PCCP

PAPER

Computational analysis of the far infrared spectral

region of various deuterated varieties of ethylene
Cite this: Phys. Chem. Chem. Phys.,
2020, 22, 23785 glycol†
Rahma Boussessi* and Marı́a Luisa Senent

Received 20th June 2020,
Accepted 26th September 2020
DOI: 10.1039/d0cp03315d
rsc.li/pccp
The far infrared spectra of three deuterated isotopologues of ethylene glycol, CH2OD–CH2OD,
CH2OD–CH2OH and CH2OH–CH2OD, where the latter two species differ in their intramolecular
hydrogen-bonding arrangement, are studied using highly correlated ab initio methods, vibrational
second order perturbation theory and a variational procedure of reduced dimensionality. New subroutines
suitable for the study of large systems with more than two interacting large amplitude motions were
implemented and applied. The molecular symmetry of ethylene glycol decays by the formation of weak intra-
molecular bonds producing very asymmetrical stable structures. Three internal rotations contribute to the
formation of a very anisotropic potential energy surface and to the puzzling distribution of the rovibrational
energy levels. The ground vibrational state rotational constants and the centrifugal distortion constants
(S-reduction, Ir representation) corresponding to the aGg0 (G1) and gGg0 (G2) forms are provided for the
studied isotopologues. The low-lying vibrational levels up to 550 cm1 are obtained variationally for J = 0.
Two series of sublevels of the ground vibrational state are obtained: eight components localized in G1 lying
between 0.0 and 0.3 cm1 and eight sublevels localized in G2 lying between 138.1 and 138.4 cm1. The gap
between both sets is lower in CH2OD–CH2OD and more dispersed in the monodeuterated variety.

Introduction
Although the most popular application of ethylene glycol
(CH2OH–CH2OH) is as antifreeze, the molecule represents a
high-symmetry non-rigid species of astrophysical relevance. It
was identified in the Murchison and Murray meteorites1 and in
ices in the hot core of Orion.2 Together with other organic
compounds, it represents a key species in understanding the
composition of extra-terrestrial ices. Even if it is assumed to be
of low abundance in the gas phase, ethylene glycol was detected in
emission from the galactic center source Sagittarius B2(N-LMH) by
means of several millimeter-wave rotational torsional transitions
of its lowest energy conformer.3 Very recently, both lowest state
conformers, aGg0 (G1) and gGg0 (G2), were observed in the gas
phase in the protostar IRAS 16293-2422, G2 for the first time
in the interstellar medium, using the ALMA observatory.4
Both structures were identified by ALMA toward the Orion
Kleinmann–Low (Orion-KL) nebula, with similar relative abundances
observed for the two G1:G2 conformers.5 In both papers,4,5
the abundance ratio is the object of discussion, and nothing is
Departamento de Quı́mica y Fı́sica Teóricas, Instituto de Estructura de la Materia,
IEM-CSIC, Unidad Asociada GIFMAN, CSIC-UHU, Serrano 121, Madrid 28006,
Spain. E-mail: ml.senent@csic.es
† Electronic supplementary information (ESI) available. See DOI: 10.1039/d0cp03315d
said about the job played by the minimum interconversion that
can occur at low temperatures because the torsional barriers are
low. The aim of the present paper is to analyse the interconversion
pathways for the low-energy structures and their effect on the
spectroscopic properties and on the low-lying vibrational
(torsional) states. It has to be considered that the torsional
states can be populated at very low temperatures. Abundant
molecules such as methyl formate or dimethyl ether have been
observed in excited torsional states.6,7
Ethylene glycol observation in extraterrestrial gaseous sources
is arduous, not only because of its supposed low abundance, but
also because it is a species not entirely characterized from the
spectroscopic point of view in the gas phase. Publications explor-
ing the processes of its formation and destruction, or especially its
technical properties as an antifreeze, are common. However, while
necessary, few works address the unequivocal determination of its
spectroscopic properties at low temperatures. One of the reasons
for this lack of data availability is the enormous complexity of the
low-frequency spectral region. Even though it seems like a high
symmetry species as it contains two identical CH2OH alcoholic
groups, this symmetry decays by the formation of weak intra-
molecular bonds producing very asymmetrical stable structures.
Three internal rotations contribute to the formation of a very
anisotropic potential energy surface and to the puzzling distribu-
tion of the rovibrational energy levels.

