cleavage. In order
to identify photoproducts, mass spectra of the sample were collected during photolysis.
Mass spectra had been reported previously for HMTD and a
15
N/13C isotopologue [17]. In that report, four peaks were assigned
to the parent (208 m/z), and three fragments (176, 88, and 42 m/z).
Of these four peaks, only two (208, 176 m/z) could be definitively
identified using the 15N/13C isotope analog of HMTD. In the present
work, investigations of HMTD and two of its isotopologues allow us
to assign all the fragments in the mass spectra, as summarized in
Table 1. Our results confirm that the 88 m/z peak tentatively
assigned to NC3O2H6 in the prior report is correct.
Upon exposure to UV light, HMTD forms photoproducts that are
evident in the UVRR and mass spectra. We combine these experimental results with computational data, and propose the following
set of reactions (Scheme 1): HMTD releases formaldehyde and O2
to form a compound with formula N2C5O3H10 (146 m/z). This compound can then lose another oxygen molecule to form N2C5OH10
(114 m/z). An alternative hypothesis for the first step, whereby
CO2 and water are released instead of O2 and formaldehyde, is unlikely for two reasons. First, O2 production from decomposition is
favored by peroxides. Second, the carbon atoms in the parent
molecule are bound to a single oxygen; therefore, production of
CO2 would require rearrangement. The parent molecule and/or
the 146 m/z product could decompose to yield a 73 m/z fragment
that we attribute to NC2O2H3. The proposed structure of this species is that of an imide which could react in the condensed phase.
The UVRR spectrum supports this assignment of an imide-like
photoproduct. The calculated peaks for the 73 m/z imide photoproduct at 1711 and 1440 cm
1 (unscaled, data not shown) are similar
to the experimental values of 1736 and 1435 cm
1; additionally,
Table 1
Results from mass analysis of isotopologues shown in
Fig. 7.
m/z

Formula
Unphotolyzed

58
73
88
104
112
117
176
208

NC2OH4
NC2O2H3
NC3O2H6
NC3O3H6
N2C6H12
N2C4O2H9
N2C6O4H12
N2C6O6H12
Additional and enhanced
peaks post photolysis

73
114
146

NC2O2H3
N2C5OH10
N2C5O3H10

4.2. Identification of photoproducts

The UV resonance Raman spectra (Figs. 5 and 6) are strikingly
different from the off-resonance spectra. In fact, even at very low
UV power of 40 lW, the characteristic peroxide peak at 773 cm
1
disappears, and three new bands centered at 894, 1435, and
1736 cm
1 appear even for a relatively short (1 min) acquisition
time. These features are not present in the off-resonance spectra.
For HMTD, UV absorption is characterized as an electronic transition from non-bonded orbitals on N and O to the OO antibonding
orbital [24]. Therefore, it is reasonable to anticipate photoproducts

Scheme 1. Proposed photolysis products and corresponding m/z.

