Article

pubs.acs.org/JPCA

Theoretical Characterization of Dimethyl Carbonate at Low

Temperatures
R. Boussessi,† S. Guizani,† and M. L. Senent*
Departamento de Química y Física Teóricas, I. Estructura de la Materia, IEM-CSIC, Serrano 121, Madrid 28006, Spain

N. Jaïdane
Laboratoire de Spectroscopie Atomique, Moléculaire et Applications-LSAMA LR01ES09, Faculté des sciences de Tunis, Université de
Tunis El Manar, 2092, Tunis, Tunisie

ABSTRACT: Highly correlated ab initio methods (CCSD(T)

and RCCSD(T)-F12) are employed for the spectroscopic char-
acterization of the gas phase of dimethyl carbonate (DMC) at
low temperatures. DMC, a relevant molecule for atmospheric
and astrochemical studies, shows only two conformers, cis−cis
and trans−cis, respectively, of C2v and Cs symmetries. cis−cis-
DMC represents the most stable form. Using RCCSD(T)-F12
theory, the two sets of equilibrium rotational constants have
been computed to be Ae = 10 493.15 MHz, Be = 2399.22 MHz,
and Ce = 2001.78 MHz (cis−cis) and to be Ae = 6585.16 MHz,
Be = 3009.04 MHz, and Ce = 2120.36 MHz (trans−cis).
Centrifugal distortions constants and anharmonic frequencies for all of the vibrational modes are provided. Fermi displacements
are predicted. The minimum energy pathway for the cis−cis → trans−cis interconversion process is restricted by a barrier of
∼3500 cm−1. DMC displays internal rotation of two methyl groups. If the nonrigidity is considered, the molecule can be classified
in the G36 (cis−cis) and the G18 (trans−cis) symmetry groups. For cis−cis-DMC, both internal tops are equivalent, and the
torsional motions are restricted by V3 potential energy barriers of 384.7 cm−1. trans−cis-DMC shows two different V3 barriers of
631.53 and 382.6 cm−1. The far-infrared spectra linked to the torsional motion of both conformers are analyzed independently
using a variational procedure and a two-dimensional flexible model. In cis−cis-DMC, the ground vibrational state splits into nine
components: one nondegenerate, 0.000 cm−1 (A1), four quadruply degenerate, 0.012 cm−1 (G), and four doubly degenerate
0.024 cm−1 (E1 and E3). The methyl torsional fundamentals are obtained to lie at 140.274 cm−1 (ν15) and 132.564 cm−1 (ν30).

■ INTRODUCTION
At room temperature, dimethyl carbonate (DMC, CH3O−CO−
OCH3, dimethyl ester) is a liquid (melting point = 2−4 °C and
boiling point = 90 °C) usually employed as a methylating agent
and as a solvent. It is considered to be a green reagent, and it has
been exempted from classification as a volatile organic
compound (VOC).1 Because DMC shows very high oxygen
content, it has been suggested as potential oxygenated fuel
additive.2 This application has motivated studies of its environ-
mental impact when it is released into the atmosphere where it
develops a rich green atmospheric chemistry.2
The structure DMC has attracted special attention because the
molecule presents various conformers that intertransform
through internal rotation.3 It has also attracted interest because
DMC shares the empirical formula of C3H6O3 with a large list of
isomers, which have been the object of previous microwave
spectroscopy studies4 motivated by the astrophysical search in
the space where isomerism is a frequent fact.5 Their relative
abundances in extraterrestrial sources have been discussed
in terms of relative stability and on the basis of molecular
properties (i.e., the collisional parameters) that can be keys of the
detectability.5,6 Not necessarily are the most abundant isomeric
forms in astrophysical sources the more stable ones. For example,
among the C2H4O2 compounds, methyl formate is more abun-
dant in the interstellar medium than acetic acid. For C3H6O3
molecules, nothing can be said because only dihydroxyacetone
has been astrophysically discovered.7,8 The facts that only lactic
acid and DMC are commercialy available and some species show
very low dipole moment, can explain why these species have not
been detected.
Recently, Lovas et al.4 have determined the binding energies of
13 C3H6O3 isomers. In this ranking of stabilities, DMC is placed
in the fourth position with a relative energy of ∼4500 cm−1 with
respect to the most stable one, the lactic acid.4 Furthermore,
DMC shows at least two conformers cis−cis and trans−cis, and a
third near-trans−near-trans stable structure has been postulated.3
Recently, the microwave spectrum of the cis−cis form was
measured by Lovas et al.4 over the frequency ranges of 8.4−25.3
Received: February 24, 2015
Revised: March 31, 2015
Published: March 31, 2015

