Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255

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Spectrochimica Acta Part A: Molecular and Biomolecular

Spectroscopy
journal homepage: www.elsevier.com/locate/saa

The vibrational properties of the bee-killer imidacloprid insecticide:

A molecular description
Antônio A.G. Moreira a,⁎, Pedro De Lima-Neto a, Ewerton W.S. Caetano b, Ito L. Barroso-Neto a, Valder N. Freire c
a
Departamento de Química Analítica e Físico-Química, Universidade Federal do Ceará, 60440-900 Fortaleza, CE, Brazil
b
Instituto de Educação, Ciência e Tecnologia do Ceará, 60040-531 Fortaleza, CE, Brazil
c
Departamento de Física, Universidade Federal do Ceará, Caixa Postal 6030, 60455-760 Fortaleza, CE, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The chemical imidacloprid belongs to the neonicotinoids insecticide class, widely used for insect pest control
Received 12 September 2016 mainly for crop protection. However, imidacloprid is a non-selective agrochemical to the insects and it is able
Received in revised form 3 February 2017 to kill the most important pollinators, the bees. The high toxicity of imidacloprid requires controlled release
Accepted 23 May 2017
and continuous monitoring. For this purpose, high performance liquid chromatography (HPLC) is usually
Available online 29 May 2017
employed; infrared and Raman spectroscopy, however, are simple and viable techniques that can be adapted
Keywords:
to portable devices for field application. In this communication, state-of-the-art quantum level simulations
Imidacloprid were used to predict the infrared and Raman spectra of the most stable conformer of imidacloprid. Four molec-
Infrared ular geometries were investigated in vacuum and solvated within the Density Functional Theory (DFT) approach
Raman employing the hybrid meta functional M06-2X and the hybrid functional B3LYP. The M062X/PCM model proved
Vibrational to be the best to predict structural features, while the values of harmonic vibrational frequencies were predicted
DFT more accurately using the B3LYP functional.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction imidacloprid, clothianidin and thiamethoxam; the revision of this re-

Insect pest control has been a human concern since about three
millennia [1]. In the absence of suitable technology for pesticide
manufacturing in the past, ingredients extracted from plants as nicotine
from tobacco around the 1690s, pyrethrins from pyrethrum flower and
rotenone from derris roots around 1800s were used. Between 1940 and
1970, the organic synthesis of insecticides allowed the commercial use
of organophosphates, methylcarbamates, organochlorines and pyre-
throids [2]. Over time, insect species developed resistance and a new
and more effective insecticide class called neonicotinoids was devel-
oped. Imidacloprid - released in 1991 - is the precursor of the
neonicotinoids and it is considered the most important chemical insec-
ticide of this class [3,4]. Unfortunately, imidacloprid and other
neonicotinoids induce the decline of beneficial insects such as bees.
The bees contributes approximately with 80% of insect pollination [5–
10], therefore, its reduction could generate a large environmental im-
pact [9,11–13]. Aiming to mitigate the harmful effect, the imidacloprid
is commonly applied in seed treatment; however, such strategy is not
effective because imidacloprid is a systemic insecticide [5,14]. The con-
cern lead the European Union (EU) to apply a restriction to the use of
⁎ Corresponding author.
E-mail address: aureliomoreira@alu.ufc.br (A.A.G. Moreira).
striction began in 2016 and will be completed, probably, in 2017 [15–
17]. In the same year, the UK's Food & Environment Research Agency
conducted its first study with free bees in the field under realistic; the
analysis showed that bee colony is affected by neonicotinoids [18,19].
Besides, several countries of EU (e.g., France, Germany, Italy, Slovenia)
agreed with the neonicotinoids ban, similar positions being taken by
Canada and the United States [20,21].
Some people have criticized the imidacloprid toxicity arguing that
many essays were performed using high dosages and that the bees
can avoid treated crops [6,11,19]. However, Kessler et al. considered re-
alistic dosages of imidacloprid, thiamethoxam and clothianidin compa-
rable to those found in the nectar and pollen; they concluded that the
honey bees (Apis mellifera) and bumblebee (Bombus terrestris) tend to
prefer the treated crop [8]. In turn, Rundlöf et al. studied the effects of
the clothianidin under field conditions, showing a reduction of the den-
sity of wild bees (bumblebee and solitary bees), the nesting of solitary
bees (Osmia bicornis L.), and decreased of reproduction and colony
growth of bumblebee [6]. While Dively et al. showing that the exposure
to high dosages of imidacloprid over field conditions (20 μg kg−1; 100
μg kg−1) had no significant effect on foraging and performance of hon-
eybee colonies up to 12 weeks of exposure [22]; the resilience can be
due the large colony sizes [6,23]. In this sense, the harmful effect of
neonicotinoid to the bees can be linked to other stressors: varroa

http://dx.doi.org/10.1016/j.saa.2017.05.051
1386-1425/© 2017 Elsevier B.V. All rights reserved.
246 A.A.G. Moreira et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255

