ARTICLE

pubs.acs.org/JPCA

Fourier Transform Infrared Spectroscopy and Theoretical Study of

Dimethylamine Dimer in the Gas Phase
Lin Du and Henrik G. Kjaergaard*
Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark
bS Supporting Information
ABSTRACT: Dimethylamine (DMA) has been studied by gas-phase Fourier
transform infrared (FTIR) spectroscopy. We have identified a spectral
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transition that is assigned to the DMA dimer. The IR spectra of the dimer
in the gas phase are obtained by spectral subtraction of spectra recorded at
different pressures. The enthalpy of hydrogen bond formation was obtained
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for the DMA dimer by temperature-dependence measurements. We comple-

ment the experimental results with ab initio and anharmonic local mode model
calculations of monomer and dimer. Compared to the monomer, our calcula-
tions show that in the dimer the N
H bond is elongated, and the NH-
stretching fundamental shifts to a lower wavenumber. More importantly, the
weak NH-stretching fundamental transition has a pronounced intensity
increase upon complexation. However, the first NH-stretching overtone
transition is not favored by the same intensity enhancement, and we do not
observe the first NH-stretching overtone of the dimer. On the basis of the measured and calculated intensity of the NH-stretching
transition of the dimer, the equilibrium constant for dimerization at room temperature was determined.

’ INTRODUCTION overtone range of the NH-stretching vibration as a function

Dimethylamine [(CH3)2NH, DMA] has been studied both
experimentally and theoretically. Fang et al. reported the gas-
phase overtone absorption spectra of DMA by intracavity laser
photoacoustic and FTIR spectroscopy in an attempt to detect
aggregates.1 They measured the temperature and pressure de-
pendence of the NH-stretching overtone intensities of DMA. No
relative intensity changes of the various NH-stretching overtone
bands were observed when the vapor pressure of DMA changed
from 3 to 100 Torr or when the temperature was increased from
0 to 80
C. On the basis of these results, they concluded that
formation of aggregates is unlikely in their experiments. In 2007,
Marinov et al. reported high-resolution absorption spectrum for
gas-phase DMA in the region of the first NH-stretching overtone
by cavity-ringdown spectroscopy.2 They measured the spectra
at room temperature and at pressures in the range from 29.4
to 204.4 mbar. Very recently, Miller et al. measured absolute
intensities of the fundamental to third NH-stretching overtone
transitions in DMA.3
Several studies have been aimed at understanding the struc-
ture and bonding of molecular complexes involving NH3 and
methylamines.4
17 However, the DMA dimer [(DMA)2] has
been the subject of only a few studies. Early in 1950, Lambert
and Strong studied the dimerization of ammonia and amines
and pointed out that the dimerization is attributed to hydrogen
bonding.18 The energy of the N
H 3 3 3 N bond in the DMA
dimer was determined to be 10.5 kJ mol
1 by measuring the
compressibility of the vapor. Wolff and Gamer investigated
the infrared spectra of DMA in the fundamental and in the first
of concentration and temperature in different solutions (CCl4,
n-hexane) and identified a characteristic band from DMA
associates.19 The self-association of DMA was also examined in
Bernard-Houplan and Sandorfy’s low temperature infrared study
of dissolved DMA.20 The solvents were 1:1 mixtures of CCl3F
and CF2Br-CF2Br and of CCl3F and methylcyclohexane, which
can form rigid glasses near liquid nitrogen temperature. Odutola
et al. performed an electric deflection study of (DMA)2 and
found that the dipole moment of (DMA)2 is greater than 0.3 D.21
It is more favorable for the dimer to exhibit a linear hydrogen-
bonded conformation, compared with a cyclic structure with two
hydrogen bonds between N and H atoms, which would have a
dipole moment of only a few tenths of a Debye. Bohn and
Andrews identified bands of (DMA)2 in their measured FTIR
spectra of NH3
DMA complexes in solid argon.22 On the basis
of the spectrum, they proposed that the two submolecules are
inequivalent in (DMA)2 like in (NH3)2.13 Several years later,
Tubergen and Kuczkowski measured the rotational spectra for
six isotopmers of (DMA)2 using a Fourier-transform microwave
spectrometer and determined the most stable structure of the
DMA dimer.23 In addition, the ultraviolet photoelectron spec-
trum of (DMA)2 was obtained in the vapor phase by spectrum
stripping and assigned with the help of ab initio molecular orbital
(MO) calculations.24 The calculated orbital energies based on a
Received: July 15, 2011
Revised: September 23, 2011
Published: September 27, 2011

