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Influence of intermolecular interactions on the

infrared complex indices of refraction for binary
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Cite this: Phys. Chem. Chem. Phys.,

2022, 24, 22206 liquid mixtures†
Tanya L. Myers, * Bruce E. Bernacki, Michael J. Wilhelm,
Karissa L. Jensen, Timothy J. Johnson, Oliva M. Primera-Pedrozo,
Russell G. Tonkyn, Steven C. Smith, Sarah D. Burton and Ashley M. Bradley

This paper investigates the accuracy of deriving the composite optical constants of binary mixtures
from only the complex indices of refraction of the neat materials. These optical constants enable the
reflectance spectra of the binary mixtures to be modeled for multiple scenarios (e.g., different
substrates, thicknesses, volume ratios), which is important for contact and standoff chemical detection.
Using volume fractions, each mixture’s complex index of refraction was approximated via three different
mixing rules. To explore the impact of intermolecular interactions, these predictions are tested by
experimental measurements for two representative sets of binary mixtures: (1) tributyl phosphate
combined with n-dodecane, a non-polar medium, to represent mixtures which primarily interact via
dispersion forces and (2) tributyl phosphate and 1-butanol to represent mixtures with polar functional
groups that can also interact via dipole–dipole interactions, including hydrogen bonding. The residuals
and the root-mean-square error between the experimental and calculated index values are computed
and demonstrate that for miscible liquids in which the average geometry of the cross-interactions can
be considered isotropic (e.g., dispersion), the refractive indices of the mixtures can be modeled using
Received 27th June 2022, composite n and k values derived from volume fractions of the neat liquids. Conversely, in spectral
Accepted 4th September 2022 regions where the geometry of the cross-interactions is more restricted and anisotropic (e.g., hydrogen
DOI: 10.1039/d2cp02920k bonding), the calculated n and k values vary from the measured values. The impact of these interactions
on the reflectance spectra are then compared by modeling a thin film of the binary mixtures on an
rsc.li/pccp aluminum substrate using both the measured and the mathematically computed indices of refraction.

I. Introduction can be used along with other methods to estimate plume

temperature and path length. For solid materials, databases
Detection of solids, liquids and gases is important for a wide of reflectance spectra are often employed12–17 whereas trans-
range of environmental, industrial and national security appli- mittance (absorbance) data are more commonly used for
cations, including extraterrestrial exploration,1–3 pollution moni- liquids.18,19 Liquids, however, are seldom observed in the
toring4,5 and hazardous chemical detection.6 Spectroscopic environment in pure bulk form except for bodies of water,
methods7 are often used and typically involve applying detection and only seldom for most solids. Thus, for both solid- and
(or spectral matching) algorithms8–10 that rely on a set of library liquid-phases, there has been an ever-increasing need to model,
spectra containing both target and background materials for rather than measure, the reflectance (or emittance) spectra that
material identification. For gases, databases of absorbance can account for the sundry morphological forms that may exist
spectra allow identification of unknown gases in plumes11 and in natural and industrial environments, including thin vs. thick
layers, mixtures, particles, droplets, etc.16,20–23 Such modeling
Pacific Northwest National Laboratory, P.O. Box 999, Richland, WA 99352, USA. can be undertaken by knowing or anticipating the suspected
E-mail: [email protected] geometry (e.g. liquid layer thickness), and then ray tracing
† Electronic supplementary information (ESI) available: FTIR data collection using the Beer Lambert Law, Snell’s Law and the Fresnel
parameters, the n(l) and k(l) spectra for neat TBP, n-dodecane and 1-butanol,
equations.19 The real, n(n), and imaginary, k(n), components
the calculated intermolecular interactions, the measured and modeled n-values
for mixtures of TBP with n-dodecane and 1-butanol at 10 000 cm1, 1H NMR
of the complex refractive index, however, are a prerequisite
spectra and 31P NMR spectra for the TBP:n-butanol mixtures and the spectral to such calculations, which can be used to simulate the
deconvolution plots (PDF). See DOI: https://doi.org/10.1039/d2cp02920k reflectance spectra and account for the multiple phenomena