© 2015 American Chemical Society 4057 DOI: 10.1021/acs.jpca.5b01836

J. Phys. Chem. A 2015, 119, 4057−4064
The Journal of Physical Chemistry A Article

and 227−350 GHz. The analysis and assignments were Thus, anharmonic quadratic, cubic, and quartic force field was
accomplished with the Xiam and Erham programs developed obtained with Möller−Plesset theory (MP2) in connection with
for systems with two identical methyl tops.9,10 The dipole the cc-pVTZ correlation-consistent basis set (denoted in this
moment has been evaluated to be 0.293(3) debye.4 Article by VTZ).26
Measurements of the Raman spectrum of DMC started very The torsional parameters and the torsional energy levels were
early.11,12 In 1966, Collingwood et al. recorded the infrared determined using a variational procedure for solving a vibrational
spectrum between 4000 and 400 cm−1.13 Later, in 1974, Katon Hamiltonian of reduced dimensionality. For this purpose, we
and Cohen reported studies in liquid and solid phases.14 In 1999, employed our code ENEDIM.27 All of the kinetic and potential
Bohets and van der Veken have analyzed and assigned both parameters of the two-dimensional Hamiltonian were computed
infrared and Raman spectra in vapor, and in amorphous and using a set of MP2 geometries. Single point CCSD(T) calcula-
crystalline solid phases between 4000 and 50 cm−1, respectively, tions were performed on the MP2 geometries to obtain refined
on the basis of MP2/6-31G(d,p) and DFT/6-31G(d,p) ab initio potential parameters. The augmented correlation-consistent
calculations.3 Other previous theoretical studies are also basis set aug-cc-pVTZ (denoted in this Article by AVTZ) was
available.15,16 The harmonic frequencies for all of the vibrational used.28
modes were determined at different levels of theory by Sun et al.15 Equilibrium Geometries. After an exhaustive search of
In this Article, we provide accurate theoretical molecular prop- equilibrium structures using MP2/AVTZ, we concluded that
erties that we expect can help future experimental assignments DMC shows only two planar conformers of C2v and Cs symmetry,
of spectra motivated by the search of new molecules in respectively (see Figures 1 and 2). In this Article, we refer to
astrophysical sources. For this purpose, we use state-of-the-art
ab initio methods to focus on the spectroscopic characterization
of DMC at low temperatures. Under these conditions, the lower
torsional energy levels can be populated. DMC displays a
complex far-infrared spectrum because four internal rotations,
the C−OCH3 torsions (denoted by α1 and α2 in this Article) and
the two methyl group torsions (denoted by θ1 and θ2 in this
Article), are responsible for the nonrigid properties. The α1 and
α2 torsions cause the conformer intertransformation, whereas θ1
and θ2 transform equivalent minima. For each conformer, we
analyze the far-infrared spectra (FIR and Raman) using a two-
dimensional variational model for which independent coor-
dinates are θ1 and θ2. The study is applied to the cis−cis and
trans−cis conformers independently, on the basis that the energy
barrier between both structures (∼3500 cm−1) is sufficiently high
to justify this theoretical treatment. Spectroscopic parameters
obtained using second-order perturbation theory are also
provided for all of the vibrational modes, and they are used to Figure 1. CCSD(T) pathway corresponding to the intertransformation
help the variational calculations. of the two conformers of dimethyl carbonate.