r 2011 American Chemical Society 12097 dx.doi.org/10.1021/jp206762j | J. Phys. Chem. A 2011, 115, 12097–12104
The Journal of Physical Chemistry A
nearly linear hydrogen bonded dimer structure show reasonably
good agreement with the experimental values. Recently,
Cabaleiro-Lago and Ríos studied the interaction in the DMA
dimer and trimer with the HF, DFT/B3LYP, and MP2 ab initio
methods in conjunction with the 6-31+G* and aug-cc-pVDZ/
cc-pVDZ (i.e., the aug-cc-pVDZ set for carbon and nitrogen
atoms and the cc-pVDZ set for hydrogen atoms) basis sets.25
They found the most stable conformer for DMA dimer to have Cs
symmetry and a close to linear hydrogen bond.
Vibrational spectroscopy is extensively applied to the study of
hydrogen bonded complexes; however, measurements in solu-
tion and in matrices are affected by solvent effects. Gas-phase
spectroscopy can be used to quantify the complexes and the
equilibrium constant of their formation. On the basis of previous
experience with FTIR and quantum chemical calculations of
weakly bound methanol clusters in the gas phase,26,27 we have
recorded the FTIR spectra of the DMA dimer and supported
these experiments with ab initio calculations of the monomer and
dimer. The NH-stretching wavenumbers and oscillator strengths
for DMA and its dimer were calculated with an anharmonic
oscillator local mode model.28
31 Furthermore, by measuring
the dimer spectra over a range of temperatures, the dimerization
enthalpy ΔH was obtained and compared with the theoretical
results. The equilibrium constant of the DMA dimerization
reaction was also estimated based on experimental and calculated
NH-stretching intensities.
’ EXPERIMENTAL AND THEORETICAL METHODS
The IR spectra were recorded at 1.0 cm
1 resolution with a
VERTEX 70 (Bruker) FTIR spectrometer fitted with a CaF2
beam splitter and an MCT detector. During the experiments, the
FTIR spectrometer was purged with dry nitrogen gas to mini-
mize the interference by water and CO2. Several gas cells with
different path lengths were used, including a 10-cm cell equipped
with KBr windows and a 2.4 m and a 4.8 m path length
multireflection gas cell (Infrared Analysis, Inc.) fitted with Infrasil
quartz windows. The 2.4 m cell was equipped with a heating
jacket, and the temperature was controlled by a Digi-Sense
electronic temperature controller (Eutech Instruments Pte
Ltd., Model 68900
03). The gas samples were prepared on a
glass vacuum line (base pressure less than 1  10
4 Torr)
equipped with a Varian cold cathode vacuum gauge (1  10
7 to
1  10
2 Torr, Model 860A). Sample pressures were measured
with a Varian diaphragm pressure gauge (1
1500 Torr, DV100).
In the variable temperature experiment, the DMA spectra were
measured with the 2.4 m cell in the temperature range from
296 to 368 K. The pressure was measured at room temperature,
and the ideal gas law used to calculate the pressure at the elevated
temperature. Before each measurement, we waited for at least
20 min to let the temperature of the gas in the cell stabilize. The
adsorption of DMA to the cell walls was observed, however the
rate of adsorption was slow and did not affect our measurement
significantly. DMA (anhydrous, 99+%) was purchased from
Aldrich and used without any further purification.
Gaussian 03 (revision E.01)32 and MOLPRO (version
2009.1)33 were used to perform the calculations. The geometries
of DMA and (DMA)2 were optimized using B3LYP hybrid
density functional theory and QCISD ab initio theory with the
aug-cc-pVDZ and aug-cc-pVTZ basis sets, and using CCSD theory
with the cc-pVDZ basis set. The optimization threshold criteria
of the MOLPRO calculations were set to: gradient = 1  10
5 au.,
12098
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step size = 1  10
5 au., and energy = 1  10
7 au., and the global
thresholds for single-point calculations were set to energy = 1 
10
8 au. The harmonic frequencies were calculated with the
B3LYP/aug-cc-pVTZ and QCISD/aug-cc-pVDZ methods with
MOLPRO. The integration grid-size used for the B3LYP density
functional calculations was set with an overall target accuracy of
1  10
8 au. Unless otherwise stated, QCISD calculations were
performed with MOLPRO and B3LYP calculations were carried
out with Gaussian 03. We have used the Boys and Bernardi
counterpoise correction procedure (CP) to reduce the basis
set superposition error (BSSE) in the dimer calculations.34 We
apply the CP correction only to the energy of the non-CP
optimized geometry. The CP-correction method has been shown
to improve interaction energies of weakly bound complexes with
some methods.8
10,35
37
Furthermore, the behavior of the NH-stretching vibration is a
very sensitive probe for the local environment. An anharmonic
oscillator local mode model was used to calculate the NH-
stretching frequencies and intensities.30,31 Previously, the NH-
stretching modes in a range of molecules have been shown to
be isolated from other vibrational modes, and hence are well
described by the local mode model of vibration.38
40 We assume
that the NH-stretching vibrations can be described by a Morse
oscillator, with the vibrational energy levels given by
   