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(reflection, refraction and absorption) that affect the spectral of the two dipoles and therefore tends to be localized to specific
content of the light reflected from condensed phase materials functional groups within the pair of molecules. In the limit of two
deposited on different substrates.24 interacting molecules, the distribution of energetically favorable
To this end, work has been undertaken in our laboratory to dipole–dipole interactions is not randomly distributed (i.e., there
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catalog the complex index of refraction for numerous liquids18 is a preferred orientation). Consequently, dipole–dipole inter-
that can provide an alternative approach to identifying unknown actions should have a greater tendency to influence the spectral
liquid substances. In the event of chemical spills, for example, responses of the functional groups involved in the interaction.
liquids are more likely encountered as thin films (submicron Conversely, dispersion interactions simply involve transient per-
to 100’s of microns) on metallic or dielectric substrates whereby turbations to the electron clouds of the interacting molecules.
Open Access Article. Published on 12 September 2022. Downloaded on 3/29/2025 12:25:36 AM.

both the substrate as well as the liquid contribute to the Unlike dipole–dipole, the distribution of dispersion interactions
composite reflectance signature. By knowing the complex index is reasonably isotropic (i.e., there is not a preferred orientation
of refraction of a liquid (as well as the substrate) the arrangement since the geometry of the interaction is not limited to a specific
can thus be modeled (by varying liquid thickness, substrate type, functional group, and the two molecules can adopt any orienta-
angle of incidence, polarization) using methods such as ray tion relative to one another). As a result, dispersion interactions
tracing or thin film modeling along with the transfer matrix should have comparatively little influence on spectral properties,
method (TMM)25 until a match is obtained for the previously especially if both molecules exhibit comparable dispersion
unknown acquired signature. For the present purposes, the interactions. Thus, to gain a better quantitative understanding
complex index of refraction is defined as below in eqn (1) where of the role of intermolecular interactions on the optical con-
n(l) governs the refraction and reflection of light, and k(l) is stants of mixtures, we examine two representative cases: (1) a
concerned with attenuation and the reflectance of light, espe- binary mixture capable of interacting predominantly through
cially in metals. dispersion interactions (and therefore exhibiting well-behaved
spectral responses, characteristic of a linear combination of
ñ(l) = n(l) + ik(l) (1)
the neat spectra) and (2) a binary mixture that is also capable
Most modeling efforts have focused on a single material of hydrogen bonding (dipole–dipole) interactions which are
deposited on a substrate even though mixtures are more likely more likely to impact the infrared spectral features. Specifically,
to be encountered in the environment and are more challen- the first case combines tributyl phosphate (TBP), [(CH3CH2-
ging for spectral identification compared to their neat liquid CH2CH2O)3PQO], a polar organophosphate compound, with
counterparts. Generation of reference spectra for liquid mixtures26 n-dodecane, [CH3(CH2)10CH3], a long non-polar hydrocarbon
using simply the experimentally determined complex index chain. The PQO functional group in TBP leads to dipole–dipole
of refraction data for the neat liquids along with the ratio of interactions for neat TBP, whereas n-dodecane experiences
each component is appealing since preparing and measuring stronger dispersion forces due to its long, linear hydrocarbon
all possible combinations of mixtures that may be present is chain.37 These intermolecular interactions in the neat liquids
impractical. Other approaches involve post-processing using are quite strong as evidenced by the high boiling points
spectral unmixing algorithms to estimate the abundances of (i.e., TBP = 289 1C and n-dodecane = 216 1C).38 In addition to
each of the constituents from the neat end-member spectra.27 dispersion, dipole–induced dipole interactions can also occur
These methods, however, are only effective if the individual between these two liquids. Prior studies have shown, however,
components of the mixture do not interact strongly with one that n-dodecane does not interact significantly with TBP;39
another and often require a priori knowledge of the materials in thus, it is expected that these binary mixtures should lead to
the scene. more ideal spectral responses. The second case mixes TBP with
Many prior studies have investigated the optical and ther- 1-butanol, [CH3(CH2)3OH], a polar protic solvent with an OH
modynamic properties of binary liquid mixtures due to their moiety capable of hydrogen-bonding. Similar to the TBP:n-dode-
relevance for solvation and extraction chemistries.28–36 The cane mixtures, TBP:1-butanol is capable of both dispersion
earlier studies mostly focused on predicting the real part of and dipole–induced dipole interactions. However, due to the
the refractive index in non-absorbing spectral regions, e.g., in presence of the OH and PO moieties, the TBP:1-butanol mix-
the visible region at select wavelengths such as 589 nm,28,29 tures are also capable of hydrogen bonding (dipole–dipole)
546 nm and 436 nm.30,31 This study examines the complex interactions. Consequently, it is expected that these binary
refractive index in absorbing regions from 1 to 25 mm (10 000 to mixtures should lead to non-ideal spectral responses, particu-
400 cm1) as this spectral region is most important for larly in regions associated with functional groups involved in
chemical detection, containing both the fundamental absorp- the interaction.
tion bands as well as weaker overtone and combination bands. A series of binary mixtures is prepared for both TBP:
Different van der Waals forces, including London dispersion, n-dodecane and TBP:1-butanol with different volume percentages
dipole–induced dipole, and dipole–dipole interactions have the to experimentally derive the composite index of refraction for
potential to influence the various functional groups within both sample cases and investigate its impact on the resulting
the mixtures and can therefore perturb the resulting spectra. quality of the predicted spectra. The complex refractive indices
Specifically, for dipole–dipole interactions, including hydrogen- of the binary mixtures are computed using three different
bonding, the interaction is determined by the relative orientation mixing rules along with the measured optical constants of the