■ RESULTS AND DISCUSSION

Computational Details. The structural parameters of the
two DMC conformers and the equilibrium rotational constants
have been computed using the explicitly correlated coupled-
cluster method CCSD(T)-F12b,17,18 implemented in MOLPRO
(2012).19 The default options were selected. The atomic orbitals
were described by the cc-pVTZ-F12 basis set of Peterson et al.20
(denoted in this Article by VTZ-F12) in connection with the
corresponding basis sets21 for the density fitting and the resolu-
tions of the identity. The rotational constants were enhanced
adding a core−valence correlation correction determined with
CCSD(T) (coupled-cluster theory with singles and doubles sub-
stitutions, augmented by a perturbative treatment of triple
excitations)22 and the cc-pCVTZ basis set.23,24
The rotational parameters (rotational constants at the
vibrational levels as well as the centrifugal distortion constants)
and the harmonic and anharmonic frequencies for all of the
vibrational modes were calculated using vibrational second-order
perturbation theory (VPT2) as implemented in Gaussian 09.25
To limit computational expense, which is significant given the
molecular size (DMC contains six heavy atoms and six hydrogen
atoms), different levels of theory were combined. For the first-
order properties, such as the rotational constants or the harmonic
fundamentals, very accurate methods were employed. However,
anharmonic effects were computed at lower levels of theory.
4058
Figure 2. Equilibrium geometry of cis−cis dimethyl carbonate.
Definition of the torsional coordinates.
them as cis−cis-DMC and trans−cis-DMC. cis−cis-DMC is the
most stable conformer. If the methyl group internal rotational
rotation is considered, the corresponding molecular symmetry
groups (MSG) are the G36 and G18. The structural parameters are
shown in Table 1, as well as the rotational constants. The search
for more minimum energy geometries (i.e., near-trans−near-trans3)
has been unproductive. We found a structure with imaginary
frequencies.
Figure 1 shows the minimum energy pathway for the cis−cis →
trans−cis conversion process, which is restricted by a barrier
of 3501 cm−1 when CCSD(T) theory is employed. At the
CCSD(T)-F12 level of theory, the trans−cis-DMC lies 1091.5 cm−1
DOI: 10.1021/acs.jpca.5b01836
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The Journal of Physical Chemistry A Article

Table 1. CCSD(T)-F12/VTZ-F12 Total Electronic Energies (E, in au), Relative Energies (Er, in cm−1), Structural Coordinates
(Distances in Å, Angles in deg), Rotational Constants (in MHz), and MP2/AVTZ Dipole Moment (in debye) of the Two
Conformers of DMC
cis−cis trans−cis cis−cis trans−cis
C2v Cs C2v Cs
O2C1 1.3325 1.3335 E −343.219689 −343.214716
O3C1 1.3325 1.3434 Er 0.0 1091.5
C4O2 1.4315 1.4316 θ1 0.0 0.0
C5O3 1.4315 1.4329 θ2 0.0 0.0
O6C1 1.2043 1.1982 C4O2C1O3 180.0 0.0
H7C4 1.088 1.0854 C5O3C1O2 180.0 180.0
H8C4, H9C4 1.0850 1.0879
H10C5 1.0850 1.0853 calcd exp4 calcd
H11C5, H12C5 1.0850 1.0876 μ 0.3498 3.9212
O3C1O2 108.2 112.2 Ae 10 493.15 6585.16
O6C1O2 125.9 122.8 Be 2399.22 3009.04
O6C1O3 125.9 125.1 Ce 2001.78 2120.36
C4O2C1 113.4 118.6 A0 10 432.29 10 411.707 (5) 6544.72
C5O3C1 113.4 113.3 B0 2379.08 2371.5263 (9) 2981.28
H7C4O2 105.4 105.1 C0 1986.12 1980.2513 (9) 2102.67
H8C4O2, H9C4O2 110.4 110.9
H10C5O3 105.4 105.5
H11C5O3 110.4 110.2
H12C5O3
H7C4O2C1 180.0 180.0
H8C4O2H7−H9C4O2H7 119.6 119.0
H10C5O3C1 180.0 180.0
H11C5O3H10−H12C5O3H10 119.6 119.0