1 1 2
EðvÞ=ðhcÞ ¼ v þ ω
~
v þ ω
~x ð1Þ
2 2
The Morse oscillator frequency ω~ and anharmonicity ω ~x are
found from the second, third, and fourth-order derivatives of the
potential energy curve.31 These derivatives are found by fitting an
eighth-order polynomial to a symmetric 9-point ab initio calcu-
lated potential-energy curve, obtained by displacing the N
H
bond from
0.20 to 0.20 Å in 0.05 Å steps around equilibrium
bond length. This range and step size of the potential-energy
curve ensure converged energy derivatives.41 The dimensionless
oscillator strength f of a transition from the ground vibrational
state 0 to an excited vibrational state v is given by42
fv, 0 ¼ 4:702  10
7 ½cmD
2 ~vv, 0 jμ
~v, 0 j2 ð2Þ

1
where ~vv,0 is the transition frequency in cm and μBv,0 = Æv|μB|0æ
is the transition dipole moment in Debye (D). The transition
dipole moment matrix element can be expanded as a Taylor
series in the NH-stretching displacement coordinate q, and we
limit the expansion to fifth-order terms. The dipole moment
coefficients are found by fitting an eighth-order polynomial to a
9-point dipole moment curve calculated at the same points as the
potential. The integrals Æv|qn|0æ needed for the transition dipole
moment were evaluated numerically.
’ RESULTS AND DISCUSSION
Geometries. The optimized geometries of DMA and two
different DMA dimer conformers are shown in Figure 1. DMA
has Cs symmetry, and the QCISD/aug-cc-pVTZ calculated
N
H bond length is 1.011 Å, which agrees well with the 1.022 Å
bond length derived from the microwave spectrum.43
Compared with the monomer, much less structural informa-
tion is available on the dimer. Motivated by the potential
similarity between the DMA dimer and the ammonia dimer,
Tubergen and Kuczkowski obtained sufficient experimental
information to rule out many possible dimer conformers and
dx.doi.org/10.1021/jp206762j |J. Phys. Chem. A 2011, 115, 12097–12104
The Journal of Physical Chemistry A
concluded that the two most likely structures have nonlinear
hydrogen bonds.23 With the help of ab initio calculations and a
distributed multipole analysis to estimate the electrostatic en-
ergy, they concluded that one particular structure is most
likely. Wales et al. studied the potential energy surface of the
DMA dimer by using a semiempirical potential function and
identified two minima on the potential surface.17 One of them
corresponded to the structure proposed by Tubergen and
Kuczkowski;23 however, the other minimum that previously
had not been reported agreed very well with experimental values.
Mayer et al. performed an ab initio study on the DMA dimer at
the MP2/6-31G* level and found only one minimum, which was
similar to the structure derived from microwave spectrum.44
They claimed that no other stable orientation of the two
monomers could be found on the MP2/6-31G* surface. To
eliminate these discrepancies, Cabaleiro-Lago and Ríos studied
the DMA dimer using DFT and MP2 methods in conjunction
with different basis sets.25 They identified minima for three
different dimer conformers, which they called 2A, 2B, and 2C.
Among them, structure 2B is a minimum on the potential surface
with all the methods and basis sets used and has the lowest energy
compared with the other two structures. The properties of
structure 2C depend largely on the particular method used
and introducing dispersion with the MP2 method substantially
alters the structure of this minimum. Structure 2A is similar to 2B
except that the H-donor DMA molecule is rotated about the
N 3 3 3 N axis.25 The region of the potential surface near structures
2A and 2B is very flat, and the molecules can rotate relatively
freely about the N 3 3 3 N axis. They concluded that the most
stable minimum corresponds to structure 2B, which is similar to
that derived from the microwave spectrum for the dimer.25
On the basis of previous studies, we include only the two
conformers A and B (Figure 1), which correspond to structure
2A and 2B in ref 25. After preliminary examination, the geometry
Figure 1. Optimized structures of DMA and two conformers of
its dimer.
Table 1. Selected Optimized Geometric Parameters (Ångstroms and Degrees) in the DMA Dimer