destructor mites, viruses, fungi, poor nutrition and loss of food source. pellets (120 mg, 1 wt%), with 120 scans at a resolution of 2 cm−1, rang-
Thus, more studies are necessary to prove that neonicotinoids alone ing from 400 to 4000 cm−1. The absorption measurements were per-
cause colony collapse disorder (CCD) [19,21,23]. formed in an FTLA 2000 Series Laboratory, ABB Bomem. Baseline
Currently, the high-performance liquid chromatography (HPLC) is corrections were made to allow a better comparison with the DFT-
the most used laboratory analytical method for imidacloprid monitor- based theoretical calculations. The FT Raman spectrum was recorded
ing in samples of soil, water, vegetables, formulations and honey [24– with a Bruker Vertex 70 spectrometer with Raman attachment RAM II
27]. However, HPLC demand a long time, materials consumption and re- that uses a 1064 nm Nd-YAG laser and a liquid-nitrogen cooled Ge de-
quest a complex process of sample extraction, pre-concentration and tector line as the excitation source to register the Raman spectrum in
cleaning [28,29]. Gas chromatography (GC) is little used as imidacloprid the 400–4000 cm− 1 wavenumber range. The spectral curves of the
exhibits high thermal instability [30,31]. Other less used laboratory sample were measured inside the hemispheric bore of an aluminum
methods are capillary electrophoresis enzyme-linked immunosorbent sample holder. The Raman spectrum was set for 1024 scans at a laser
assays (ELISAs) and electroanalytical [32–35]. power of 150 mW and resolution of 2 cm−1.
The ability to quantitatively measure a compound under field condi-
tions is indeed a practical task. In this sense, Infrared Spectroscopy and 2.2. Computational Methods
Raman Spectroscopy can be adapted to portable devices and provide a
low operation cost [28,29,36]. For instance, Ma et al. measured the con- The imidacloprid structure with the highest concentration in the
tent of imidacloprid analyzing the infrared spectrum for quantitative physiological pH (7.4) was taken into account for all calculations. The
determination [29]. Quintás et al. evaluated the spectral curve to esti- thermodynamically most stable conformers were found from quantum
mate the imidacloprid amount in commercially formulations [24]. By chemistry calculations according to the values of their free energies
the way, Hou, Pang & He developed an in situ surface enhanced through a relaxed potential energy surface scan (RPESS) [61] by rotating
Raman spectroscopy (SERS) strategy that was shown to be a simple, the dihedral angles of imidacloprid (Fig. 1a). The dihedral angles ∅1-
rapid and sensitive way to detect imidacloprid on plant surfaces or C6C1C7N8 and ∅ 2-C1C7N8C12 were rotated in 11 steps of 30°, the
food [28]. Similarly, Zhang has fabricated a SERS array that provides total energies of the corresponding conformers being evaluated using
rapid, simple and inexpensive detection of imidacloprid in wastewater Density Functional Theory (DFT), adopting a 6–311 ++G(d,p) basis
[37]. Moreover, the vibrational spectroscopy is useful in the develop- set and using the M06-2X and B3LYP exchange-correlation potentials
ment of controlled release formulations (CRF). For example, the use of implemented in the Gaussian 09 code [62]. The following convergence
submicron particles made of chitosan and D,L-lactide grafted with thresholds were applied: maximum force per atom smaller than
imidacloprid aiming to reduce its harmful effects on non-target organ-
isms was characterized by Infrared Spectroscopy [38]. Similarly, Flo-
res-Céspedes et al. carried out a polymeric matrix of lignin
polyethylene glycol (PEG) for controlled delivery of imidacloprid, prob-
ing the imidacloprid-nanocomposites using Infrared Spectroscopy [39].
Adak et al. have synthetized an amphiphilic nano-polymer based in
polyethylene glycol and the di-acids glutaric acid, adipic acid, pimelic
acid and suberic acid; they have characterized the PEG, polymer and
imidacloprid formulation using Infrared Spectroscopy [36].
After careful investigation, we could not find any theoretical studies
describing the imidacloprid vibrational modes and its infrared and
Raman spectra using standard computational chemistry [39]. In this
work, we aim to supply this gap by providing for the first time the the-
oretical infrared and Raman spectra of the imidacloprid using Density
Functional Theory (DFT) employing the M06-2X and B3LYP exchange-
correlation potentials [40–42], which provide cost-effective computa-
tion time and accuracy [43,44]. This work was carried out within a re-
search frontier that encompasses our interest in understanding the
structural, electronic and vibrational properties of biomolecules of phar-
macological interest, e.g., psoralens compounds (photobiological and
phototherapeutic activities) [45], lamivudine (reverse transcriptase in-
hibitor for the human immunodeficiency virus HIV) [46],
naphthofuranquinones (antitrypanocidal activity) [47], sodium
alendronate (applied in the osteoporosis treatment) [48], haloperidol
(a first generation antipsychotic for schizophrenia) [49], and the
antitrypanocidal drug benznidazole [50]. Due to the limitations on
disregarding intermolecular interactions of the imidacloprid crystal
probed by vibrational spectroscopy [51], this work will be followed
soon by a DFT-based description of the vibrational properties of
imidacloprid crystals as we have performed for several molecular crys-
tals to describe their structural, electronic, optical, vibrational and pho-
non properties [51–60].