This journal is © the Owner Societies 2020 Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 | 23785
Paper
Experimental spectroscopic studies of ethylene glycol started
early, although few of them paid attention to the far infrared
region.8 From the beginning, tentative assignments of the
rotational spectra revealed complications arising from the com-
plexity and anisotropy.9–16 The effect of the weak intramolecular
hydrogen bonds on the OH stretching transitions has attracted
special attention.17,18 The first works based on ab initio calculations
found unexpected outcomes when computed parameters were used
to help the interpretation of the experiments.19
Motivated by the recent astrophysical observations, the main
isotopologue and the deuterated species have attracted more
attention,14–16 although to our knowledge, the earlier work of
Buckley and Giguère8 is unique in offering far infrared spectral
information in the gas phase. Unfortunately, their spectra were
recorded at low resolution, insufficient for resolving the torsional
splittings. Prominent Q branches observed at 375 cm1, 325 cm1,
230 cm1 and 210 cm1 were assigned to the torsional motions of
the most stable gauche conformer. The ethylene glycol infrared
spectrum has also been recorded in Ar and Xe matrices20–22 and in
liquid and solid phases,23,24 but these measures are not suitable to
illustrate the low-frequency region.
When experimental work is intricate, theoretical procedures
can be crucial for assignments. Although ab initio results are
not exact, if they are accurate enough, they can provide sufficient
insight to make easy the analyses. This is the object of our
research. In a previous work,25 with the aid of explicitly correlated
coupled cluster theory and a variational procedure of reduced
dimensionality, we explored the spectrum of the main isotopolo-
gue of ethylene glycol (denoted by H1H2) in the far infrared region.
Nine different cis–gauche, trans and trans–gauche conformers were
identified. The ground state potential energy surface was found to
be very anisotropic in the gauche region and isotropic in the trans
region. Effects of intramolecular hydrogen bond effects, which
stabilize the low-lying structures, are reflected in the OH stretching
transitions and at the OH torsional levels. We found that a large
density of vibrational states derives from excitations of three
interacting torsional modes.
This new paper attends to three deuterated isotopologues
of ethylene glycol, CH2OD–CH2OD (denoted by D1D2), and
CH2OD–CH2OH (denoted by D1H2), and CH2OH–CH2OD
(denoted by H1D2). We provide a map of the low-lying vibrational
states computed using both a variational procedure and second
order vibrational theory (VPT2). The favored conformers contain a
unique hydrogen bond that breaks the symmetry (see Fig. 1 and 2).
Then, when VPT2 is employed, D1H2 and H1D2 are treated
differently because the theory has been developed for semi-rigid
species showing a unique minimum. However, the variational
procedure attends to the minimum interconversion. In this case,
both D1H2 and H1D2 are different minima of the same potential
energy surface. We assume that the first hydroxyl group hydrogen
(H1 or D1) atom is the one that contributes to the weak
intramolecular interaction.
The main challenge of this work is to get the correct classification
of the variational energy levels. In the anisotropic region, the
presence of different minima separated by more or less low
barriers draws a really asymmetrical shape. Tunneling effects
23786 | Phys. Chem. Chem. Phys., 2020, 22, 23785--23794
PCCP
Fig. 1 The three torsional coordinates responsible for the minimum
interconversion drawn on G1.
Fig. 2 The two low-lying conformers of ethylene glycol. Structures and
energies computed using CCSD(T)-F12.
cause splittings of the energy levels into many components, very
close in energy. For their classification, new procedures based
on contracted basis sets are implemented. Isotopic shifts are
employed to help assignments and to review previous results.25
The procedure followed in this work can be applied to other
organic molecules. Organic compounds showing non-rigidity are
frequent in astrophysical sources. Many of them show other
interests and applications. In these species, weak intramolecular
interactions can play important roles and can have strong effects
on the spectroscopic constants. Therefore, ethylene glycol can be
considered a good target to explore this effect.
Computational and theoretical procedures
Two different theoretical approaches were applied to describe the
ethylene glycol far infrared region. In a first step, vibrational second
order perturbation theory (VPT2)26 implemented in GAUSSIAN27
was employed to obtain anharmonic band positions and rotational
properties from full-dimensional force fields and previously com-
puted equilibrium structures.25 In a second step, the torsional
energy levels were obtained using a variational procedure of reduced
dimensionality implemented in the ENEDIM code.28–30 This proce-
dure considers implicitly the minima interconversion.
Both steps require electronic structure calculations performed
using the codes MOLPRO31 and GAUSSIAN.27 It is essential to
realize that while VPT2 delivers two different sets of properties for
D1H2 and H1D2, the variational procedure supplies a unique set
because they are treated as different minima of the same potential
energy surface.
New subroutines suitable for the study of large systems with
more than two interacting large amplitude motions were
implemented in ENEDIM.28–30 They are applied for the first
time in the present paper where ethylene glycol is employed as a
benchmark. Great effort has been made for the implementation
This journal is © the Owner Societies 2020
PCCP
of contracted basis sets very efficient for the reduction of
dimensionality and for the classification of the levels.
Full dimensional rovibrational analysis
In our previous paper devoted to the main isotopologue of ethylene
glycol,25 nine stable conformers were established. The low-lying
geometries were determined using explicitly correlated coupled
cluster theory, CCSD(T)-F12b,32,33 implemented in MOLPRO.31
The procedure was applied using the default options, the aug-
cc-pVTZ basis set (AVTZ)34 and the corresponding basis sets for
the density fitting and the resolutions of the identity. The entire
basis set is denoted by AVTZ-F12. The core-valence electron
correlation effects on the rotational constants were introduced
at the CCSD(T)35 (coupled-cluster theory with single and double
substitutions and perturbative treatment of triples) level of
theory in connection with the cc-pCVTZ basis set (CVTZ).36
In the present paper, devoted to the deuterated isotopologues,
the corresponding anharmonic fundamentals and rovibrational
spectroscopic parameters are determined using Vibrational
Second Order Perturbation Theory (VPT2)26 and an anharmonic
MP2/AVTZ force field.37 Centrifugal distortion constants
(S reduction, I r representation) are computed.38 The previous
computed parameters for the main isotopologue25 are employed
to compute isotopic shifts.
The variational procedure of reduced dimensionality
In ethylene glycol, three interacting torsional motions, the inter-
nal rotation of the two hydroxyl groups y1 and y2 and the central
bond torsion y, interconvert various minima of the potential
energy surface (PES). The minima are separated by dissimilar low
energy barriers causing tunneling splittings. An accurate analysis
of the far infrared (FIR) region requires considering explicitly the
minimum interconversion, as it is implemented in the ENEDIM
Fortran code.28–30
In our previous paper,25 we determined a three-dimensional
PES, V(y, y1, y2), very anisotropic in the gauche region and very
isotropic in the trans region. In principle, it was constructed
using 322 geometries defined for different values of three
dihedral angles.25 The density of selected geometries around the
gauche minima was enhanced to describe well the anisotropy
using a total number of 428 structures. In all the geometries,
21 internal coordinates were optimized at the MP2/AVTZ level of
theory. Further CCSD(T)-F12/AVTZ-F12 single point calculations
were performed to determine accurate energies. Details concern-
ing the definitions of coordinates and the PES computation and
fitting to an analytical equation retaining the symmetry (R2 =
1.0000; s = 0.195 cm1) can be found in our previous paper.25
The previously computed geometries and the 3D-surface, mod-
ified for the deuterated forms, were employed for constructing a
torsional Hamiltonian for J = 0:28–30
X3 X 3    
@ @
H ðy; y1 ; y2 Þ ¼  Bqi qj ðy; y1 ; y2 Þ
i¼1 j¼1
@qi @qj (1)
þ V eff ðy; y1 ; y2 Þ qi qj ¼ y; y1 ; y2
This journal is © the Owner Societies 2020
Paper
All the Hamiltonian parameters must be computed in all
the geometries, and later on, they are fitted to analytical
expressions. Bqiqj represents the mass-dependent kinetic energy
parameters.29 The mass-dependent effective potential Veff (y, y1, y)
depends on three terms,29
Veff(y, y1, y2) = V(y, y1, y2) + V 0 (y, y1, y2) + VZPVE(y, y1, y2)
(2)
V(y, y1, y2) is the ab initio isotopic invariant surface whereas
V 0 (y, y1, y2) and VZPVE(y, y1, y2) are two mass-dependent para-
meters, the Podolsky pseudopotential, which has been computed
to be negligible, and zero point vibrational energy corrections.
VZPVE(y, y1, y2) can be constructed by computing the EZPVE
energies in all the geometries:
X
1 i¼3N6
E ZPVE ¼ oi (3)
2 i¼4
where oI represents the harmonic fundamentals of the neglected
vibrational modes.
All the Hamiltonian parameters (kinetic parameters, V 0 , etc.)
are computed for all the selected geometries and fitted to triple
Fourier series25 obeying the symmetry requirements of the isotopo-
logue Molecular Symmetry Groups (MSGs). H1H1 and D1D2 show
two identical alcoholic groups connected by the C–C central bond
and can be classified into the double symmetry group G8 defined for
water peroxide.39,40 G8 contains eight non-degenerate irreducible
representations (A1, A2, A3, A4, A1d, A2d, A3d, and A4d).25 On the other
hand, the single MSG G2 group of the monosubstituted isotopolo-
gue encloses 2 representations (A1, A2). In Table 1, the correlation
between the G2 and G8 representation is established.
Since G8 is a double group, the 2a coordinate (2a = y) is
employed to distinguish between all the splitting components
although this effect is relevant for J 4 0. A symmetry adapted
triple Fourier series, jvNL, was used to factorize the Hamiltonian
matrix of H1H2 in boxes of low-dimensionality. For a more
efficient reduction, a new efficient procedure based on contracted
basis sets has been implemented for the reduction of dimension-
ality and for the classification of the levels. For the symmetric
species, a contracted basis set was employed for the 2a = y
coordinate:
X
jvNL ð2a; y1 ; y2 Þ ¼ jM ð2MaÞ½jN ðNy1 ÞjL ðLy2 Þ
M
(4)
 jL ðLy1 ÞjN ðN y2 Þ
where jM refers to solutions of the one-dimensional Hamiltonian
@ @
H ð2aÞ ¼  B2a þ Vð2aÞ (5)
@2a @2a
Table 1 Correlation table for the symmetry group G8 to G2
H1H2, D1D2 D1H2 (or H1D2)
G8 G2
A1 + A4, A1d + A4d A1
A2 + A3, A2d + A3d A2
Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 | 23787
Paper PCCP