conformer method R(NHb)
A B3LYP/aug-cc-pVTZ 1.0160
CCSD/cc-pVDZ 1.0256
QCISD/aug-cc-pVDZ 1.0235
B B3LYP/aug-cc-pVTZ 1.0161
CCSD/cc-pVDZ 1.0256
QCISD/aug-cc-pVDZ 1.0234
QCISD/aug-cc-pVTZ 1.0149
a
Change in the NH bond length upon complexation, R(NHb)
RNH.
ARTICLE
changes of DMA upon dimerization is very similar for confor-
mers A and B. The QCISD/aug-cc-pVDZ energy of conformer B
is 1.6 kJ mol
1 lower than that of conformer A, and for simplicity
only conformer B was optimized at higher levels and used in our
discussion. We also calculated the NH-stretching frequencies
and intensities for conformer A with a few methods and found
the results to be close to those of conformer B. The comparison
between conformer A and B results is given in the Supporting
Information.
As shown in Figure 1, conformer B is a hydrogen-bonded
complex of Cs symmetry. To discuss more clearly, geometric
parameters are defined: RNH is the N
H bond length in DMA,
and R(NHb) and R(NHf) are the bonded and free N
H bond
length in the dimer, respectively, d is the length of the hydrogen
bond (the H 3 3 3 N distance), ψ is the angle between the CNC
plane of the acceptor DMA molecule and the donor H, and θ is
the N
H 3 3 3 N angle or H-bond angle. The R(NHb), R(NHf), and
change in N
H bond length upon complexation (Δr), together
with the d, ψ, and θ angels obtained at different computational
levels, are listed in Table 1. The z-matrix of DMA and (DMA)2
at the QCISD/aug-cc-pVTZ level are given in Supporting
Information.
Generally, due to the lack of dispersion forces, DFT methods
predict complexes too loosely bound. As seen in Table 1, the
B3LYP method predicts larger d value compared to the other
methods. At the QCISD/aug-cc-pVTZ level, the change in the
N
H bond length upon complexation is 0.0036 Å, while this
change was reported to be 0.005 Å in the previous MP2 study.25
The geometry change with dimerization is small, which suggests
that the hydrogen bond in the dimer is weak. The NHf
bond length of the dimer is roughly the same as in the isolated
molecule. The length of the hydrogen bond (the H 3 3 3 N
distance) is calculated to be 2.1810 Å (QCISD/aug-cc-pVTZ),
which is shorter than the hydrogen bond in the ammonia dimer
(2.38 Å) as expected, but it is close to the hydrogen bond length
in the CHCl3
NH3 complex (2.25 Å).9 The angle between the
CNC plane of the acceptor and Hb is calculated to be 99
at the
QCISD/aug-cc-pVTZ level. This is smaller than the comparable
angle in DME-MeOH but larger than in DMS-MeOH.27 In an
ideal hydrogen bond, the N
H 3 3 3 N angle θ is close to 180
.45
In DMA dimer there is a 25
deviation from linearity of the
hydrogen bond, which again suggests that the hydrogen bond is
not strong in this complex. As in the ammonia dimer, this
deviation can be rationalized by electrostatic interactions.9
Besides the primary hydrogen bond, there is a secondary inter-
action between the positive region on the N
H bond in the
hydrogen bond acceptor DMA with the negative region around
the partially negatively charged N of the donor which makes the
deviation from linearity energetically favorable.9
R(NHf) Δra d ψ θ
1.0120 0.0048 2.2912 133.1 171.5
1.0240 0.0023 2.2059 143.6 152.9
1.0199 0.0033 2.1888 111.6 165.4
1.0117 0.0049 2.2698 114.1 167.5
1.0231 0.0023 2.1932 100.3 147.8
1.0198 0.0031 2.1655 99.6 155.0
1.0115 0.0036 2.1810 99.3 154.6
12099 dx.doi.org/10.1021/jp206762j |J. Phys. Chem. A 2011, 115, 12097–12104
The Journal of Physical Chemistry A
Table 2. Calculated BEs of the DMA Dimer (Conformer B)
method
BE/kJ mol
1
BE (CP corrected)/ kJ mol
1
B3LYP/aug-cc-pVTZ a 7.65 7.35
CCSD/cc-pVDZ a 23.60 7.49
QCISD/aug-cc-pVDZ a 21.41 13.37
QCISD/aug-cc-pVTZ a 18.34 14.93
a
BE includes zero-point vibrational energy (ZPVE) correction (ZPVEtot =
ZPVEdimer
2ZPVEmonomer), obtained from unscaled B3LYP/aug-cc-
pVTZ harmonic frequencies and amount to 2.79 kJ mol
1.
Figure 2. DMA spectra in the fundamental NH-stretching region
measured at 700 and 2 Torr vapor pressures with a path length of
10 cm and 4.8 m, respectively, at 296 K. The left-hand side ordinate
corresponds to the spectrum at 700 Torr. The absorbance is obtained