2. Materials and Methods

2.1. Experimental Methods

Fig. 1. Imidacloprid planar structure (a); the most stable conformers performed with M06-
Imidacloprid with at least 98% purity was purchased from Sigma-Al- 2X functional in vacuum (b) and PCM framework (c); the most stable conformers from
drich. The FTIR spectrum of the imidacloprid was measured on KBr B3LYP functional in vacuum (d) and PCM (e).
 A.A.G. Moreira et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255
1.5 × 10 5 Ha Å−1, RMS force per atom smaller than 1.0 × 10–5 Ha Å−1,
self-consistent-field energy variation smaller than 10−7 Ha, and maxi-
mum atomic displacement smaller than 6.0 × 10−5 Å. The polarization
continuum model (PCM) was used to simulate solvation of the mole-
cules in water. By the way, we previously discussed in another paper
these conformers in terms of their structural parameters and electronic
properties [63], So, we present in this communication only the vibra-
tional properties to the most stable conformers found in that work. In
order to generate the theoretical vibrational spectra curves, the full
width at half maximum (FWHM) was set to 10 cm−1 to the theoretical
infrared spectra and 4 cm−1 to the theoretical Raman spectra. The
Raman intensities were obtained using the GaussSum code [64]; to
more details, the reader should consult the works of Durig et al. [65],
Krishnakumar et al. [66], and Keresztury et al. [67]. All the computed in-
frared and Raman intensities were normalized to unity and the theoret-
ical vibrational frequencies were placed in unscaled form. The VEDA
code was employed to compute the potential energy distribution
(PED) of each vibrational normal mode calculated before using DFT [68].
3. Results and Discussion
3.1. The Imidacloprid Conformers
The largest population of imidacloprid found in the physiological pH
(7.4) is deprotonated, with zero total charge as shown in Fig. 1 (a) [69].
According to Tomizawa & Casida, at pH 7.4 the protonation of
imidacloprid structure is below of 0.0002% [70]. Hence, the initial
imidacloprid structure for quantum chemical calculations in the Gauss-
ian 09 software was prepared deprotonated.
In a paper we published recently, a scan/geometry optimization pro-
cedure was performed in Gaussian 09 to explore the set of minimum en-
ergy conformers - see the work of Moreira et al. [63]. The global energy
minimum conformers found using the M06-2× and B3LYP exchange-
correlation potential in PCM framework and vacuum are shown in Fig.
1(b–e). The conformers obtained from M06-2X functional was labeled
IMI1-MV (MV standing for M06-2X-vacuum) (Fig. 1b), and IMI1-MP
(MP stands for M06-2X-PCM) (Fig. 1c); on the other hand, the calcula-
tions performed with the B3LYP functional produced the global mini-
mum conformer IMI1-BV (Fig. 1d) (BV means B3LYP-vacuum), and
IMI1-BP (Fig. 1e) (BP means B3LYP-PCM). Bond lengths, bond angles
and dihedral angles including the global and local minimum energy
conformers are available in the Supporting Information (S1).
The main rotational degree of freedom of the imidacloprid are relat-
ed to the dihedral angles that encompass the methylene group (i.e., ∅1
and ∅ 2). The values found for ∅ 1 and ∅ 2 were, respectively, 107.4°
and − 64.8° in the case of IMI1-MP, 94.4° and − 67.2° for IMI-MV, −
45.7° and −74.2° for IMI1 BP and, lastly, 116.9° and −75.2° for IMI1-
BV [63]. Despite the small interconverting energy barrier between the
imidacloprid conformers, e.g., 0.398 kcal mol−1 according to the M06-
2X calculation and 0.412 kcal mol−1 using the B3LYP functional (Fig.
S2, Supporting Information), the main contributions for the vibrational
system properties are assigned to the thermodynamically most stable
conformer as the infrared and Raman spectra of the other conformers
do not differ significantly - see their spectra in the Supporting Informa-
tion S2.2-S2.4. Therefore, we have explored only the vibrational spectra
of the global or lowest energy conformers IMI1-MP, IMI1-MV, IMI1-BP
and IMI1-BV. To facilitate the discussion and improve the viewing of vi-
brational modes, we have split the spectral curves into three distinct re-
gions: 400–1200 cm−1; 1200–2000 cm−1 and 2800–3800 cm−1.
3.2. Vibrational Analysis
The support of theoretical computations is very helpful in the iden-
tification of the vibrational signatures, overcoming limitations of exper-
imental guesses [68]. The analysis of simulation data can be performed
by direct visualization or by using the potential energy distribution
247
(PED) of each vibration. In the latter case, the potential energy distribu-
tion (PED) of the internal coordinates belonging to a given vibration
normal mode is employed to perform the assignment, which is useful
to avoid mistakes by overestimation of the contributions from hydrogen
atoms when purely visual analysis is used. In this work, we use the
VEDA software for quantify the PED of each calculated normal mode.
In addition, the results may exhibit differences as one switches from
one functional to another (e.g., M06-2X to B3LYP). Then, for each
mode we prefer to assign the strongest PED contributions common to
both approaches. In addition, to decide which experimental bands are
matched by the theoretical peaks, we checked both the calculated infra-
red and Raman spectra (see Supporting Information, S2.2-S2.4). We also
remark that the experimental Raman spectra is very useful to assist in
the assignment of infrared bands common to both measurements, as
the Raman bands are thin and well resolved in comparison to the infra-
red bands.
3.3. Spectra in the 400–1200 cm−1 Range
Fig. 2 show the infrared (left) and the Raman (right) spectra of
imidacloprid in the 400–1200 cm−1 range. The experimental spectrum
is show in the top of Fig. 2 followed by the computed spectrum using the
M06-2X functional in PCM framework, B3LYP functional in PCM, the
M06-2X in a vacuum, and lastly the B3LYP in a vacuum. The assign-
ments of the main experimental absorption bands are shown in Table
1 (400–1200 cm−1) and 2 (1200–3800 cm− 1), for which only the
modes common to both M06-2X and B3LYP PCM methods are taken
into account obeying the highest potential energy distribution (PED)
description. A table with all normal mode matches between the M06-
2X and B3LYP functional in vacuum approaches is available in the
Supporting Information (Table S3.1). Larger tables with all the normal
modes according to the M06-2X and B3LYP functional in PCM (Table
S3.6-S3.8) and vacuum (Table S3.9-S3.11) are also available there.
In the infrared experimental spectrum, the main bands are E2, E5,
E6, E10, E14, E15, E20, E25, E27 and E29 (See Fig. 2, left). Each experi-
mental band (e.g., E2) is related to a M06-2X and B3LYP theoretical ab-
sorption in PCM (e.g., P2) and to a M06-2X and B3LYP theoretical
absorption in vacuum (e.g., V2). The band E2:420 cm−1 can be matched
to CCC out-of-plane bending-16a (we note that the vibrational modes of
the substituted pyridine ring are assigned here following the Varsanyi's
nomenclature) [71] (Table 1). The E5:493 cm−1 band is related to CCC
out-of-plane bending-16b. The mode E6:587 cm−1, in turn, was
assigned to an out of plane angular deformation of H23N10
(δH23N10); likely, this band is wide due to the hydrogen bonds be-
tween imidacloprid molecules. The mode E10:718 cm−1 was related
to an out of plane vibration to the group C9N8N10N13 (∅
C9N8N10N13), in which three surrounding atoms (N8N10N13) vibrate
out of the plane in one direction whereas the central atom (C9) vibrates
in the opposite direction. The experimental mode E14:785 cm−1 was
assigned to ∅ N13N14O15O16. The mode E15:812 cm−1 is related to
CCC in-plane bending-6a and torsion of the group H18H19C2C3
(τH18H19C2C3). The most intense mode in the 400–1200 cm− 1
range is the E20:943 cm− 1 and it was matched to a torsion of
H20C1C6C7. The illustration related to the E20 vibration is shown in
the Fig. 3, on which the dark green and brown arrows indicate, respec-
tively, the intensity of atomic displacement computed with M06-2X and
B3LYP functionals. Although the mode E20 possesses several vibrations,
the τH20C1C6C7 prevails; its PED value are 69% compute with M06-2X,
and 38% with B3LYP (Table 1). Moreover, about the high-intensity
modes, the supporting information S4.1 show the movies to the
modes computed with M06-2X and B3LYP, both PCM and vacuum,
while S4.2 show the pictures to the modes computed in vacuum. The
second most intense movement is the mode E25:1053 cm−1 and it
was identified as asymmetric stretching of C11C12N10 (illustration in
Fig. 3; movie in S4.1); its PED value is 54% given by B3LYP functional.
The PED value to the mode E25 obtained with M06-2X functional was
248 A.A.G. Moreira et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255