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neat liquids.30,40–42 The experimentally derived and computed The optical cells were placed in sample holders in both
optical constants of the mixtures are compared to assess the Bruker Tensor 37 and Bruker Vertex 70 instruments for mid-
impact of the various intermolecular interactions. Finally, to infrared (MIR) and near-infrared (NIR) measurements, respec-
investigate the efficacy of using the predicted optical constants tively. Cell path lengths of approximately 3000, 1000, 500, 200
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for modeling reflectance spectra, thin liquid layers of the binary and 100 mm were analyzed using the (NIR) Vertex 70 and cell
mixtures are modeled on an aluminum substrate using both sets path lengths of approximately 500, 200, 100, 50, 20, 10, 5, 2, and
of index values. 1 mm were analyzed using the (MIR) Tensor 37. Typically, for
the 500, 200 and 100 mm path lengths, the same cell with
the same liquid fill was used for both systems. The spectro-
II. Methods
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meter sample compartment was continuously purged with

ultra-high purity N2 during data collection. The FTIR experi-
A. Experimental
mental parameters are provided in Table S1 of the ESI.†
The measurement of the complex index of refraction of the A daily calibration was conducted for both the MIR and NIR
liquid mixtures was performed as described in detail in a systems to ensure consistent optimal performance. The x-axis
previous publication for neat species.18 These vetted protocols (frequency) was calibrated by comparing an absorbance spectrum
are readily applied to the binary mix measurements: a wide of air (obtained by opening the sample chamber) to reference
range of cell path lengths are used to determine the k-vector CO2 and H2O lines from the PNNL gas-phase database.46 The
spectrum as a single sample cell cannot usually yield a com- y-axis (transmission) was calibrated with an MRC Infrared
plete k-vector, because strong bands saturate in the long path Linearity Standard (MRC-910-NG11 S/N 0108) where known
cells, while weak bands are often obscured by noise in the short transmission values were compared to measured values at
path cell data. From the multiple cell spectra, the resulting various wavelengths across the spectrum. A signal-to-noise test
k-vectors are baseline corrected and then spliced together using was also performed to check for drift or reduction in the IR signal.
selected bands over their linear domains to form a composite
k-vector that is valid for both weak and strong bands, extending C. Experimentally-derived optical constants
across the full spectral range of the instrument. This k-vector is Typically, six spectra of each cell path length were recorded.
smoothed (in select regions) if necessary and the associated Replicate spectra of a single sample were evaluated for consis-
n-vector is determined by application of the Kramers–Kronig tency and an average spectrum calculated in OPUS,47 excluding
relations.43 The final calculation of the n-vector is a key product any outlier spectra. The measured cell path lengths were
of the analysis; all the intermediate n-vectors calculated for adjusted using Beer–Lambert Law plots in which the NIR and
individual cells (which are not valid across entire spectral MIR data were analyzed independently. The imaginary part of
range) are discarded. the refractive index, or k vector, was determined for each
absorbance file as per Bertie’s program ‘‘RNJ46A’’45,48 which
B. Data acquisition takes into account the reflective losses due to the KCl or KBr
The following chemicals were used either as neat materials or cell windows. The k vectors were created via a classical,
mixtures in selected proportions: tributyl phosphate (Sigma- weighted, linear, least squares fit using the output files of
Aldrich, 499%), n-dodecane (Alfa Aesar, 499%) and 1-butanol program ‘‘RNJ46A’’ in which individual absorbance values were
(Sigma-Aldrich, 99.8%). Mixtures were prepared by carefully weighted by T2 (transmission squared) and all absorbance
combining appropriate mass amounts of the two chemicals. values Z2.5 were given zero weight to ensure linearity across
The scalar refractive indices of the samples were measured the entire spectral range. The individual k vectors for each cell
using an Abbe refractometer at fixed wavelengths in the near- path length were baseline-corrected prior to creating composite
infrared and visible domain. As suggested by Bertie, the refrac- k vectors using data from appropriate cell path lengths and
tive index at the highest wavenumber is determined from a fit spanning appropriate wavenumber ranges.18,49 Finally, a single
of n to the measured values.44,45 composite k vector was prepared for each of the MIR and NIR
Commercially prepared optical cells (International Crystal data. The two composite k vectors representing the MIR and
Laboratories) with either potassium bromide (KBr) or potas- NIR data were then merged over a narrow spectral range
sium chloride (KCl) windows were used with path lengths of (typically of 100–500 cm1 width, near 3300 cm1) in the
approximately 3000, 1000, 500, 200, 100, 50 or 25 micrometer overlap region where both MIR and NIR data were collected
(mm). In addition, cells of shorter path length, e.g., approxi- with few absorption features, i.e. near the baseline.50
mately 15, 10, 5, 2 and 1 mm, were prepared by compressing the The real part of the complex index of refraction (n) was
25 mm commercial cells with a hydraulic press. Prior to analyz- determined by first measuring the n-values for the binary
ing the liquid chemicals, a survey IR spectrum was recorded, mixtures at 480, 486, 546, 589, 644, 656 and 1550 nm using
and the path length of the empty cell was estimated from the an ATAGO refractometer. A modified-Sellmeier equation was
fringe spacing using the equation d = (2  n  Dv)1 where then used to interpolate n at 10 000 cm1.51 The final n vector
n refers to the refractive index of air (n = 1) and Dv is the fringe for each point mixture was calculated using the composite k
spacing. The liquid sample was loaded into the optical cell vector and the refractive index at 10 000 cm1 per Bertie’s
using a syringe. ‘‘LZZKTB’’ program with the Kramers–Kronig relation. The real