For the low symmetry species D1H2, the basis set of eqn (4) is not Table 2 CCSD(T)-F12 relative energies (Er, in cm1), vibrationally corrected
sufficient. In this case, double contracted functions are more relative energies (EZPVE
r , in cm1), equilibrium rotational constants (in MHz),
dipole moment (m, in Debyes), and torsional coordinates (y, y1, y2, in degrees)
inexpensive:
X X G1
jvNL ðy; y1 ; y2 Þ ¼ jM ðMyÞ jN ðN y1 y2 Þ (6)
M N Er 0.0a y 61.7
m 2.5187 y1 193.0
In eqn (6), jM refers to solutions of the one-dimensional y2 51.4
Hamiltonian depending on y, and jN refers to solutions of a
two-dimensional Hamiltonian depending on y1 and y2. H1H2 D1H2 H1D2 D1D2
The new implemented contracted basis set signifies pre- EZPVE
r 0.0 666.3 655.0 1343.3
diagonalization that reduces the dimensionality. The small off- Ae 15386.062 14662.400 15146.090 14432.910
Be 5671.285 5623.450 5385.700 5342.210
diagonal matrix elements corresponding to large |M–M 0 | and Ce 4672.141 4571.600 4463.870 4370.770
|N–N 0 | values are negligible. In addition, the coefficients of the
contracted functions in the three-dimensional wave functions G2
(3D-WF) can help the classification of the levels. Since G8 is a Er 121.8 y 57.3
double group, the 2a coordinate (2a = y) is required to distinguish m 2.4650 y1 74.3
between all the splitting components. y2 43.9
For the classification of the levels, other complementary
H1H2 D1H2 H1D2 D1D2
arguments can be employed: probability integrals can help the
localization of the levels in the PES minima; expectation values ErZPVE 46.0 611.9 599.8 1287.0
Ae 15210.250 14512.030 14688.290 14032.530
of the one-dimensional Hamiltonians (computed using the Be 5615.620 5573.390 5395.920 5355.740
3D-WF) allow assignation of the energies to the torsional Ce 4651.000 4555.590 4528.400 4437.030
modes; expectation values of relevant properties such as rotational
G3
constants, kinetic energy, etc. can be significant. Relative intensi-
ties Ir of the transition between the Ei and Ef levels with respect to Er 296.9 y 60.9
m 0.2513 y1 80.7
the intensity of the most prominent band (IMAX r ) are also useful: y2 80.7
Ff i
Ir ¼ f i
(7) H1H2 D1H2 = H1D2 D1D2
FMAX
EZPVE
r 84.4 586.0 1135.0
where Ae 15128.419 14402.020 13733.060
Be 5571.240 5478.550 5389.010
F i!f ¼ ðEf  Ei ÞðPf  Pi Þ o jfnNL k ma;b;c ðy; y1 ; y2 ÞjinNL 4 2 Ce 4566.448 4448.890 4338.060
a
Pi and Pf are Boltzmann populations, and ma,b,c represents the E(CCSD(T)-F12 = 230.007080 hartrees.
principal axis components of the dipole moment.