Fig. 2. Infrared (left) and Raman (right) spectra for imidacloprid from 400 to 1200 cm−1; experimental spectrum are located in the top of figure, followed by M06-2X functional in PCM,
B3LYP in PCM, M06-2X in vacuum and lastly, B3LYP in vacuum.

computed to a set of vibrations other than νaC11C12N10; to more infor-
mation the reader should refer to the Table S3.7 in supporting informa-
tion. In the mode E27:1107 cm−1, there were no common vibrations,
thus we have choosing the modes with highest PED to assign; it was
matched to Breathing-1 in the chloropyridine ring according to M06-
2X functional (see Table 1), and as bend of H24H25C11 and
H26H27C12 (βH24H25C11, βH26H27C12) according to B3LYP. The
mode E29:1148 cm−1 was assigned to the vibrations: νaC9C12N8,
νsC9N8N10 and νsN13N14O15O16 (Table 1).
The most intense experimental Raman absorptions from 400 to
1200 cm−1 range are E4, E7, E12, E15, E16, E18, E21, E23, E26 and E27
(Fig. 2, right), while the modes E15 and E27 were discussed previously
in the infrared spectrum. The experimental mode labeled E4:476 cm−1
corresponds to a set of bendings, i.e., βC7C9N8, βC9N8N10 and

Table 1
Assignment of the most intense experimental vibrational normal modes for imidacloprid from 400 to 1200 cm−1 range, in PCM framework, according to M06-2X and B3LYP functional.

Mode EXP M06-2X B3LYP Assignment

ωIR ωR ωT ωT M06-2X and B3LYPa or M06-2X/B3LYPb

02 420 421 425.57 420.79 CCC out-of-plane bending-16a (M:24;B:93)