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and imaginary parts of the complex index of refraction are Each of these expressions use the n and k values of the neat
provided for the neat substances in Fig. S1 and S2 of the ESI.† materials, which were experimentally derived (Section II.C). The
simplest approach for calculating the complex refractive index for
D. Binary sample preparation and measurement mixtures is that of Dale–Gladstone and Arago–Biot40 that takes the
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Two sample series based on binary mixtures of TBP with either form shown below in eqn (2) and is referred to as the Arago–Biot
n-dodecane or 1-butanol were prepared. Each chemical was (AB) method. Here ñmix is reported as a function of wavelength (l)
prepared and analyzed in its original form, and in mixtures in and is defined as the complex index of refraction previously
select proportions to yield a 7-point mixing line: 100/0%, defined in eqn (1), in which fa and fb are proportionality
90/10%, 70/30%, 50/50%, 30/70%, 10/90% and 0/100% based constants based on volume fraction.
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on mole percentages. These mixtures were prepared by care- ñmix(l) = faña(l) + fbñb(l) (2)
fully combining appropriate mass amounts of the two chemi-
cals to obtain the desired mole percentages. As the mixing rules Another variation referred to as the Newton method,30 is shown
are based on volume fraction (f), the volume percentages in eqn (3). This method is based on the relative permittivity,41
(f  100%) were calculated using the reported densities38 where e signifies the relative permittivity of the liquid and is
and are summarized in Table 1 for both series of mixtures. defined as e = (ñ)2.
The calculated volume percentages for the TBP:n-dodecane ñmix2(l) = faña2(l) + fbñb2(l) (3)
mixtures (Table 1) are almost equivalent to the mole percen-
42
tages since the two species have similar molar volumes (Vm) Finally, the Lorentz–Lorenz (L–L) equation as detailed in
whereas the calculated volume percentages for TBP:1-butanol eqn (4) is similar to the Newton method with some additional
mixtures (Table 1) are significantly different than the mole factors:
percentages. (The reported densities and molar masses can
n~mix 2 ðlÞ  1 n~a2 ðlÞ  1 n~b2 ðlÞ  1
be used to calculate the molar volumes: Vm is equal to ¼ fa þ fb (4)
n~mix 2 ðlÞ þ 2 n~a2 ðlÞ þ 2 n~b2 ðlÞ þ 2
273.8 cm3 mol1 for TBP, 227.3 cm3 mol1 for n-dodecane
and 91.6 cm3 mol1 for 1-butanol, respectively). To provide These three methods are all predicated on the following
similar proportions for the volume percentages for the TBP–1- assumptions:
butanol mixtures, an additional mixture was prepared to 1. The liquids are assumed to be non-reacting with
include a 10 : 90 volume percent ratio, and the 90 : 10 mole each other.