Results and discussion
Low-lying conformers of ethylene glycol
Ethylene glycol shows nine different conformers that interconvert
by the internal rotation of the central bond and the two hydroxyl
groups.25 The relative position of the two oxygen atoms with
respect to the central bond allows their classification into 5 cis–
gauche (G1, G2, G3, G4, G5), 1 trans (T1), and 3 trans–gauche forms
(T2, T3, T4). The minimum energy path of the cis–gauche - trans
transformation is restricted by a barrier of B900 cm1.25 This
barrier has been estimated using the three-dimensional potential
energy surface computed using CCSD(T)-F12/AVTZ.
The two structures, G1 and G2, represented in Fig. 2, denote
prominent stabilities. Both are cis–gauche forms that stabilize by
the formation of a unique intramolecular hydrogen bond. They are
separated by a barrier of B400 cm1. Although G3 shows real
harmonic wavenumbers and a very small dipole moment, it is
ignored in a part of this study because the G3 - G1 process
follows a barrier-less pathway when vibrational energies increase.25
Table 2 collects the CCSD(T)-F12/AVTZ-F12 equilibrium
rotational constants and the MP2/AVTZ dipole moments of
the three conformers. The coordinates y, y1, and y2 coincide with
the dihedral angles O2C2C1O1, H1O1C1C2, and H2O2C2C1,
respectively.
G1 and G2 dipole moments were computed to be 2.5187 Debyes
and 2.4650 Debyes, respectively. Harmonic and anharmonic funda-
mentals were determined using VPT2 for all the isotopic varieties to
assure the minimum energy character of the conformers. VPT2
assumes a unique minimum in the PES because it is a theoretical
model developed for semi-rigid species. Therefore, it derives two
different transition series for D1H2 and H1D2 in the asymmetric G1
and G2 conformers. In G3, in the absence of intramolecular bonds
breaking the symmetry, the two alcoholic groups behave as
indiscernible units.
Table 3 summarizes the OH-stretching fundamentals for
three (or four) ethylene glycol isotopologues. In G1 and G2, the
pair of transitions, nOH1 and nOH2, evidence the existence of one
hydrogen bond breaking the symmetry, because the two transitions
split by 52 cm1 (3680/3628 cm1) and 40 cm1 (3655/3615 cm1),
respectively. In G3, both fundamentals converge to the same
value (3667/3667 cm1), confirming the lack of weak intra-
molecular interactions.

23788 | Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 This journal is © the Owner Societies 2020
PCCP Paper

Table 3 OH-Stretching anharmonic fundamentals (in cm1) Table 4 Band center positions (in cm1) below 550 cm1 computed using
VPT2
H1H2 D1H2
Assig.a H1H2 D1H2/H1D2 D1D2
Assign. nOH1 nOH2 nOH1 nOH2
G1 3628 3680 2676 3681 n24 G1 161 158/155 157
G2 3615 3655 2667 3655 G2 154 155/157 153
G3 3667 3667 2700 3674 n23 G1 214 211/163 163
G2 238 231/192 190
n22 G1 311 342/317 338
Assign. H1D2 D1D2 G2 321 299/325 288
G1 nOH1 nOH2 nOH1 nOH2 2n24 G1 326 315/302 312
G2 3629 2715 2676 2715 G2 302 314/308 307
G3 3616 2695 2666 2695 n24 + n23 G1 373 369/317 319
3674 2700 2706 2704 G2 390 284/348 343
n21 G1 380 268/379 268
G2 380 335/382 327
2n23 G1 396 385/304 308
The isotopic shifts of the OH-stretching fundamentals G2 432 441/357 357
evidence the asymmetric character of G1 and G2. While the n24 + n22 G1 469 500/454 496
G2 458 458/478 435
G3 vibrational spectrum can be described in terms of symmetry 3n24 G1 481 471/461 465
coordinates nSYM (nSYM = pDOH1  qDOH2), in G1, the OH G2 458 462/467 461
transition must be described in terms of local modes (nOH1 = n20 G1 519 513/511 504
G2 515 522/524 518
pDOH1 and nOH2 = qDOH2). In G1-D1H2, one band center n23 + n22 G1 521 549/467 497
coincides with one of G1-H1H2 (nOH2 = 3681 cm1) and the G2 555 527/512 475
other one coincides with one of G1-D1D2 (nOH1 = 2676 cm1). n24 + n21 G1 533 423/530 423
G2 526 487/533 480
When the vibrational energy increases, the hydrogen bonds 2n24 + n23 G1 537 525/471 474
vanish and the molecule gains symmetry. This must be taken G2 542 535/502 496
into consideration for spectrum assignments. a
n24 = CC torsion; n21, n23 = OH torsion; n22 = CCO bending; n20 = CCO
Table 4 shows the low-energy transitions computed with bending.
VPT2. This theoretical model, not sufficient for large amplitude
motions, provides the first assignment of the far infrared
region. Estimated displacement by Fermi resonances is con- The far infrared (FIR) spectrum
sidered and allowed to evaluate the validity of the variational
model of reduced dimensionality applied below. The torsional energy levels were calculated by solving variation-
Table 5 collects the ground vibrational state rotational ally the Hamiltonian of eqn (1). The effective potential defined
constants and the centrifugal distortion constants (S-reduction, Ir in eqn (2) depends on two mass dependent properties, V 0 (y, y1,
representation)38 corresponding to the G1 and G2 forms and y2) and VZPVE(y, y1, y2), which were computed for the deuterated
isotopologues. Computed data are compared with parameters forms. For the main isotopologues, previous parameters25 were
fitted using experimental lines.11,13,15,16 The ground vibrational employed. While the V 0 effect is very small, VZPVE is not
state rotational constants41 are derived using the equation:42 negligible. The kinetic energy parameters Bqiqj(y, y1, y2) were
fitted to the symmetry adapted triple Fourier series and inde-
B0 = Be(CCSD(T)-F12/AVTZ-F12) + DBcore
e (CCSD(T)/CVTZ) pendent A000 coefficients are collected in Table 6.
+ DBvib(MP2/AVTZ) (8) Fig. 3 shows the surface in the gauche region. The whole of
the surface encloses 25 minima (50 minima for the G8 species),
where Be represents the equilibrium parameters (see Table 2) which is consistent with the existence of nine conformers.
and DBvib is the vibrational contribution derived from the VPT2 air It has to be considered that each conformer corresponds
vibration–rotation interaction parameters.41 DBcore e was deter- to a number of minima that depends on its symmetry.
mined using Be (CV) and Be (V), which were calculated correlating For the asymmetric forms, each conformer corresponds to
both core and valence electrons (CV) and just only considering four minima (Gi(y, y1, y2), G0i ðy; y2 ; y1 Þ, G00i ðy; y1 ; y2 Þ,
the valence electrons (V) in the post-SCF process:42 G000
i ðy; y2 ; y1 Þ).

DBcore = Be (CV)  Be (V) (9)
e
The geometries computed with CCSD(T)/CVTZ are provided
as ESI.† As already proven in previous studies of other
molecules,42–45 the followed methodology produces very accurate
results. In G1 (H1H2) and G1 (D1H2), the agreement is impressive
for both the rotational constants and the quartic centrifugal
distortion constants. For species for which experimental data are
not available, these computations can be excellent tools for future
spectrum assignments.
Fig. 4 depicts one-dimensional cuts of the 3D-PES. The
curves A and B reveal the height of the potential energy barriers
restricting the interconversion of two minima corresponding
to a unique conformer following the more probable pathway.
G1 - G1 0 and G2 - G2 0 barriers were estimated to be
B950 cm1 and B1000 cm1, respectively. The C and D curves
illustrate the G1 - G3 and G2 - G3 processes. The C curve
evidences the barrier-less character of the G1 - G3 pathway.
Therefore, the torsional levels can be localized in G1 and G2 but
not in G3. The G1 - G2 barrier (B440 cm1) is shown in Fig. 2.