04 475 476 485.05 483.49 [βC7C9N8, βC9N8N10, βN13N14O15 (M:40)]/[βC7C9N8, βC9N8N13 (B:30)]
05 493 495 534.91 511.28 CCC out-of-plane bending-16b (M:43;B:62)
06 587 587 555.64 559.35 δH23N10 (M:60;B:87)
07 628 633 640.24 641.94 CCC in-plane bending-6b (M:79;B:82)
10 718 718 738.19 722.85 ∅C9N8N10N13 (M:83;B:80)
12 753 753 780.30 772.83 CCC puckering-4 (M:55;B:see SI)
14 785 791 821.64 790.05 ∅N13N14O15O16 (M:93;B:87)
15 812 816 843.09 831.42 [CCC in-plane bending-6a, τH18H19C2C3 (M:67;B:50)]
16 826 830 871.59 848.62 τH18H19C2C3 (M:66;B:38)
18 885 886 930.09 913.59 [βC9C12N8, βC11C12N10, βC11C12N8, βH26H27C12,
βH24H25C11, βC9N13N14, βN13N14O16, βC9C11N10 (M:29;B:75)]
20 943 945 971.83 962.06 τH20C1C6C7 (M:69;B:38)
21 958 960 992.68 976.05 νsC11C12N10 (M:54;B:see SI)
23 995 1001 1041.05 1020.94 [νC12N8, νN13N14, νsN14O15O16 (M:see SI;B:see SI)]
24 1025 1022 1050.42 1038.47 CCC trigonal bending-12 (M:see SI;B:84)
25 1053 1053 1077.55 1053.16 νaC11C12N10 (M:see SI;B:54)
26 1097 1096 1125.33 1105.53 [βH24H25C11, βH26H27C12 (M:77)]/Breathing-1 (B:64)
27 1107 1110 1133.96 1123.06 Breathing-1 (M:63)/[βH24H25C11, βH26H27C12 (B:88)]
29 1148 1151 1182.44 1166.55 [νaC9C12N8, νsC9N8N10, νsN13N14O15O16 (M:49;B:47)]
a
The M06-2X and B3LYP functional possesses common modes.
b
There are no common modes between M06-2X and B3LYP functional. ν:stretching; β:bending; τ:torsion; ∅:out; s:symmetric a:asymmetric; δ:out-of-plane. ωIR: experimental in-
frared frequency; ωR: experimental Raman frequency; ωT: theoretical frequency (M:PED): PED value to the vibrations from M06-2X; (B:PED): PED to the vibrations from B3LYP. [vibra-
tion1, vibration2, … (M:PED; B:PED)]: the PED value was computed to the all vibrations inside the bracket. (M or B: see SI): the PED value are computed to common modes and other than
common modes.
 A.A.G. Moreira et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255 249

Fig. 3. Illustration of some intense vibrations from infrared and Raman spectra for imidacloprid, and their respective assignments according to the computed theoretical normal modes in
the PCM using the M06-2X (dark green) and B3LYP (brown) in the 400–1200 cm−1 range. (For interpretation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)

βN13N14O15 computed with the M06-2X functional; while according
to B3LYP functional, prevailed in the E4 mode the vibrations βC7C9N8
and βC9N8N13 (Table 1). At the E7:633 cm−1 mode - the second
most intense mode other than E15 and E27 described before in the in-
frared spectra - we observe the vibration CCC in-plane bending-6b, in
the chloropyridine ring, in which the Fig. 3 shown its illustration
(movie: S4.1). The PED values to the mode E7 are 79% related to the
M06-2X functional, and 82% to B3LYP (Table 1).The E12:753 cm− 1
mode was assigned as CCC puckering-4, while the E16:830 cm−1 band
is due to a τH18H19C2C3. The E18:886 cm− 1 mode was matched to
the bendings: βC9C12N8, βC11C12N10, βC11C12N8, βH26H27C12,
βH24H25C11, βC9N13N14, βN13N14O16, βC9C11N10. In turn, in the
E21:960 cm− 1 band the symmetrical stretching of C11C12N10
dominates (νsC11C12N10). The first most intense Raman mode -
other than E15 and E27 described before in the infrared spectra - is
E23: 1001 cm−1 and it was assigned to the symmetrical stretching of
N14O15O16 and the stretching of the groups N13N14 and C12N8
(νC12N8, νN13N14, νsN14O15O16). The illustration of the E23 mode
vibrations is shown in the Fig. 3 (movie: S4.1) on which we have
highlighted the νsN14O15O16; to most information about the PED
values, the reader should refer to the Table S3.7 because the PED in-
cludes a set of vibrations other than the common modes shown in
Table 1. To the E26:1096 cm−1 mode, prevailed the vibrations
βH24H25C11 and βH26H27C12 as result of M06-2X functional; the
E26 mode was related to the Breathing-1 in the chloropyridine ring
when computed by B3LYP functional.
250 A.A.G. Moreira et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255

Fig. 4. Infrared (left) and Raman (right) spectra for imidacloprid from 1200 to 2000 cm−1; experimental spectrum are located in the top of figure, followed by M06-2X functional in PCM,
B3LYP in PCM, M06-2X in vacuum and lastly, B3LYP in vacuum.

3.4. Spectra in the 1200–2000 cm−1 Range
In this region there are many intense experimental bands overlap-
ping. The infrared strongest lines are E33, E35, E37, E43, E44, E47, E48
and E49 (Fig. 4, left). The E33:1233 cm−1 mode is characterized by
stretchings at the nitroguanidine moiety and imidazolidine ring:
νaC9N10N13, νaN13N14O16, νaC1C7N8, νsC9C11N10 and
νaC9N13N14 (Table 2); it atomic displacement are exhibit by the illus-
tration in Fig. 5 (movies: S4.1). The mode E33 possesses a contribution
of 56% to total PED considering the M06-2X, and 59% to B3LYP (Table
2). The mode E35:1279 cm−1 is related to the bending of the methylene
groups H24H25C11, H26H27C12. For the E37:1295 cm−1 mode, the

Table 2
Assignment of the most intense experimental vibrational normal modes for imidacloprid from 1200 to 3800 cm−1 range, in PCM framework, according to M06-2X and B3LYP functional.