B.S. Leigh et al. / Forensic Chemistry 2 (2016) 2228

the predicted isotope downshifts match the experimental observations of Fig. 6, and thereby supports the proposed identities of the
photoproducts. Each HMTD molecule is capable of forming two
imide daughters, each of which possesses two carbonyls. We attribute the large 1736 cm
1 signal in the UV Raman to this increase in
carbonyl concentration or better resonance enhancement. This
peak is four to five times more intense than the 773 cm
1 peroxide
peak of HMTD. This carbonyl-rich photoproduct can be used as an
indicator of the presence of HMTD when utilizing UVRR spectroscopy. We note however that the products from UV photolysis
are different from those produced by thermal decomposition.
Specifically, the thermal pathway does not show an increased signal at 73 m/z, and the 114 and 146 m/z peaks are absent [28]. However, thermal degradation results in an increased 88 m/z peak
which was proposed to be an N-methyl imide, analogous to the
NH imide with 73 m/z proposed in the present work.
In addition to imide-like products, photolysis also yields organic
peroxides. Previous studies reported the generation of H2O2 upon
UV-photolyis; the peroxide was detected electrochemically or with
an enzyme assay [2931]. The peroxide stretch of H2O2 appears at
876 cm
1 and should not exhibit a 13C or 15N isotope shift. In the
present study, the experimental peak at 894 cm
1 downshifts to
868 cm
1 for the 13C HMTD photoproduct (Fig. 6) and therefore,
we attribute this peak to an organic peroxide.
We can estimate the efficiency of HMTD photoconversion in the
solid samples used in UVRR experiments. The HMTD photolysis
yield is defined as the fraction of HMTD molecules in solid phase
converted to imide and peroxide products per photon incident on
the solid sample. We assume that all the light is absorbed by the
opaque sample which had a maximum thickness of 1 mm. With
knowledge of the laser power, experimental conditions, rate of disappearance of UVRR HMTD bands, and assumed radius of a single
HMTD molecule of 3.7 , we estimate the yield is at least 1% with
228 nm excitation. This yield is a lower limit based on photoconversion of a monolayer of HMTD; we expect the yield to be larger
than 1% because it is expected that the UV beam will penetrate the
sample beyond a single monolayer. It is difficult to quantify the
depth of penetration; the fact that the product imide and peroxide
peaks become more intense in the UVRR spectra indicates that the
photoproduct is likely a solid that displaces HMTD. The prior works
that probed formation of H2O2 did not estimate the photolysis
yield, but described use of a 500 W arc lamp or ND:YAG laser
(48 mJ/pulse) as the UV sources [29], or 15-min exposure periods
[30]. These conditions of the earlier studies suggest that relatively
large doses of UV light were required to detect peroxide product.
4.3. Implications for the use of Raman spectroscopy for detection of
HMTD
Vibrational spectroscopy is an excellent tool that can be used
for the detection and molecular identification of explosives. The
ability to use Raman spectroscopy for stand-off detection makes
it an especially valuable technique. Both visible and UVRR methods
are viable methods; in particular, UVRR offers advantages in terms
of enhanced efficiency of the Raman scattering process as well as
capabilities for use in ambient conditions of daylight. However,
given the inherent instability of HMTD, absorption of UV light
results in homolytic cleavage of the OO bond. This analysis of
HMTD photoproducts is similar to a recent report on the photochemistry of TNT [32,33].
5. Conclusion
The combination of Raman spectroscopy, mass spectrometry,
and normal mode calculations of HMTD and its 13C and 15N iso-

27

topologues have revealed the vibrational structure and photoproducts of this high-energy molecule. The calculated isotope shifts are
in good agreement with the observed shifts. Thus, isotopologues
serve a dual purpose: they aid in the assignment of normal modes
in the expected manner, but also help validate calculations for a
class of compounds that are unusually strained. Results presented
here not only provide fundamental insight into the structure of
HMTD and its photoproducts, but also highlight the value of Raman
spectroscopy for stand-off detection and characterization of explosives. Raman spectra of the UV-photoproducts serve as signatures
of HMTD, and provide another set of vibrational markers for this
challenging peroxide-based explosive.
Acknowledgements
We thank Dr. Yongxuan Su of the UCSD Molecular Mass Spectrometry Facility, Dr. Jordi Cirera, Prof. Francesco Paesani, Rachel
H. Kim, and Prof. Michael J. Tauber at UCSD for valuable assistance
and discussions. The Ondax SureBlock filter was a generous loan
from Ondax, Inc. (Monrovia, CA). This is publication 14-13 of the
Federal Bureau of Investigation (FBI). Names of commercial manufacturers are provided for identification purposes only, and inclusion does not imply endorsement by the FBI. The project was
supported by a grant from the Intelligence Community Postdoctoral Research Fellowship Program through funding from the Office
of the Director of National Intelligence. All statements of fact, opinion, or analysis expressed are those of the authors and do not
reflect the official positions or views of the Intelligence Community
or any other U.S. Government agency. Nothing in the contents
should be construed as asserting or implying U.S. Government
authentication of information or Intelligence Community endorsement of the views of the authors.

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.forc.2016.08.002.
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