by log(I0/I).
The binding energy (BE) defined as the energy difference
between the dimer (ED) and the two monomers (EM), i.e., BE =
ED
2EM, was calculated at various levels and are given in
Table 2. Zero-point vibrational energy corrections (ZPVE) were
included in the BE and obtained from the unscaled B3LYP/aug-
cc-pVTZ harmonic frequencies. The B3LYP/aug-cc-pVTZ har-
monic frequencies are given in Table S1 of the Supporting
Information. The binding energy of the QCISD/aug-cc-pVTZ
optimized dimer is calculated to be
18.3 kJ mol
1, which the
CP correction on the energy changes to
14.9 kJ mol
1. The
magnitude of the CP correction decreases with increase in basis
set size, as expected. Very recently, optimization of the DMA
dimer with the explicitly correlated coupled cluster method
CCSD(T)-F12/VDZ-F12 found the binding energy of confor-
mer B to be
18.6 kJ mol
1.46 The CCSD(T)-F12/VDZ-F12
method have been found to give binding energies for small
complexes that are in good agreement with CCSD(T) results at
the complete basis set limit.10
FTIR Spectra of the DMA Dimer. Fang et al. measured the
temperature and pressure dependence of the NH-stretching
overtone intensities of DMA and no relative intensity changes
of the various NH-stretching overtone bands were observed
with a DMA vapor pressure range from 3 to 100 Torr and a
temperature from 0 to 80
C.1 However, when we focused on the
fundamental NH-stretching region and changed the vapor
pressure from 2 to 700 Torr, a new feature appears in the spectra
to the low energy side of the DMA NH-stretching band
(Figure 2). The relative intensity of the low energy shoulder
12100
ARTICLE
Figure 3. The DMA dimer spectra in the fundamental NH-stretching
region as a result of spectral subtraction of DMA spectrum from the
spectra measured at different vapor pressures. The spectra were mea-
sured with a 10 cm cell at 296 K. The higher pressure spectra are offset to
avoid overlapping between the spectra. The absorbance is obtained by
log(I0/I).
increases with pressure. To confirm that the difference between
the two spectra arises from DMA dimer, a series of spectra at
different pressures were measured.
We measured DMA spectra at pressures of 2, 70, 204, 315,
445, and 700 Torr. The spectrum at 2 Torr was measured with a
path length of 4.8 m and the other spectra with a path length of
10 cm. The spectrum at 2 Torr is subtracted with appropriate
weights taking into account the pressure and path length
difference of the FTIR spectra recorded at the five higher
pressures. All spectra were measured at 1.0 cm
1 resolution.
We also measured a few spectra at 0.2 cm
1 resolution. These
higher resolution spectra were almost identical to the spectra
recorded with 1.0 cm
1 resolution, and no fine structure was
observed at higher resolution. We assign the residual to be the
fundamental NH-stretching band of DMA dimer located at
3339 cm
1. This position is found by fitting a Lorentzian
function to the observed band. In the region from 2400 to
7000 cm
1, we did not observe any other transitions that we
could assign to the DMA dimer. The spectra obtained after
subtraction are shown in Figure 3.
According to the chemical equilibrium for DMA dimerization,
2DMA / ðDMAÞ2 ð3Þ
Kp ¼ pD =pM 2 ð4Þ
where Kp is the equilibrium constant and pD and pM are the vapor
pressures of the dimer and monomer, respectively. At a given
temperature, Kp is a constant, and therefore, pD is proportional to
pM2. In the IR absorption spectrum, the integrated intensity of
the DMA dimer band is proportional to pD, providing the same
path length is used. We integrated the band areas shown in
Figure 3, and plot the band area vs pM2 in Figure 4. The results fit
well with a linear fit (Figure 4), which suggests that the complex
formed at higher pressures is (DMA)2 and not large aggregates
and also support our assignment of the measured band to the
DMA dimer.
We have calculated IR frequencies and intensities of DMA and
DMA dimer both with a harmonic oscillator linear dipole (HO)
dx.doi.org/10.1021/jp206762j |J. Phys. Chem. A 2011, 115, 12097–12104
The Journal of Physical Chemistry A ARTICLE