This journal is © the Owner Societies 2020 Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 | 23789
Paper PCCP

Table 5 Rotational constants and centrifugal distortion constants (in Table 5 (continued)
MHz, S reduction, Ir representation) of ethylene glycol and deuterated
isotopolgues G1 (D1H2) G2 (D1H2)
11
Calc. Exp. Calc.
G1 (H1H2)
HJ  109 37.5 37.1
Calc. Exp.15 HK  109 1483.3 1712.6
A0 15369.6 15361.185615 (294) HJK  109 297.0 323.7
B0 5579.9 5588.242718 (74) HKJ  109 1090.9 1258.7
C0 4610.1 4614.489567 (76) h1  109 17.6 16.4
DJ  103 7.339 7.360176 (12) h2  109 2.3 2.0
DJK  103 28.566 31.5764 (75) h3  109 0.1 0.1
DK  103 65.249 75.5929 (122)
d1  103 2.326 2.327997 (117) G1 (H1D2) G2 (H1D2)
d2  103 0.173 0.169245 (134) 13
HJ  109 31.1 11.136 Calc. Exp. Calc.
HK  109 2172.0 3000.3 (39) A0 15140.8 14126.955 (34) 14719.7
HJK  109 322.8 329.28 (99) B0 5301.5 5311.085 (22) 5301.3
HKJ  109 1420.9 1817.39 (217) C0 4407.5 4412.157 (12) 4464.4
h1  109 14.1 DJ  103 6.608 6.75 (29) 7.044
h2  109 1.6 DJK  103 28.866 32.4 (5) 28.273
h3  109 0.1 DK  103 72.202 93 (6) 63.506
d1  103 2.050 2.062
G2 (H1H2) d2  103 0.144 0.130
HJ  109 26.2 28.5
Calc. Exp.16 HK  109 1986.0 2133.7
A0 15229.8 15210.05783 (35) HJK  109 271.8 324.5
B0 5518.5 5542.434000 (188) HKJ  109 1289.2 1436.8
C0 4586.8 4595.444993 (135) h1  109 12.0 10.9
DJ  103 7.445 7.37399 (41) h2  109 1.5 0.9
DJK  103 31.268 29.674 (41) h3  109 0.1 0.0
DK  103 68.917 71.674 (41)
d1  103 2.273 2.25978 (65)
d2  103 0.157 0.18229 (71)
HJ  109 31.7 26.27 (55) Table 6 A000 coefficients of the Bqiqj (y, y1, y2) analytical expression of the
HK  109 2482.2 5742.0 (192) kinetic energy parameters (in cm1)a
HJK  109 360.8 2091.0 (45)
HKJ  109 1648.1 1568.0 (135) H1H2 D1D2 D1H2 (H1D2)
h1  109 13.6
h2  109 1.3 A000(B2a2a) 0.5255 0.4793 A000(Byy) 2.0072
h3  109 0.1 A000(By1y1) = A000(By2y2) 22.1877 11.8024 A000(By1y1) 11.7975
A000(By2y2) 22.1867
G1 (D1D2) G2 (D1D2) A000(B2ay1) = A000(B2ay2) 0.3559 0.2363 A000(Byy1) 0.4677
13
A000(Byy2) 0.7058
Calc. Exp. Calc. A000(By1y2) 0.0269 0.1290 A000(By1y2) 0.0933
A0 14403.1 14394.114 (64) 14033.5 a
The 324 coefficients are provided as ESI.
B0 5267.8 5276.246 (21) 5273.1
C0 4319.3 4323.647 (18) 4379.5
DJ  103 6.837 7.31 (28) 7.270
DJK  103 25.918 30.6 (11) 25.725
DK  103 58.613 65.3 (44) 51.760
d1  103 2.143 2.13 (27) 2.150
d2  103 0.155 0.139
HJ  109 31.2 32.0
HK  109 1389.0 1462.8
HJK  109 251.4 285.9
HKJ  109 1005.0 1087.7
h1  109 14.6 12.6
h2  109 2.0 1.3
h3  109 0.1 0.0

G1 (D1H2) G2 (D1H2)
Calc. Exp.11 Calc.
Fig. 3 The gauche region (y = 61.71) of the potential energy surface
A0 14621.8 14620.287 (22) 14502.4
(in cm1). The anisotropy of the PES is clearly observed.
B0 5543.2 5548.481 (13) 5487.6
C0 4515.0 4517.854 (13) 4497.3
DJ  103 7.615 8.27 (31) 7.731
DJK  103 25.641 30.4 (5) 28.482
DK  103 52.795 51 (3) 56.360 A correct convergence of the levels computed variationally
d1  103 2.440 2.386 requires a long basis set of at least 99 functions (50 cosines
d2  103 0.187 0.169
and 49 sines) to describe the CC-torsion and 51 functions

23790 | Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 This journal is © the Owner Societies 2020
PCCP Paper

Table 7 Low-lying torsional energy levels (in cm1)