Mode EXP M06-2× B3LYP ASSIGNMENT

ωIR ωR ω ω M06-2X and B3LYPa or M06-2X/B3LYPb

33 1233 1232 1276.45 1248.40 [νaC9N10N13, νaN13N14O16, νaC1C7N8, νsC9C11N10, νaC9N13N14 (M:56;B:59)]
34 1243 1245 1288.74 1276.09 [CH in-plane trigonal bending-15, νaC7C12N8 (M:75;B:47)]
35 1279 1277 1310.13 1285.58 [βH24H25C11, βH26H27C12 (M:45;B:33)]
37 1295 1294 1347.75 1321.91 [βH23C9N10, βH26H27C12, βH24H25C11, νN14O15, νaC11C12N10,
νaC11C12N8 (M:see SI;B:71)]
40 1366 1373 1420.17 1399.44 [βH24H25C11, βH26H27C12 (M:see SI;B:see SI)]
43 1447 1447 1498.91 1475.07 [βH24H25C11, βH26H27C12 (M:76)]/βH21H22C7 (B:88)
44 1456 1456 1510.97 1486.27 CC stretching-19a (M:74;B:see SI)
45 1470 1470 1522.25 1505.33 [βH24H25C11, βH26H27C12 (M:92:B:86)]
46 1491 1484 1537.79 1519.81 [νC9N8, νaN14O15O16 (M:54)]/[βH26H27C12, βH24H25C11 (B:86)]
47 1551 1552 1595.04 1563.89 [νaC9N8N10, νaN14O15O16 (M:66;B:60)]
48 1570 1568 1627.79 1590.78 [νaC9N8N10N13, νN14O15 (M:67;B:52)]
49 1585 1585 1648.96 1606.15 CH in-plane bending-9a (M:76;B:69)
53 2896 2899 3092.67 3049.41 νsH21H22C7 (M:94)/νsH24H25C11 (B:89)
54 2928 2931 3142.29 3109.52 νaH26H27C12(M:88)/νaH21H22C7 (B:91)
55 2944 2956 3154.49 3114.88 νaH21H22C7 (M:93)/νaH26H27C12 (B:82)
57 2987 2989 3173.28 3172.06 νsH24H25C11 (M:89)/νH20C6 (B:100)
58 3047 3058 3204.75 3178.92 νH18C2 (M:96;B:96)
59 3079 3093 3233.88 3217.95 νH19C3 (M:96;B:97)
60 3374 3651.80 3618.72 νH23N10 (M:99;B:99)
a
The M06-2X and B3LYP functional possesses common modes.
b
There are no common modes between M06-2X and B3LYP functional. ν:stretching; β:bending; τ:torsion; ϕ:out; s:symmetric a:asymmetric; δ:out-of-plane. ωIR: experimental infrared
frequency; ωR: experimental Raman frequency; ωT: theoretical frequency (M:PED): PED value to the vibrations from M06-2X; (B:PED): PED to the vibrations from B3LYP. [vibration1,
vibration2, … (M:PED; B:PED)]: the PED value was computed to the all vibrations inside the bracket. (M or B: see SI): the PED value are computed to common modes and other than com-
mon modes.
 A.A.G. Moreira et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255 251

common vibrations are bendings in the imidazolidine ring, i.e., [74]. Shandran et al. measured and computed the infrared and Raman
βH23C9N10, βH24H25C11, βH26H27C12, and stretchings in the nitro spectra of the compound (E)-4-((anthracen-9-ylmethylene)amino)-N-
and imidazolidine: νN14O15, νaC11C12N10 and νaC11C12N8. The carbamimidoylbenzenesulfonamide, which has an NH group similar to
next two strongest modes E43:1447 cm− 1 and E44:1456 cm− 1 are imidacloprid [75]. Those authors performed calculations of the theoret-
very close. The mode E43 are originating from the bending of the meth- ical infrared spectrum using the B3LYP functional and have found that
ylene groups H24H25C11 and H26H27C12 in M06-2X functional; ac- the bands at wavenumbers 3466 cm−1 and 3355 cm−1 are due to the
cording to B3LYP, in the mode E43 prevailed the bend of H21H22C7. NH stretching, with respective experimental absorption bands at
The E44:1456 cm−1 mode was identified as being produced by the CC
stretching-19a. The E47, E48 and E49 bands form a broad structure.
The E47:1551 cm−1 mode was assigned to asymmetric stretchings of
N14O15O16 and C9N8N10 (νaC9N8N10, νaN14O15O16). For the
mode E48:1570 cm− 1, we have the asymmetric stretching of
C9N8N10N13 and the stretching of N14O15 (νaC9N8N10N13,
νN14O15); these vibrations - illustration in Fig. 5; movie in S4.1 - con-
tributes with a 67% to total PED according the M06-2X, and 52% related
to B3LYP system (Table 2). With respect the mode E49:1585 cm−1, the
CH in-plane bending-9a dominates (Table 2).
The highlighted modes in the Raman spectra are E34, E35, E37, E40,
E45, E46, E48 and E49, however, the modes E35, E37, E48 and E49 have
been argued before in the infrared spectra. In the E34:1245 cm−1 mode,
prevails the common vibrations CH in-plane trigonal bending-15 and
νaC7C12N8 (Table 2). The E40:1373 cm−1 and E45:1470 cm−1 modes
are matched to the bendings in the methylene groups: βH24H25C11
and βH26H27C12. As an example, the atomic displacement to E40
mode are demonstrated in Fig. 5 (movies: S4.1) and the PED values
should be assessed in the Table S3.7. There are no common vibrations
between the theoretical models M06-2X and B3LYP to the mode 46,
thus, the E46:1484 cm−1 was matched to the νC9N8 and
νaN14O15O16 (PED:54%) according to M06-2X, and to the
βH26H27C12 and βH24H25C11 (PED:86) as a result from B3LYP (See
Fig. 5; Table 2).