over the cis−cis-form (see Table 1). As was expected, the process
carries out a significant change of the dipole moment (from
0.3498 to 3.9212 D). However, with the exceptions of three
angles, O3C1O2, C4O2C1, and O6C1O2, the process occurs with-
out significant changes in the structural parameters. The two
methyl groups display a slightly distorted C3v structure.
Table 1 displays the equilibrium and the ground vibrational
state rotational constants. The last are compared to previous
experimental data derived from microwave spectroscopy.4 cis−
cis-DMC is a near prolate top (κ ≈ −0.91), and trans−cis-DMC is
a clear asymmetric rotor (κ ≈ −0.60). The equilibrium param-
eters of the cis−cis and trans−cis forms were computed to be Ae =
10 493.15 MHz, Be = 2399.22 MHz, and Ce = 2001.78 MHz and
to be Ae = 6585.16 MHz, Be = 3009.04 MHz, and Ce = 2120.36
MHz, respectively. The ground vibrational state rotational con-
stants were obtained using the equation:
B0 = Be + ΔBe core + ΔBvib
Here, ΔBecore regards the core−valence-electron correlation
effect on the equilibrium parameters. It was computed at the
CCSD(T)-cc-pCVTZ level of theory as the difference between
Be(CV) (calculated correlating both core and valence electrons)
and Be(V) (calculated correlating just the valence electrons).
ΔBvib represents the vibrational contribution to the rotational
constants derived from the VPT2 αri vibration−rotation interac-
tion parameters determined using the MP2 cubic force field (see
below). The resulting corrections are
form ΔAvib ΔAecore ΔBvib ΔBecore ΔCvib ΔCecore
cis−cis −94.61 33.95 −25.46 5.32 −20.47 4.81
trans−cis −58.35 17.91 −34.48 6.72 −22.74 5.05
The ground vibrational state rotational constants of the most
stable cis−cis form has been estimated to be A0 = 10 432.29 MHz,
B0 = 2379.08 MHz, and C0 = 1986.12 MHz in good agreement
4059
with the experimental parameters of ref 4 (A0 = 10 411.707(5)
MHz, B0 = 2371.5263(9) MHz, and C0 = 1980.2513(9) MHz).
They are shown in Table 1.
Full-Dimensional Anharmonic Analysis. The anharmonic
force field has been computed at the MP2/VTZ level of theory.
In Table 2, VPT2 harmonic and anharmonic frequencies are com-
pared to the experimental infrared and Raman transitions recently
measured by Bohets and van der Veken.3 The experimental band
centers, which are emphasized in bold, correspond to the Raman
transitions.3 The calculated values have been tentatively assigned to
local modes (s = stretching, b = bending, and t = torsions) and have
been classified following the representation of the C2v and Cs groups.
Especially tricky is the correlation of normal torsional modes
and local modes. For the low frequency modes, this correlation is