percent mixture was excluded from the analysis since it was 2. The total volume or mass of the mixture is equal to the
mostly TBP, i.e. 96% TBP by volume. sum volume or mass of the two liquids being mixed.
3. All measurements and analyses are assumed at a fixed
E. Computational temperature, e.g., 27 1C.
Three different mixing rules of varying complexity were used to
compute the composite optical constants of the binary mixtures.
III. Results and analysis
A. Passive influence of dispersion interactions: mixtures of
Table 1 Summary of the parameters for the TBP:n-dodecane and TBP:1-
butanol mixtures
tributyl phosphate and n-dodecane
The neat liquids of TBP and n-dodecane provide a case study for
TBPa Volume Mole Volume
mass Mole percent n-dodecane b
percent percent mixtures that primarily interact through the dispersion forces
(g) percent (%) (%) mass (g) (%) (%) between the alkyl chains present in both liquids (though
13.1898 91 92 0.8750 9 8 dipole–induced dipole interactions may also occur due to the
11.7638 70 74 3.2448 30 26 polar PQO group in TBP, see S3 in ESI†). Specifically, due to the
9.1543 50 55 5.8678 50 45 isotropic nature of dispersion interactions (i.e., the interaction
6.0559 30 34 8.9859 70 66
2.2163 9 10 15.0088 91 90 is not localized to a specific functional group/molecular orien-
tation), these mixtures are predicted to demonstrate more ideal
TBP Mole Volume Mole Volume behavior in which the calculated n and k spectra are expected to
mass percent percent 1-Butanolc percent percent
(g)
better match the measured spectra. As indicated in Table 1,
(%) (%) mass (g) (%) (%)
volume percent ratios of 100 : 0, 92 : 08, 74 : 26, 55 : 45, 34 : 66,
1.7677 4 10 13.2375 96 90
10 : 90 and 0 : 100 were prepared and measured for TBP and
4.3186 10 25 10.8129 90 75
9.0966 30 56 5.9073 70 44 n-dodecane mixtures. The first number refers to the TBP
11.7396 50 75 3.2715 50 25 volume percent, the second to the n-dodecane volume percent.
13.4146 70 88 1.5923 30 12
Fig. 1 presents the experimental progression of both the real (n)
14.9555d 90 96 0.4479 10 4
and imaginary part (k) of the index as the volume mixture
a
TBP properties: M = 266.32 g mol1, r = 0.9727 g cm3. b n-Dodecane percentage varies from 100% TBP (black trace in Fig. 1) to 100%
properties: M = 170.33 g mol1, r = 0.7495 g cm3. c 1-Butanol properties:
M = 74.121 g mol1, r = 0.8095 g cm3, Vm = 91.6 cm3 mol1. d Mixture n-dodecane (purple trace in Fig. 1). The strongest absorption
excluded from analysis since it is predominantly TBP. features for TBP include the triplet peak centered at 1029 cm1

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Fig. 1 The measured (a) real part of the index of refraction n and (b) imaginary part of the index of refraction k as the percent volume mixture ratio
progresses from 100 : 0 to 0 : 100 for TBP:n-dodecane. The spectra are offset for clarity.