3.5. Spectra in the 2800–3800 cm−1 Range

Theoretical calculations predict that absorptions related to symmet-

ric and asymmetric stretchings of CH and CH2 saturated carbons occur
for wavenumbers between 2800 and 3000 cm−1, while the vibrations
of CH stretching in unsaturated carbons (alkenes and aromatic) range
from 3150 to 3500 cm−1 [72]. Absorptions ranging from 3300 to
3500 cm−1 are the result of NH stretchings [73]. The E53:2896 cm−1 in-
frared normal mode (Fig. 6, left) in the M06-2X functional is related to
the symmetrical stretching of H21H22C7, while the B3LYP assigns a
symmetrical stretching of H24H25C11 (Table 2). The E58:3047 cm−1
and E59:3079 cm−1 infrared bands are due to the stretching on the pyr-
idine ring of H18C2 and H19C3 respectively. The absorption line labeled
E60:3374 cm−1 corresponds to a H23N10 stretching (illustration in Fig.
5; movie: S4.1); indeed, this is an isolated vibration with a high PED
value of 99% either M06-2X and B3LYP. While the absorption bands lo-
cated at the right and left sides of E60 in the infrared spectrum (Fig. 6,
left) are likely due to the effect of hydrogen bonding with neighbor
molecules.
In M06-2X functional, the Raman normal mode E54:2931 cm−1 (Fig.
6, right; Table 2) is an asymmetrical stretching of the groups H26H27C12
(illustration in Fig. 5; movie: S4.1) and PED value of 88%, considering the
M06-2X functional; the vibration to B3LYP model was matched to an
asymmetric stretching of H21H22C7 (Fig. 5; movie: S4.1), with 91% of
contribution to total PED. Otherwise, the mode E55:2956 cm−1 according
to M06-2X functional (B3LYP) is an asymmetrical stretching of
H21H22C7 (H26H27C12). For the E57:2989 cm−1 mode, the symmetric
stretching of H24H25C11 prevails in the M06-2X functional, and the
B3LYP is related to the stretching of H20C6 group in the chloropyridine
ring. The experimental mode E60:3374 cm−1 is active in the infrared
spectrum but inactive in the Raman spectrum, corresponding to the Fig. 5. Illustration of some intense vibrations from infrared and Raman spectra for
imidacloprid, and their respective assignments according to the computed theoretical
stretching of the H23N10 bond (Fig. 6). Singh (2008) found experimen- normal modes in the PCM using the M06-2X (dark green) and B3LYP (brown) in the
tally that the NH group of the amino uracil compound is infrared and 1200–3800 cm−1 range. (For interpretation of the references to colour in this figure
Raman active while the uracil is infrared active and Raman inactive legend, the reader is referred to the web version of this article.)
252 A.A.G. Moreira et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255

Fig. 6. Infrared (left) and Raman (right) spectra for imidacloprid from 2800 to 3800 cm−1; experimental spectrum are located in the top of figure, followed by M06-2X functional in PCM,
B3LYP in PCM, M06-2X in vacuum and lastly, B3LYP in vacuum.