almost impracticable because the α coordinates (C−OCH3
torsions) are strongly coupled with the θ coordinates (methyl
torsions) in the normal coordinates.
The experimental sample3 contains a mixture of the two DMC
conformers. The main observed bands were assigned to the most
stable one.3 Some of the unassigned transitions observed at
(1105, 1047, 633, and 578 cm−1) were correlated to the second
conformer. On the basis of the agreement between our anharmonic
values and the experimental data for the previously assigned bands,
we propose new assignments of the unclassified trans−cis transi-
tions to the fundamentals band centers ν13, ν14, ν16, and ν17.
Focusing on the torsional two-dimensional analysis (see
below), one of the most beneficial uses of the VPT2 theory is the
prediction of Fermi interactions. Calculated bands for which
the expected Fermi displacements are larger than 5 cm−1 are
emphasized in bold. This occurs with ν2(a1) and the ν18(b2)
methyl stretching fundamentals of the cis−cis form. In the case of
the trans−cis form, three fundamental ν3(a′), ν4(a′), and ν18(a′)
are also displaced.
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Table 2. Harmonic and Anharmonic Fundamental Frequencies (ω and ν, in cm−1) of DMC Calculated with MP2/VTZ
cis−cis trans−cis
assign. ω νa expb assign. ω ν expc
ν1 a1 CH3 s 3220 3082 3037 a′ CH3 s 3219 3081
3036
ν2 CH3 s 3095 3031 2968 CH3 s 3213 3075
2970
ν3 CO s 1812 1784 1774 CH3 s 3097 3016
1774
ν4 CH3 b 1524 1495 CH3 s 3094 3039
ν5 CH3 b 1476 1442 1435 CO s 1838 1808
ν6 CH3 b 1242 1214 1210 CH3 b 1525 1491
1215
ν7 CH3−O s 1159 1126 1130 CH3 b 1521 1480
1130
ν8 CO2 s 936 917 921 CH3 b 1506 1484
921
ν9 CO2 b 521 514 516 CH3 b 1478 1443
517
ν10 COC b 246 241 244 CO2 s 1308 1268
250
ν11 b1 CH3 s 3189 3050 3006 CH3 b 1227 1199
ν12 CH3 b 1509 1468 1456 CH3 b 1211 1183
ν13 CH3 b 1198 1174 1167 CH3−O s 1137 1106 1105
ν14 CO3 b 812 800 798 CH3−O s 1068 1039 1047
ν15 CH3 t 175 169 126 CO2 s 881 861
ν16 CO t 132 128 118 OCO2 b 647 637 633
ν17 b2 CH3 s 3220 3082 3037 CO2 b 585 576 578
3036
ν18 CH3 s 3094 2963 2968 COC b 357 359
2970
ν19 CH3 b 1522 1494 COC b 253 245
ν20 CH3 b 1502 1464 1456 a″ CH3 b 3194 3054
ν21 CO2 s 1334 1293 1293 CH3 s 3190 3052
ν22 CH3 b 1218 1192 CH3 b 1515 1486
ν23 CH3−O s 1020 990 990 CH3 b 1506 1475
ν24 OCO2 b 703 694 693 CH3 b 1197 1172
ν25 C−O−C b 359 356 373 CH3 b 1192 1167
ν26 a2 CH3 s 3189 3050 3006 CO3 s 799 786
ν27 CH3 b 1508 1467 1456 CH3 t 227 218
ν28 CH3 b 1195 1171 CH3 t 185 169
ν29 OC t 212 207 OC t 168 167
ν30 CH3 t 158 154 OC t 138 131
a
Δν = Fermi displacements (emphasized in bold if Δν > 5 cm−1). bInfrared frequencies of ref 3; Raman transitions emphasized in bold. cInfrared
frequencies of ref 3; new assignments [this work].