We believe that a VTZ quality basis set is necessary to describe

the dimer well.
In the spectrum of DMA, two transitions at 3374 and
3359 cm
1 are observed in the NH-stretching region, due to
splitting by tunneling in the inversion mode. The higher fre-
quency transition arise from the ground state and is observed to
be slightly more intense.3 In our measurements, the DMA dimer
transition observed at 3339 cm
1 leads to an observed gas-phase
frequency redshift of 35 cm
1. Our QCISD/aug-cc-pVTZ AO
calculated red shift of the NHb-stretching vibration is 61 cm
1.
However, it has been observed that the coupling to lower
frequency modes ignored in the AO model can change the
stretching frequencies.48 If we compare the HO and AO calcu-
lated redshift with the B3LYP/aug-cc-pVTZ method we find that
the shift is about 20 cm
1 larger with the AO model. A 20 cm
1
decrease of the QCISD/aug-cc-pVTZ calculated shift would
bring it in very good agreement with the observed shift.
In the Ar matrix experiment, the NH-stretching fundamental
Figure 4. The linear fitting between integrated area of the DMA dimer transition in DMA is assigned to a peak at 3377 cm
1, and only
absorption band and pM2. These integrated areas are obtained from one transition is assigned. However, this transition is higher than
room temperature spectra at 296 K. both transitions observed in the gas phase, and with the usual
redshift caused by the Ar matrix we believe that this assignment is
perhaps incorrect. It should also be noted that the NH-stretching
Table 3. Observed and Calculated NH-Stretching Funda- transition in DMA is about 100 times weaker than normal
mental Frequency (cm
1) and Relative Intensities for the NH-stretching transitions, and perhaps difficult to assign in the
DMA Dimer matrix experiment.3 Thus, the reported redshift of 73 cm
1
from the solid Argon matrix FTIR experiment is likely too
method υN
H Δυa fD/fMb
high.22
harmonic B3LYP/aug-cc-pVTZ 3445 82 363 One should also take into consideration that we measure at
QCISD/aug-cc-pVDZ 3477 45 952 room temperature but calculate at 0 K. Previously, a difference
anharmonic B3LYP/aug-cc-pVTZ 3277 103 835 between room temperature redshift and low temperature
QCISD/aug-cc-pVDZ 3313 57 144
redshift has been found for the CHCl3
NH3 complex.9 The
redshift of the CH-stretching vibration in the jet-cooled spec-
QCISD/aug-cc-pVTZ 3348 61 571
trum (38 cm
1) is somewhat larger than the observed redshift at
Bohn and Andrewsc
observed 3304,3313 73
room temperature (17.5 cm
1). The reason for this discrepancy
this work 3339 35 is a temperature effect. At room temperature, the low-frequency
a
Δv = vmonomer
vdimer b fD/fM is the oscillator strength of dimer vs intermolecular vibrational modes are expected to be populated,
monomer. c Taken from ref 22. which lead to a broadening of the band and an overall redshift of
the band maximum.9
approximation and with an anharmonic oscillator local mode The fundamental NH-stretching transition in DMA is very
(AO) model. The calculated DMA dimer NH-stretching funda- weak is due to a very small dipole moment derivative.3 Thus,
mental frequency and intensity relative to that of the monomer deviations from a harmonic oscillator and a linear dipole become
are listed in Table 3. Additional results of the calculated important, and intensity ratio between dimer and monomer
frequencies and absolute intensities are given in Tables S1
S3 NH-stretching transitions (fD/fM) is likely more reliable with the
of Supporting Information. The calculations at all levels predict AO model. We believe that fD/fM ≈ 600 is a reasonable value for
an H-bonded dimer with a characteristic redshift and a very the intensity enhancement based on our QCISD/aug-cc-pVTZ
pronounced intensity increase of the NHb-stretching vibration. calculations. In comparison, the recent CCSD(T)-F12/VDZ-
The measured peak of the dimer band at 3339 cm
1 is in F12 value for fD/fM is 611.46 This is significantly higher than the
reasonable agreement with our QCISD/aug-cc-pVTZ anharmo- predicted values for trimethylamine-methanol (TMA-MeOH),
nic oscillator (AO) calculated NHb-stretching vibration fre- dimethylsulfide-methanol (DMS-MeOH), and dimethylether-
quency of 3348 cm
1. It is also in good agreement with peaks methanol (DME-MeOH) dimers,26,27 which all lie in the range
at 3312.8 and 3304.3 cm
1 observed in the Ar-matrix and of fD/fM ≈ 13
68.
assigned to (DMA)2.22 In an argon matrix, one typically observes An IR intensity increase is often observed for the hydrogen
a redshift of transitions by around 25 cm
1.47 stretching vibration of a hydrogen bond donor and is often
It is clear from Tables 2 and 3 that there is a large variation in considered as a defining feature of a typical hydrogen bond.45
the calculated binding energies and the calculated frequency shift In the ammonia dimer, the NH-stretching vibration is increased
and intensity enhancement with the range of theoretical methods by up to a factor of 9 compared to the monomer.49 However,
used. The large CP correction in the calculated binding suggests the NH-stretching fundamental transition in (DMA)2 is calcu-
that the cc-pVDZ and aug-cc-pVDZ basis sets are too small to lated to be ∼600 times stronger than that of the monomer.
describe well the weak interactions in the dimer. The calculated The IR intensity is determined mainly by the derivative of
IR intensities also vary significantly between the HO and AO the electronic dipole moment of the molecule, which changes
vibrational models when the aug-cc-pVDZ basis set is used. significantly between the monomer and the dimer. Furthermore,
12101 dx.doi.org/10.1021/jp206762j |J. Phys. Chem. A 2011, 115, 12097–12104
The Journal of Physical Chemistry A ARTICLE