 
Assignment n CC n OH n iOH0
H1H2 D1D2 D1H2

ZPVE 394.325 311.853 363.852

0001 A1, A1d 0.000 0.000 0.000
A3, A3d 0.000 0.000 0.000
A2, A2d 0.311 0.012 21.731
A4, A4d 0.311 0.012 21.737
0002 A1, A1d 138.187 130.221 137.556
A3, A3d 138.187 130.221 137.560
A2, A2d 138.305 130.226 181.753
A4, A4d 138.305 130.226 181.761
A1 and A2 A1
0101 A1 168.5 140.4 166.5
A2 182.9 141.3 197.3
Fig. 4 Preferential energy paths for minimum interconversion. 1001 A1 176.8 168.4 172.2
A2 177.2 168.7 211.7
0102 A1 263.1 229.4 269.0
A2 313.2 248.5 295.8
1002 A1 319.5 295.3 322.6
(26 cosines and 25 sines) for each one of the hydroxyl groups. In A2 320.1 294.6 371.3
H1H2 and D1D2, the Hamiltonian matrix dimensions (402 975  1101 A1 335.2 310.0 350.9
402 975) are reduced using the symmetry wavefunctions25 and A2 353.6 299.7 377.3
2001 A1 348.9 332.1 343.2
the contractions collected in eqn (4). By using 13 contracted basis A2 350.2 332.7 396.9
sets to describe the CC-torsion, the dimensionality decreases to 0201 A1 361.6 288.1
52 650  52 650. This last matrix factorized by symmetry into A2 393.1 316.0
0011 A1 367.8 278.4 309.6
8 submatrices.25 A2 368.3 282.0 381.5
In the case of the low-symmetry species D1H2, 13 one- 1102 A1 425.1 378.3 426.8
dimensional contracted functions and 46 two-dimensional A2 479.6 407.0
0202 A1 442.5 323.4 437.3
contracted functions were employed to build the basis set of A2 493.0 356.5
eqn (6). The resulting Hamiltonian matrix dimensions are 2002 A1 494.9 454.8 499.6
504  504. The symmetry factorizes the matrix into 2 submatrices. A2 497.4 454.0 506.5
1
210 A1 498.6 468.7 531.3
Using eqn (6) instead of eqn (4), the diagonalization is simple but A2 524.3 458.0 554.0
the computation of matrix elements is hard. 0012 A1 505.3 399.5 515.2
The contracted basis sets simplify the matrix diagonalization A2 514.8 404.0
3001 A1 518.2 492.1 514.0
but make hard the computation of the matrix elements. The A2 520.6 493.3 578.1
number of integrals arising from the long Fourier series describ- 1201 A1 533.5 437.6 458.1
ing the Veff and the kinetic parameters should be taken into A2 570.1 441.9 475.7
1011 A1 538.4 447.5 483.4
consideration. They contain 139 terms each, as detailed in our A2 538.4 447.6 566.4
previous paper.25 Time can be saved because some off-diagonal 0111 A1 542.4 422.9 494.4
elements are not necessary if an accuracy of 0.001 cm1 is required. A2 558.9 423.6 515.3
Tests were performed for the totally symmetric representation.
The A1 and A2 components of torsional states referring to the
zero-point vibrational energy (ZPVE), as well as all the sub- 0.3 cm1 and eight sublevels localized in G2 (i = 2) lying
components of the ground vibrational state, are shown in between 138.1 and 138.4 cm1 (H1H2). The gap between both
Table 7. Some of them can be compared with the VPT2 states of sets is lower in D1D2 and more dispersed in D1H2.
Table 4. An arrangement of four quantum numbers n CC n OH n iOH0 The low-lying vibrational states of H1H2 and D1D2 are
characterizes the levels. nCC, nOH and nOH0 denote excitations of the compared in Fig. 5, which highlights the isotopic shifts, very
CC torsion (n24) and the two OH torsional modes (n23 and n21), relevant for the two OH torsional excitations. While the assign-
respectively. The i = 1, 2 digit discriminates two series of energies ment of the nCC quantum number is straightforward using the
localized in the G1 and G2 minima. For H1H2, small discrepancies contributions of the contracted basis set to the 3D-WF, the assign-
with the respect to our previous work25 are due to the enlargement ment of the nOHnOH0 pair is hard. For H1H2, the CC-torsional
and accuracy of the contracted basis set. fundamental (n24) was established at 176.803/177.087 cm1 (1001)
The energy levels split into 16 components in species of G8 and 319.544/320.085 cm1 (1002). For the isotopologues D1D2 and
symmetry (H1H2 and D1D2) and into 8 components in D1H2. D1H2, the four components are obtained to be 168.361/168.679
For the G8 isotopic varieties, the gap Aid  Ai (quantifiable using (1001) cm1 and 295.339/294.611 (1002) cm1, and 172.155/
the double symmetry group) is negligible for J = 0 but can be 211.685 (1001) cm1 and 322.613/371.264 (1002) cm1, respectively.
relevant for higher rotational excitations ( J = 1 or J = 2). Two The assignment of the nOHnOH 0 pair to the torsional states is
series of sublevels of the ground vibrational state are obtained: hard. The vibrational excitations cause the breaking of hydro-
eight components localized in G1 (i = 1) lying between 0.0 and gen bonds and ethylene glycol gains symmetry. Transitions to

This journal is © the Owner Societies 2020 Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 | 23791
Paper PCCP

Table 8 A1 - A2 and A1 - A2 components (n, in cm1) of the IR bands.

Relative intensities at 273 K (Ir) (s = strong; w = weak)