Strong Fermi interactions among the torsional modes and modes and the remaining vibrations. Under these conditions,
the remaining vibrations are not predicted (see Table 3). This it is possible to define the following torsional Hamiltonian for
validates the two-dimensional model employed below. Few J = 0:29,30
possible displacements are obtained; that is, the combination 2 2
⎛ ∂ ⎞ ⎛ ∂ ⎞
levels ν15 + ν29 and ν15 + ν30 interact with the COC bending Ĥ (θ1 , θ2) = −∑ ∑ ⎜ ⎟Bθθi j (θi , θj)⎜⎜ ⎟⎟
fundamental (ν25). This effect displaces ∼10 cm−1 the torsional i = 1 j = 1 ⎝ ∂θi ⎠ ⎝ ∂θj ⎠
combination bands, in the cis−cis conformer.
In the case of the trans−cis-conformer, the overtone 2ν28 + V eff (θ1 , θ2) (1)
(methyl torsion) is strongly coupled with the COC bending
fundamental (ν18). The corresponding torsional band can be where the independent coordinates θ1 and θ2 are identified with
displaced an amount of 13 cm−1 to the lower frequencies. the two CH3 torsions (see Figure 1). These two coordinates are
defined as a function of three dihedral angles:31
Table 3 displays rotational constants in the torsional
fundamentals and centrifugal distortion constants. θ1 = (H 7C4 O2 C1 + H8C4 O2 C1 + H 9C4 O2 C1)/3 − π
Variational Torsional Analysis. The methyl torsional
energy levels were determined variationally assuming very small, θ2 = (H10C5O3C1 + H11C5O3C1 + H12C5O3C1)/3 − π
almost negligible, interactions between the two methyl torsional (2)

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The Journal of Physical Chemistry A Article

Table 3. Rotational Spectroscopic Parameters of DMC (in MHz) Calculated with MP2/VTZ
cis−cis trans−cis
κ −0.905150 κ −0.596560
Ae 10 379.8 Ae 6525.35
Be 2387.37 Be 3000.69
Ce 1989.45 Ce 2110.04
A0 10 285.19 A0 6467.00
B0 2361.91 B0 2966.21
C0 1968.98 C0 2087.30
ν15 = 169 cm−1 ν27 = 218 cm−1
A (ν15) 10 272.81 A (ν27 = 1) 6470.63
B (ν15) 2357.30 B (ν27 = 1) 2955.35
C (ν15) 1966.22 C (ν27 = 1) 2084.43
ν30 = 154 cm−1 ν28 = 169 cm−1
A (ν30) 10 271.97 A (ν28 = 1) 6441.19
B (ν30) 2358.38 B (ν28 = 1) 2965.22
C (ν30) 1967.06 C (ν28 = 1) 2087.01
ΔJ 0.1876 × 10−3 ΔJ 0.4510 × 10−3
ΔK 0.4359 × 10−2 ΔK 0.5585 × 10−2
ΔJK 0.1330 × 10−2 ΔJK −0.5872 × 10−3
δJ 0.3109 × 10−4 δJ 0.1526 × 10−3
δK 0.5422 × 10−3 δK 0.6118 × 10−3
Predicted Fermi Displacements (in cm−1)
ν25 (COC bending) 357.5 → 356.0 2ν28 335.4 → 321.9
ν15 + ν30 318.2 → 311.1 2ν29 (CO torsion) 331.4 → 332.0
ν15 + ν29 (CO torsion) 372.7 → 381.3 ν29 + ν28 332.4 → 334.1
ν18 (COC bending) 347.5 → 358.6