the NH-stretching fundamental vibration of DMA is very weak

due to a very small first derivative of dipole moment function.3,50
Comparison of the experimental integrated band intensity and
the QCISD/aug-cc-pVTZ calculated oscillator strength of the
NHb-stretching band indicates that there is only about 0.1%
dimer present at room temperature with a total DMA pressure of
700 Torr. The large intensity enhancement of the NH-stretching
fundamental in the DMA dimer makes it possible to observe
the dimer in the gas phase, even at room temperature where
only a very small fraction of DMA undergoes dimerization.
The intensity of the NHf-stretching transition is calculated to
be 2.6 times stronger than the NH-stretching transition in DMA
monomer; however this small enhancement is not sufficient for
us to observe the NHf-stretching transition.
For comparison, we also calculated the intensity of the first
NH-stretching overtone transition of (DMA)2 at the QCISD/
aug-cc-pVTZ level with our AO local mode model, to see if we Figure 5. The temperature dependence of the NH-stretching band in
could record NH-stretching overtone transitions of the DMA the DMA dimer. A path length of 2.4 m was used. At a given temperature,
dimer. For the DMA monomer, it was found that the first the spectrum was measured with a total pressure of 200 Torr.
NH-stretching overtone was stronger than the fundamental
transition.3 However, we predict the first NHb-stretching over-
tone of (DMA)2 to have only 0.01% of the intensity of the
fundamental vibration of the dimer and only 1% of the intensity
of the first overtone transition of DMA. This intensity decrease
of the first NHb-stretching overtone transition is also typical for
NH or OH bonds involved in hydrogen bonding.47,50 This is part
of the reason why overtones of complexes are difficult to measure
at room temperature.1,51,52
Enthalpy of Hydrogen Bond Formation. If we assume
that the enthalpy of a chemical equilibrium is independent of
temperature, we can use the van’t Hoff equation to write53
ln Kp ¼
ΔH=RT þ C ð5Þ

where Kp is the equilibrium constant, ΔH the enthalpy of a chemical

equilibrium, R the gas constant, T the absolute temperature, and C
an integration constant. The enthalpy ΔH can be determined if we
can obtain Kp at different temperatures. In our case, Kp is the
equilibrium constant of DMA dimerization and ΔH is the enthalpy
of hydrogen bond formation for the DMA dimer. As seen in eq 4,
Kp is proportional to pD on the condition of keeping pM a constant.
The dimer pressure pD is proportional to the measured integrated
absorbance of the dimer band. Therefore, we have
0 appropriate weights on the low pressure spectrum used in the
lnðAÞ ¼
ΔH=RT þ C ð6Þ
where A is the integrated absorbance of the dimer band and C0 is a
new constant.
We recorded the IR spectra of (DMA)2 in the temperature
range from 296 to 368 K to determine the enthalpy of hydrogen
bond formation for the DMA dimer. In general, to get the dimer
spectrum at a certain temperature, two absorption spectra are
needed: a high-pressure spectrum of DMA and its dimer and
a low pressure spectrum where dimer contribution is minimal.
The latter is a pure DMA monomer spectrum necessary for
subtraction. The vapor pressure of DMA should be kept constant
for all the high pressure measurements. The pressure of the
dimer in the mixture is less than 0.2% of the total pressure and
can therefore be neglected in the total pressure. We select
the constant pressure such that the DMA dimer spectrum after
subtraction should be measurable and the absorbance of the
NH-stretching band in the spectrum should not saturate the
detector. After several test measurements, we decided to use
12102
Figure 6. Linear least-squares fitting of the van’t Hoff equation plot for
the DMA dimer.
200 Torr for the high pressure spectra. Similarly, since we will use
spectral subtraction, the pressure cannot be too low, otherwise
the uncertainties would be amplified. Finally, we decided to
use 20 Torr in the low pressure spectrum, which will need a
weighting of around 10 in the subtraction. We used the ideal gas
law to determine the filling pressure necessary to obtain 200 Torr
pressure at each of the elevated temperatures.
Representative IR spectra in the NH-stretching region of
DMA dimer after spectral subtraction are shown in Figure 5
and the van’t Hoff equation plot for DMA dimer is shown in
Figure 6. Because of the weighting of the low pressure spectra,
the quality of the spectra in Figure 5 is not as good as the spectra
in Figure 3. We used intergrated band areas as the measure
of the absorbance in each of the different temperature spectra.
After linear least-squares fitting, the dimerization enthalpy
ΔH in the temperature range 296
368 K is determined to be