3415 cm− 1 and 3323 cm− 1. However, no corresponding intensities the scaling factor is usually not adequate to describe the full spectral
were registered by the Raman measurement. range.
In order to choose the theoretical methodology (M06-2X or B3LYP)
that provides the best geometries and vibrational frequencies we com-
3.6. Comparing the M06-2X and B3LYP Results pared the theoretical data with the experimental geometry from X-ray
diffraction and infrared and Raman measurements, following the same
The theoretical vibrational frequencies calculated here using quan- procedure of other authors [77,78], which used either linear regression
tum methods differ from experimental vibrational frequencies mainly or root mean square deviation (RMSD) in their estimates. Some works
because anharmonic contributions are omitted and because the ex- report that M06-2X calculations achieve bond lengths and bond angles
change-correlation functional used are approximations within a limited closer to the experimental data for crystals [79–81]. On the other hand,
basis set expansion. Deviations of the theoretical harmonic vibrational other works indicate that the B3LYP functional leads to bond lengths
frequencies relative to the experimental data can be corrected by intro- and bond angles closer to the real crystalline structure [82–84]. The
ducing a scaling factor which facilitates the comparison [76]. However, work of Sert et al. points out that the M06-2X functional predicts bond
angles more accurately, while the B3LYP functional is superior in bond
Table 3 length estimates [85]. Shu-Gui, Hao and Ong-Zhong made a study on
RMSD values for theoretical structure of the lowest energy imidacloprid conformers in re- non-covalent interactions (dispersion interactions) and hydrogen
lation to the experimental structure: bond length, bond angles and dihedral angles (a); vi- bonds in double-helical structures of β-DNA with up to 10 base pairs,
brational frequencies of infrared (b) and Raman (c).
comparing M06-2X, B3LYP and other functionals in the gas phase [86].
(a) RMSD for Topological Parameters⁎ In their study, the M06-2X functional exhibited the smallest average de-
PARAMETER IMI1-MP IMI1-BP IMI1-MV IMI1-BV viations relative to the experimental values. The M06-2X approach de-
BOND 9.14 9.26 9.26 9.39 scribed the π-staking effect better than other functionals, while the
ANGLES 16.84 17.19 19.93 19.66 B3LYP functional provided a better description of hydrogen bonds. In-
DIHEDRAL 136.67 146.07 127.50 156.33 deed, there is not a single DFT functional that excels in the description
(b) RMSD for infrared frequencies
of all molecular properties simultaneously. For example, J. Kim, K. Kim
ω range (cm−1) IMI1-MP IMI1-BP IMI1-MV IMI1-BV & Ihee observed that the hybrid meta functional M06-2X overestimates
400–1200 30.23 17.40 31.46 19.29
the theoretical vibrational frequencies in comparison to the B3LYP func-
1200–2000 46.86 25.35 41.90 22.04
2800–3800 172.19 172.19 201.08 151.59 tional for the CF3Br compound (gas-phase) and the CF3 radical. Hybrid
(c) RMSD for Raman frequencies functionals generally provide better results than meta hybrids for vibra-
ω range (cm−1) IMI1-MP IMI1-BP IMI1-MV IMI1-BV tional frequency calculations [87].
400–1200 28.39 15.63 29.64 17.78 The RMSD is a simple statistical tool which has been used in many
1200–2000 47.44 25.91 42.64 22.68 works for the purpose of verifying the difference between theoretical
2800–3800 189.48 158.79 187.04 139.75 parameters and vibrational frequencies in relation to the experimental
⁎ Obs. Bond: (rmsd) × 100; angles:(rmsd) × 10; dihedral: rmsd. values [44,79–86,88–92]. Table 3 shows the RMSD values for bond
 A.A.G. Moreira et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 185 (2017) 245–255
length, bond angles and dihedral angles (section a), infrared frequencies
(section b) and Raman frequencies (section c) found in this work. The
RMSD values were computed for the theoretical structure of the lowest
energy imidacloprid conformers according to the M06-2X (PCM and
vacuum) and B3LYP (PCM and vacuum) methodologies relative to the
experimental crystal structure (to topological parameters) [93], and
the amorphous structure, i.e., the powder compound (to vibrational
frequencies). Clearly, the M06-2X functional in the PCM model (IMI1-
MP) has the smallest deviations for bond length, bond angles and
dihedral angles than the B3LYP-PCM system, while the M06-2X in
vacuum provided the smallest deviation for bond length and dihedral
angles. However, the B3LYP (PCM and vacuum) model achieved the
lowest RMSD values for the theoretical infrared and Raman frequencies
related to the values obtained from M06-2X system (PCM and
Vacuum).
Although the B3LYP functional give the lowest RMSD values, we
pointed out that the experimental curves are most close to the profile
of the theoretical curves obtained from M06-2X and B3LYP functionals
in PCM framework than the vacuum models. On the one hand, some-
times a model (e.g., the M06-2X-PCM) facilitates the identification of a
given experimental band; on the other hand, another theoretical system
(e.g., B3LYP-PCM) aid the identification of the experimental bands. Sim-
ilarly, a theoretical infrared (Raman) mode can aid the identification of
the experimental absorption when the profile of a theoretical Raman
(infrared) mode are not alike to the experimental band. These are the
reasons by which we have chosen several theoretical models.
4. Conclusion
Infrared and Raman spectroscopy can be very useful in the identifi-
cation and quantification of imidacloprid insecticides in field conditions,
aiding in the development of controlled released formulations for safe
delivery. In this work, we have characterized and identified the experi-
mental absorption bands of imidacloprid using a DFT approach
employing the M06-2 × and B3LYP exchange-correlation functionals.
The major part of the modes identified belong to the same type of vibra-
tion using either functional. However, for some modes the vibrational
assignments are distinct. RMSD values showed that the B3LYP function-
al within the PCM solvation model and vacuum provides the smallest
deviations relative to the experimental frequencies. The M06-2X com-
putations, on the other hand, predict the best molecular geometry for
imidacloprid. The combined analysis of the infrared and Raman theoret-
ical curves obtained from the M06-2X and B3LYP functionals in the PCM
framework was helpful for the identification of experimental spectral
features.
Acknowledgements
P. D. L.-N., and V.N.F. are senior researchers from the Brazilian Na-
tional Research Council (CNPq), and would like to acknowledge the fi-
nancial support received during the development of this work from
the Brazilian Research Agencies CAPES-PROCAD and Rede Nanobiotec,
CNPq-INCT-Nano(Bio)Simes project 573925/2008-9. E.W.S.C. received
financial support from CNPq project 307843/2013-0. The authors would
like to acknowledge the CENAPAD-UFC computer processing time allo-
cated for their Gaussian09 calculations. We also give special thanks to
M.S.A. Santana and Prof. A. P. Ayala from the Vibrational and Molecular
Spectroscopy Laboratory for helping us with the infrared and Raman
measurements.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.saa.2017.05.051.
253
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