Bθiθj and Veff(θ1,θ2) represent the kinetic energy parameters and 3N − 6

the effective potential energy surface. This last can be defined as
the sum of three terms:
V eff (θ1 , θ2) = V (θ1 , θ2) + V ′(θ1 , θ2) + V ZPVE(θ1 , θ2)
(3)
where V(θ1, θ2), V′(θ1, θ2), and V ZPVE
(θ1, θ2) are the potential
energy surface, the pseudopotential, and the zero point
vibrational energy correction, respectively.29,30,32
One aspect that is important to discuss is the validity of the
two-dimensional model for DMC because a treatment in four
dimensions appears to be more precise given the strong coupling
between α and θ coordinates. All of the out-of-plane bending
coordinates involving the O−CH3 groups contribute to the
torsional normal coordinates. In addition, in trans−cis-DMC, the
2ν29 overtone interacts with the COC bending fundamental (see
Table 3).
Although a 4D-model (or a 5D model) could provide more
accurate frequencies, it is extremely expensive from the com-
putational point of view. Furthermore, the assignments of
previous experimental microwave studies have been performed
using effective Hamiltonian for two identical tops. To our
knowledge, effective Hamiltonians depending on many vibra-
tional variables are not contemplated for future rotational
assignments. To avoid large computational effort and to consider
these interactions partially, we have employed a flexible two-
dimensional model where the α coordinates and the remaining
internal coordinates are allowed to be relaxed during the CH3
internal rotation. The potential energy surface is calculated from
the energies of 7 and 10 conformations for selected values of
the H7C4O2C1 and H10C5O3C1 dihedral angles. A set of 3N − 8
internal coordinates (N = number of atoms) are allowed to be
relaxed. For all of the structures, the zero point vibrational energy
is corrected within the harmonic approximation:
4061
ωk
EZPVE(θ1 , θ2) = ∑
k=3
2 (4)
To obtain the effective potential energy surfaces, we combine
different levels of ab initio calculations. The geometries are
optimized using MP2/VTZ; the energies are obtained in
CCSD(T)/AVTZ single point calculations, and zero point
vibrational energy correction is determined with MP2/VTZ. For
both conformers, the effective surfaces are determined by fitting
the effective energies to the double Fourier series transforming
as the totally symmetric representation of the G36 and G18
molecular symmetry groups. Thus, for cis−cis-DMC:
V eff (θ1 , θ2) = 415.378 − 192.83(cos 3θ1 + cos 3θ2)
+ 1.178 cos 3θ1 cos 3θ2 − 14.582(cos 6θ1 + cos 6θ2)
− 0.720(cos 6θ1 cos 3θ2 + cos 3θ1 cos 3θ2)
− 0.292 cos 6θ1 cos 6θ2 − 2.166 sin 3θ1 sin 3θ2
and for trans−cis-DMC:
V eff (θ1 , θ2) = 541.588 − 323.084 cos 3θ1
− 198.679 cos 3θ2 + 6.958 cos 3θ1 cos 3θ2
− 12.012 cos 6θ1 − 16.712 cos 6θ2
+ 0.431 cos 6θ1 cos 3θ2 + 0.361 cos 3θ1 cos 3θ2
+ 1.151 cos 6θ1 cos 6θ2 + 1.207 sin 3θ1 sin 3θ2
From this effective potential energy surfaces, the energy
barriers and potential parameters shown in Table 4 can be
derived. This table also shows the kinetic energy parameters
calculated with the code ENEDIM27 from the optimized geom-
etries of the conformers. The effective rotation barriers, V3, of the
DOI: 10.1021/acs.jpca.5b01836
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Table 4. Effective Potential and Kinetic Parameters (in cm−1) Table 5. Low Torsional Energy Levels (in cm−1) of cis−cis-
of DMC Calculated with CCSD(T)/AVTZ DMC and trans−cis-DMC Calculated at the CCSD(T)/AVTZ
Level of Theory
cis−cis trans−cis
calcd exp.4 calcd calcd calcd
V3 (θ1) = E(60°,0°) − E(0°,0°) 384.7 398.13 631.5 ν30 ν27
ν15 sym. E Eeff ν28 sym. E Eeff
V3 (θ2) = E(0°,60°) − E(0°,0°) 384.7 398.13 382.6
E(60°,60°) − E(60°,0°) − E(0°,60°) 4.72 7.82 00 A1 0.000 0.000 00 A1 0.000 0.000
B11 5.5883 5.4290 G 0.015 0.012 E1 0.001 0.001
B22 5.5883 5.4956 E1 0.030 0.024 E2 0.013 0.011
B12 −0.2801 −0.1153 E3 0.030 0.024 E3 0.013 0.011
E4 0.013 0.011
10 A3 127.648 132.831 10 A2 132.046 136.105
two equivalent methyl torsions of cis−cis-DMC have been G 127.340 132.564 E1 132.046 136.106
evaluated to be 384.7 cm−1. They have been found to be 631.53 E2 127.057 132.316 E2 131.512 135.615
and 382.6 cm−1 for trans−cis-DMC where the two tops are not E3 127.057 132.316 E3 131.513 135.616
equivalent. One-dimensional cuts of the surfaces are shown in E4 131.513 135.616
Figure 3. The cis-barriers are of the same order of magnitude as 01 A2 135.489 140.528 01 A2 166.779 170.358
G 135.198 140.274 E1 166.738 170.321
E1 134.882 139.999 E2 166.790 170.367
E4 134.882 140.000 E3 166.749 170.330
E4 166.749 170.330
20 A1 230.377 238.919 20 A1 233.558 239.865
G 231.000 239.622 E1 233.558 239.866
E1 237.364 245.570 E2 240.376 246.526
E3 237.358 245.565 E3 240.377 246.527
E4 240.377 246.527
11 A4 231.793 240.554 11 A1 299.420 307.677
G 238.401 246.716 E1 299.393 307.658
E2 239.258 247.627 E2 298.908 307.216
E4 239.262 247.631 E3 298.881 307.195
E4 298.881 307.195
02 A1 264.623 274.279 02 A1 314.896 320.804
G 264.245 273.935 E1 315.727 321.595
E1 263.881 273.599 E2 306.439 312.636
E3 263.874 273.593 E3 306.440 312.637
E4 306.440 312.637
ZPVE 142.507 148.771 158.863 163.256