H1H2 D1D2
r 6
n I Exp. n Ir
0001 - 0011 (n21)
A1 - A2 368.3 0.66 375s 282.0 0.46
A2 - A1 367.5 0.63 278.4 0.41
0002 - 0012 (n21)
A1 - A2 — — 375s 273.8 0.62
A2 - A1 367.0 0.55 269.3 1.00
0001 - 0012 (n21)
A1 - A2 376.6 0.28 375s
A2 - A1 — —
0001 - 0101 (n23)
Fig. 5 Low energy levels of the G8 isotopologues (E 0 = Er  n24/2). A1 - A2 182.9 1.00 210w 140.3 0.87
A2 - A1 168.2 0.75 140.3 0.84
0001 - 0102 (n23)
A1 - A2 313.2 0.12 230w 248.5 0.26
the high excited levels can be understood in terms of symmetry A2 - A1 263.1 0.42 229.3 0.28
vibrational coordinates, whereas the low-lying levels are more 0001 - 1001 (n24)
or less localized in the asymmetric minima G1 and G2. A1 - A2 — — 168.7 0.33
A2 - A1 168.3 0.26
The relative intensities shown in Table 8 correspond to the 1001 - 1101 (n24 - n23+24)
most probable transitions of H1H2 and D1D2 computed using A1 - A2 176.8 0.32 — —
eqn (7). Triple Fourier series were employed to describe the A2 - A1 158.1 0.25 141.3 0.18
1001 - 1102 (n24 - n23+24)
torsional dependence of the dipole moment components. A1 - A2 — — 238.6 0.11
As reported,46 a good selection of the axis system taking A2 - A1 248.0 0.15 209.6 0.11
into consideration symmetry requirements is relevant for the 1001 - 1011 (n24 - n21+24)
A1 - A2 361.6 0.23 273.5 0.15
computation of intensities. In principle, since the low-lying A2 - A1 269.0 0.13
conformers are asymmetric, all the possible transitions among 0101 - 0102
all the low torsional levels are infrared active. The OH torsional A1 - A2 144.7 0.38 108.2 0.56
A2 - A1 80.2 0.23 88.0 0.32
transitions are expected to show high intensities. Nevertheless, 0101 - 1102 (n23 - n23+24)
when the vibrational energy increases, the molecule gains A1 - A2 216.4 0.13 — —
symmetry and the intensity of the excitations of one of the A2 - A1 242.1 0.13
0101 - 0111 (n23 - n21+23)
torsional modes vanishes. Since ethylene glycol is near-prolate, A1 - A2 390.4 0.19 283.2 0.26
the Q branches observed in the IR spectra correspond to type A A2 - A1 — — 281.5 0.23
and type C bands. These bands depend on the mA (A4) and mC (A2) 0011 - 0111 (n21 - n21+23)
A1 - A2 191.1 0.16
components of the dipole moment. The observed Q branches6 A2 - A1 — —
must be assigned to the transitions (vCCvOHvOH0 )i - (vCCvOH + 0101 - 0201 (n23 - 2n23)
1vOH0 )i and (vCCvOHvOH0 )i - (vCCvOHvOH0 + 1)i.25 A1 - A2 — — 146.8 0.23
A2 - A1 178.7 0.10 175.7 0.24
For H1H2, the A1/A2 pairs, 168.472/182.923 cm1 (0101), 0101 - 0202 (n23 - 2n23)
263.147/313.210 cm1 (0102), 367.775/368.305 cm1 (0011), A1 - A2 — — 216.1 0.15
and 505.303/514.772 cm1 (0012), are assigned to the two OH A2 - A1 259.6 0.22 182.1 0.25
torsional modes and to the G1 (i = 1) and G2 (i = 2) minima. For
D1D2, the A1/A2 pairs were found to be 140.360/141.328 cm1
(0101), 229.351/248.516 cm1 (0102), 278.372/281.967 cm1 of the OH-torsional modes split due to the mass difference
(0011), and 399.487/403.980 cm1 (0012). The fundamentals between the OH groups. The (0101) and (0011) levels have been
assigned to G1 (i = 1) can be compared with the VPT2 values found to lie at 166.488/197.253 cm1 and 309.587/381.554 cm1,
of Table 4 and with the experimental values. The n23 and n21 respectively, although the assignment (0011) is not conclusive.
fundamentals were computed to be 214 cm1 and 380 cm1 Using VPT2, the fundamentals were found at 163/211 cm1 (n23)
(H1H2) and 163 cm1 and 268 cm1, using VPT2. The (0011) and 317/342 cm1 (n22).
level (367.775/368.305 cm1) is in good agreement with the
observation of Buckley and Giguère (375 cm1),8 although the Conclusions
experimental spectrum was recorded at low resolution.
In D1H2, the energy level pattern is absent when comparing In ethylene glycol, the formation of a unique intramolecular
with symmetrical species. Computation and assignments of the hydrogen bond that vanishes with the vibrational energy yields a
levels are required to solve a chain of problems. For example, the very anisotropic potential energy surface. The ground vibrational
low symmetry causes arrangements of the symmetry representa- state splits into 16 tunneling subcomponents. Then, the high
tions. This has many consequences such as dimensionality and excitations of the torsional modes can be understood in terms of
the presence of additional resonances. Excited vibrational levels symmetry vibrational coordinates, whereas the very low energy