23.8 ( 2.2 kJ mol
1 from the slope in Figure 6. We calculated
the enthalpy of dimerization to be
23.1 kJ mol
1 with
the QCISD/aug-cc-pVDZ method and for the higher level
dx.doi.org/10.1021/jp206762j |J. Phys. Chem. A 2011, 115, 12097–12104
The Journal of Physical Chemistry A
QCISD/aug-cc-pVTZ method with a B3LYP/aug-cc-pVTZ
thermodynamic correction we obtain
20.4 kJ mol
1, both in
good agreement with our experimental determination.
The enthalpy ΔH of H-bond formation is directly related to
the stabilization energy of a complex.54 In a stronger H-bonded
complex like methanol-trimethylamine (MeOH-TMA), the
observed enthalpy is approximately
29 kJ mol
1.55,56 The
enthalpies of H-bond formation in weaker complexes have been
determined to be
14.8 and
19.1 kJ mol
1 for DMS-MeOH
and DME-MeOH, respectively.27 However, in ref 27, no correc-
tion for change in total pressures was considered in the measure-
ments at different temperatures; therefore, at temperatures
higher than room temperature, the pressure of the monomers
are slightly higher than the pressure read when the cell was filled
with sample gas and the determined ΔH values are likely a few
kJ mol
1 too small. For comparison, we also measured ΔH without
corrections for pressure changes and obtain a value of
16.9 (
3.0 kJ mol
1. The linear least-squares fitting of van’t Hoff equation
plot of DMA dimer for the experiment without pressure correction is
given in Supporting Information (Figure S1).
Thermodynamic Dimerization Equilibrium Constant. As
seen from eq 4, at a certain temperature, the thermodynamic
dimerization equilibrium constant Kp can be determined pro-
vided that the partial pressure of DMA (pM) and DMA dimer
(pD) could be measured. This has been used to determine Kp for
dimers with large Kp values.57 However, due to the small changes
in pD for different total pressure, this is impossible for DMA.
Instead, we estimate the partial pressure of the dimer pD from the
measured and anharmonically calculated NH-stretching intensi-
ties. At the QCISD/aug-cc-pVTZ level, the NH-stretching
fundamental transition in (DMA)2 is calculated to be 571 times
stronger than that of the monomer. The ratio of the experimental
integrated band intensity and the theoretical oscillator strength
gives the partial pressure of the dimer.36 A plot of pD against
p2M for each of the experiments is shown in Figure S2 of Supporting
Information. The slope of the least-squares fitting of these data is the
thermodynamic dimerization equilibrium constant, Kp, which
we determined to be 1.4  10
3 atm
1 at a temperature of
296 K. The Kp determination method depends on the calculated
intensity enhancement, which varies with theoretical method used.
We have used our highest level value obtained with the QCISD/
aug-cc-pVTZ AO method, with a fD/fM ≈ 571. Uncertainty in the
calculated intensity will be reflected in uncertainty in the deter-
mined Kp value. However, at the aug-cc-pVTZ basis set level, the
intensity ratio of our different approaches is in the range (363 to
835), and thus our Kp value is accurate to within a factor of 2. The
decrease in band absorbance with increasing temperature, as
shown in Figure 5, clearly illustrate the decrease in the equilibrium
constant with increasing temperature. We have estimated Kp
theoretically with a statistical thermodynamics procedure and find
it to be 3.8  10
5 atm
1 at the B3LYP/aug-cc-pVTZ level and
2.6  10
3 atm
1 at the QCISD/aug-cc-pVTZ level with B3LYP/
aug-cc-pVTZ thermodynamic values.58 The loose binding of
complexes with the B3LYP method is in agreement with the
smaller Kp value obtained with this method. The better calculation
agrees reasonably well with our combined experimental and
theoretical determined value.
’ CONCLUSIONS
The dimethylamine dimer in the gas phase has been investi-
gated by FTIR and ab initio calculations. The geometry of the
12103
ARTICLE
most stable conformer of the dimer is characterized by a non-
linear hydrogen bond N
H 3 3 3 N between the two DMA
molecules. The IR spectrum of the dimer shows a characteristic
small redshift of the NH-stretching vibrational band and a
pronounced intensity increase. The large increase in IR intensity
makes it possible to obtain the IR spectrum of the dimer in the
gas phase at room temperature. The detected fundamental NH-
stretching band of the dimer is obtained by subtracting monomer
spectra and shows the expected pressure square dependence.
This provided evidence of the DMA dimer in the gas phase.
On the basis of the measurements of the temperature depen-
dence of the dimer spectra, the enthalpy of hydrogen bond
formation in DMA dimer in the temperature range of 296
368 K
was determined to be
23.8 ( 2.2 kJ mol
1 in agreement with
theoretical predictions. We combine the experimental integrated
intensity of the NH-stretching dimer band with anharmonic local
mode intensity calculations to obtain an estimate of the thermo-
dynamic dimerization equilibrium constant of 1.4  10
3 atm
1
at room temperature.
’ ASSOCIATED CONTENT
bS Supporting Information. The linear least-squares fitting
of van’t Hoff equation plot of DMA dimer without pressure
correction; a plot of pD against pM2 to determine the thermo-
dynamic dimerization equilibrium constant; calculated frequen-
cies and intensities for DMA and DMA dimer with normal mode
method; calculated NH-stretching fundamental and overtone
frequencies and oscillator strengths for DMA dimer with an AO
local mode model; calculated NH-stretching fundamental fre-
quency and relative intensities for the two conformers A and B of
DMA dimer; z-matrices of DMA and DMA dimer (conformer B)
at QCISD/aug-cc-pVTZ level. This material is available free of
charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: hgk@chem.ku.dk. Fax: 45-35320322. Phone: 45-35320334.
’ ACKNOWLEDGMENT
We thank Lauri Halonen, Benjamin J. Miller, and Joseph R.
Lane for helpful discussions and Rene W. Larsen for help with the
FTIR measurements. We are grateful for support from The
Danish Council for Independent Research—Natural Sciences
and the Danish Center for Scientific Computing.
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