intense than those of ν27(a″). Because the 2D-potential energy

Figure 3. One-dimensional cuts of the 2D potential energy barriers
surfaces, V3cis−cis (θ = θ1), V3trans−cis (θ = θ1), and V3trans−cis (θ = θ2), of the
cis−cis (in red) and trans−cis (in black) conformers.
for acetone (367.07 cm−1)33 and for methanol (377.94 cm−1).34
Table 4 shows also the difference of energies E(60°,60°) −
E(60°,0°) − E(0°,60°) that can be understood as a measure of
the two methyl group interactions. This difference is very small
as compared to other molecules such as acetone33 or dimethyl-
ether.35,36 The more significant interaction terms of the surfaces
cos 3θ1 cos 3θ2 and sin 3θ1 sin 3θ2 present expansion coefficients
almost negligible if they are compared to the heights of the
torsional barriers.
The torsional energy levels of both conformers are shown
in Table 5. The first columns are devoted to the calculations
performed using V(θ1,θ2), and the second columns to those
performed with Veff(θ1,θ2). Both groups of energies are denoted
by E and Eeff. The energy levels are classified following the
representations of the G36 and the G18 MSG and the vibrational
quanta. cis−cis-DMC presents two methyl torsional modes
ν15(b1) and ν30(a2), one active in infrared and the second one
inactive. In the case of trans−cis-DMC, both modes are infrared
active. The bands assigned to ν28(a″) are expected to be more
4062
surface shows nine minima, each level splits into nine
components. For cis−cis-DMC, the sublevels are one non-
degenerate (Ai, i = 1,2,3,4), two two-degenerate (Ei and Ej,
i = 1,2; j = 3,4)), and one four times degenerate (G). The G
components of the two fundamentals, which are expected to
be the prominent subcomponents, are calculated to lie at
140.274 cm−1 (ν15) and 132.564 cm−1 (ν30) with the isotopically
corrected potential. The (0, 0) ground-state subcomponents are
found to be 0.000 cm−1 (A1), 0.012 cm−1 (G), and 0.024 cm−1
(E1 and E3).
The trans−cis levels split into one doubly degenerate sublevel
(Ai; i = 1, 2) and four quadruply degenerate (Ei; i = 1, 2, 3, 4). In
this case, the two fundamentals are found at 170.358 cm−1 (ν28)
and 136.105 cm−1 (ν27) and the (0, 0) sublevels at 0.000 cm−1
(A1), 0.001 cm−1 (E1), and 0.0011 cm−1 (E2, E3, and E4). The
energy differences between subcomponents are smaller in the
trans−cis-form where one of the barriers is double higher than
cis−cis-DMC.
Unfortunately, there are no experimental data available with
which to compare our results. To our knowledge, the unique
observation in this spectrum region is from Bohets and Veken,3
who have observed unassigned Q branches of Type C bands
at 126 and 118 cm−1. It seems reasonable to assign them to
DOI: 10.1021/acs.jpca.5b01836
J. Phys. Chem. A 2015, 119, 4057−4064
The Journal of Physical Chemistry A
torsional out-of-plane modes. What is not possible is to clarify if
they have be assigned to methyl group torsion or to the CO bond
torsions. Furthermore, both types of torsions are participating
in all of the torsional normal modes, and this makes difficult
the calculation of the zero point vibrational correction. Large
differences between E and Eeff energies can be derived from these
interactions.
When the behavior of the cis−cis and trans−cis forms is
compared, it can be concluded that band centers are displaced to
the large frequencies in the second conformer, which shows the
smaller splittings.
■ CONCLUSIONS
The exhaustive search of equilibrium structures of DMC leads to
two planar conformers of C2v and Cs symmetry. The corre-
sponding energy difference has been calculated to be 1091.5 cm−1
and the equilibrium rotational constants to be Ae = 10 493.15
MHz, Be = 2399.22 MHz, and Ce = 2001.78 MHz (cis−cis) and to
be Ae = 6585.16 MHz, Be = 3009.04 MHz, and Ce = 2120.36 MHz
(trans−cis). The ground vibrational state rotational constants of
the most stable cis−cis form have been estimated to be A0 =
10 432.29 MHz, B0 = 2379.08 MHz, and C0 = 1986.12 MHz.
The MP2/VTZ anharmonic force field shows that the
correlation of normal torsional modes and local modes is
especially tricky given the coupling among all of the out-of-plane
vibrations of the molecule. Strong Fermi interactions among the
torsional modes and the remaining vibrations are not predicted
with the exception of the trans−cis overtone 2ν28 (methyl
torsion), which is strongly coupled with the COC bending
fundamental (ν18).
The effective rotation barriers, V3, of the two equivalent methyl
torsions of cis−cis-DMC have been evaluated to be 384.7 cm−1
and to be 631.53 and 382.6 cm−1 for trans−cis-DMC where the
two tops are not equivalent. The two fundamentals of cis−cis-
DMC and trans−cis-DMC are found at 140.274 cm−1 (ν15) and
132.564 cm−1 (ν30) and at 170.358 cm−1 (ν28) and 136.105 cm−1
(ν27), respectively. The energy differences between torsional
splittings are smaller in the trans−cis-form where one of the
barriers is double that in cis−cis-DMC.
■
AUTHOR INFORMATION
Corresponding Author
*Phone: +34915616800. E-mail: ml.senent@csic.es.
Present Address
† (16) Labrenz, D.; Schröer, W. Conformational Analysis of Symmetric
Laboratoire de Spectroscopie Atomique, Moléculaire et
Applications-LSAMA LR01ES09, Faculté des sciences de
Tunis, Université de Tunis El Manar, 2092, Tunisie.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This research was supported by the MINECO of Spain grant
FIS2013-40626-P and by the Marie Curie International Research
Staff Exchange Scheme Fellowship within the seventh European
Community Framework Program under grant no. PIRSES-GA-
2012-31754. We acknowledge the COST Actions CM1405
“MOLIM” and CM1401 “Our Astrochemical History”. We also
acknowledge the CTI (CSIC) and CESGA for computing
facilities.
4063
Article
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J. Phys. Chem. A 2015, 119, 4057−4064