23792 | Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 This journal is © the Owner Societies 2020
PCCP
levels are more or less localized in the most stable minima G1 and
G2, which are asymmetric conformers. The ground vibrational state
rotational constants and the centrifugal distortion constants are
provided for three isotopologues containing deuterium.
The torsional energy levels labelled using four quantum
numbers, n CC n OH n iOH0 , are computed variationally using a model
of reduced dimensionality. Two series of sublevels of the ground
vibrational state are obtained. One series is localized in G1 (i = 1)
and the second one is localized in G2 (i = 2). For H1H2, the zero
vibrational energy splits into eight sublevels lying between 0.0
and 0.3 cm1 and eight sublevels lying between 138.1 and
138.4 cm1. The gap between both sets is lower in D1D2
(0.0–0.012 cm1 and 130.221/130.226 cm1) and very dispersed
in D1H2 (0.0–21.731 cm1 and 137.556/137.560 cm1).
While the assignment of the nCC quantum number is
straightforward using the contributions of the contracted basis
set to the 3D-WF, the assignment of the nOHnOH 0 pair is hard.
On the basis of the computed intensities and dipole moment
variation, the prominent bands must be assigned to the OH-
fundamentals. For H1H2, the A1 - A2 and A2 - A1 components
of the n24 CC torsional mode are determined to be 176.8/
177.1 cm1 (G1) and 181.9/181.2 cm1 (G2). For D1D2, the
corresponding four components are obtained to be 168.7/
168.3 cm1 and 164.5/165.1 cm1.
For G1(H1H2), the A1 - A2 and A2 - A1 components of
n21 and n23 are determined to lie at (368.3/367.5) cm1 and
(182.9/168.2) cm1. n23 is computed to show the most intense
transition (Ir = 1.0). The corresponding values for G1(D1D2) are
determined to be (282.0/278.4) cm1 and (141.3/140.3) cm1.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This research was supported by the Ministerio de Ciencia e
Innovación of Spain through the grants EIN2019-103072 and
FIS2016-76418-P. This work has received funding from the CSIC
i-coop + 2018 program under the reference number COOPB20364.
This project has received funding from the European Union’s
Horizon 2020 research and innovation program under the Marie
Skłodowska-Curie grant agreement No. 872081. The authors
acknowledge Secretarı́a General Adjunta de Informática del CSIC
(CTI-CSIC) and the Centro de Supercomputación de Galicia (CESGA,
Spain) for computing facilities.
Notes and references
1 G. Cooper, N. Kimmich, W. Belisle, J. Sarinana, K. Brabham
and L. Garrel, Nature, 2001, 414, 879.
2 N. Brouillet, D. Despois, X.-H. Lu, A. Baudry, J. Cernicharo,
D. Bockelée-Morvan, J. Crovisier and N. Biver, Astron. Astro-
phys., 2015, 576, A129.
This journal is © the Owner Societies 2020
Paper
3 J. M. Hollis, F. J. Lovas, P. R. Jewell and L. H. Coudert,
Astrophys. J., 2002, 571, L59.
4 J. K. Jørgensen, M. H. D. van der Wiel, A. Coutens, J. M.
Lykke, H. S. P. Müller, E. F. van Dishoeck, H. Calcutt,
P. Bjerkeli, T. L. Bourke and M. N. Drozdovskaya, et al.,
Astron. Astrophys., 2016, 595, A117.
5 C. Favre, L. Pagani, P. F. Goldsmith, E. A. Bergin, M. Carvajal,
I. Kleiner, G. Melnick and R. Snell, Astron. Astrophys., 2017, 604, L2.
6 K. Kobayashi, K. Ogata, S. Tsunekawa and S. Takano, Tor-
sionally excited methyl formate in Orion KL, Astrophys. J.,
2007, 657, L17.
7 S. E. Bisschop, P. Schilke, F. Wyrowski, A. Belloche,
C. Brinch, C. P. Endres, R. Gusten, H. Hafok, S. Heyminck,
J. K. Jorgensen, H. S. P. Müller, K. M. Menten, R. Rols and
S. Schlemmer, Astron. Astrophys., 2013, 552, 122.
8 P. Buckley and P. A. Giguère, Can. J. Chem., 1967, 45, 397.
9 K. M. Marstokk and H. Möllendal, J. Mol. Struct., 1974, 22, 301.
10 E. Walder, A. Bauder and H. H. Günthard, Chem. Phys.,
1980, 51, 223.
11 W. Caminati and G. Corbelli, J. Mol. Spectrosc., 1981, 90, 572.
12 P.-E. Kristiansen, K.-M. Marstokk and H. Möllendal, Acta
Chem. Scand., 1987, A41, 403.
13 D. Christen, L. H. Coudert, R. D. Suenram and F. J. Lovas,
J. Mol. Spectrosc., 1995, 172, 57.
14 D. Christen, L. H. Coudert, J. A. Larsson and D. J. Cremer,
J. Mol. Spectrosc., 2001, 205, 185.
15 D. Christen and H. S. P. Müller, Phys. Chem. Chem. Phys.,
2003, 5, 3600.
16 H. S. P. Müller and D. Christen, J. Mol. Spectrosc., 2004, 228, 298.
17 D. L. Howard, P. Jørgensen and H. G. Kjaergaard, J. Am.
Chem. Soc., 2005, 127(48), 17096.
18 P. Das, P. K. Das and E. Arunan, J. Phys. Chem. A, 2015, 119, 3710.
19 C. Van Alsenoy, L. Van Den Enden and L. Schäfer, THEO-
CHEM, 1984, 108, 121.
20 H. Takeuchi and M. Tasumi, Chem. Phys., 1983, 77, 21.
21 T.-K. Ha, H. Frei, R. Meyer and Hs. H. Günthard, Theor.
Chim. Acta, 1974, 34, 277.
22 H. Frei, T.-K. Ha, R. Meyer and Hs. H. Günthard, Chem.
Phys., 1977, 25, 271.
23 C. Murli, N. Lu, Z. Dong and Y. Song, J. Phys. Chem. B, 2012,
116, 12574.
24 K. Krishnan and R. S. Krishnan, Proc. Natl. Acad. Sci. India,
1966, 64, 111.
25 R. Boussessi, M. L. Senent and N. Jaı̈dane, J. Chem. Phys.,
2016, 144, 164110.
26 V. Barone, J. Chem. Phys., 2005, 122, 014108.
27 M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A.
Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci
and G. A. Petersson, et al., GAUSSIAN 09, Revision A.1, 2009.
28 M. L. Senent, ENEDIM, ‘‘A variational code for non-rigid
molecules’’, 2001, (see http://tct1.iem.csic.es/senent/PRO
GRAMAS.htm, for more details).
29 M. L. Senent, Chem. Phys. Lett., 1998, 296, 299.
30 M. L. Senent, J. Mol. Spectrosc., 1998, 191, 265.
31 H.-J. Werner, P. J. Knowles, F. R. Manby, M. Schütz,
P. Celani, G. Knizia, T. Korona, R. Lindh, A. Mitrushenkov
Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 | 23793
Paper PCCP

and G. Rauhut, et al., MOLPRO, version 2010.1, a package of 39 M. L. Senent, S. Fernández-Herrera and Y. G. Smeyers,
ab initio programs, see http://www.molpro.net. Spectrochim. Acta, Part A, 2000, 56A, 1457.
32 G. Knizia, T. B. Adler and H.-J. Werner, J. Chem. Phys., 2009, 40 J. M. Flaud, C. Camy-Peyret, J. W. C. Johns and B. Carli,
130, 054104. J. Chem. Phys., 1989, 91, 1504.
33 H.-J. Werner, T. B. Adler and F. R. Manby, J. Chem. Phys., 41 I. M. Mills, in Molecular Spectroscopy: Modern Research, ed.
2007, 126, 164102. K. N. Rao and C. W. Mathews, Academic Press, New York, 1972.
34 R. A. Kendall, T. H. Dunning and R. J. Harrison, J. Chem. 42 R. Boussessi, S. Guizani, M. L. Senent and N. Jaı̈dane,
Phys., 1992, 96, 6796. J. Phys. Chem. A, 2015, 119, 4057.
35 C. Hampel, K. Peterson and H.-J. Werner, Chem. Phys. Lett., 43 S. Dalbouha, M. L. Senent, N. Komiha and R. Domı́nguez-
1992, 190, 1. Gómez, J. Chem. Phys., 2016, 145, 124309.
36 D. E. Woon and T. H. Dunning, Jr., J. Chem. Phys., 1995, 44 R. A. Motiyenko, L. Margulès, M. L. Senent and J. C. Guillemin,
103, 4572. J. Phys. Chem. A, 2018, 122, 3163.
37 C. Møller and M. S. Plesset, Phys. Rev., 1934, 46, 618. 45 M. L. Senent, J. Mol. Spectrosc., 2018, 343, 28.
38 J. K. G. Watson, J. Chem. Phys., 1968, 48, 4517. 46 J. Tennyson and B. Sutcliffe, Mol. Phys., 1992, 76, 1147.

23794 | Phys. Chem. Chem. Phys., 2020, 22, 23785--23794 This journal is © the Owner Societies 2020