(9.72 mm) assigned to the P–O–C group, the peak located at residuals show that the differences are not randomly distri-
1282 cm1 (7.8 mm) assigned to the PQO stretch and a band buted but rather centered around spectral features. These
centered around 2961 cm1 (3.38 mm) corresponding to the residuals can also be referred to as the excess spectrum, similar
C–H stretching modes.52 For n-dodecane, the dominant peaks to the excess molar volume and excess molar enthalpies
are the C–H stretching modes centered around 2924 cm1 described by other researchers.28,35,53 The differences for the
(3.42 mm). n-values (Fig. 2a) range from 0.011 to 0.015 and show the
For each of the TBP:n-dodecane mixtures, the composite n model mostly overpredicts the n-values as indicated by the
and k values were also calculated from the expressions in negative offset ca. 0.002. The root-mean square error (RMSE)
eqn (2) through eqn (4). These predicted n and k values were between the modeled and measured refractive index of the
compared to the measured n and k values presented in Fig. 1, mixtures is 0.002. For comparison, the standard measurement
and the residuals determined by subtracting the calculated error (2s) for the measured n-value at 1550 nm is 0.001. The
index of refraction from the values derived from the measure- measured and modeled n-values at 10 000 cm1 for the five
ments of the binary mixtures. As an example, the results for mixtures and the neat components are also provided in Fig. S4
the n and k spectra of the 55 : 45 mixture of TBP:n-dodecane of the ESI.† Similarly, as seen in Fig. 2b, the model mostly
along with its residuals are shown in Fig. 2. Inspection of the overpredicts the k-values, and the residuals vary from 0.16 to

Fig. 2 Plots showing (a) the real part (n) and (b) imaginary part (k) of the complex refractive index for both the experimentally measured and calculated
values (using eqn (2)) for a 55 : 45 mixture of TBP and n-dodecane. Bottom panels show the residual error between the experimental and calculated index
values.

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0.008 in which the largest differences occur at 1280 and TBP (92 : 08) has the smallest errors. Fig. 3b is plotted from
2924 cm1 corresponding to the PQO and C–H stretching 3000–2817 cm1 (3.3–3.55 mm) and highlights the C–H stretch-
regions, respectively. The RMSE between the calculated and ing region. In this spectral region, the residuals are also
measured k-values is 0.001. Note that the mixing rules require negative for most of the mixtures, particularly for the band
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the use of volume fractions vs. mole fractions; using mole located at 2924 cm1, which is assigned to the CH2 antisym-
fractions with eqn (2) through eqn (4) leads to slightly higher metric stretch for n-dodecane.55 Note that the deviation
errors in the calculated spectra since the mole fractions are between measured and computed k-values for this mode
slightly different than the volume fractions (see Table 1). increases with the n-dodecane concentration and is largest for
An expanded view of the measured (solid lines) and com- the 10 : 90 mixture. Slightly lower k-values at 2924 cm1 are
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puted k-values (dashed lines) centered in spectral regions observed for the three mixtures with the highest concentration
corresponding to the C–H and PQO stretching regions is seen of n-dodecane (i.e., 55 : 45, 34 : 66 and 10 : 90) compared to the
in Fig. 3 for all five binary mixtures of TBP:n-dodecane as well computed k-values. The alkyl chains in TBP and n-dodecane
as neat TBP and n-dodecane. Fig. 3a is plotted from 1310– will interact via London dispersion forces and these are pre-
1220 cm1 (7.6–8.2 mm) and highlights the PQO stretching dicted to be the strongest cross-interactions (see Fig. S3 of the
region. Three peaks in the PQO stretching region are observed ESI†). However, dipole–induced dipole interactions between
and have been previously attributed to different distributions of the PQO and CH2 moieties may also occur. These cross-
conformers.54 However, an ab initio calculation of the funda- interactions might explain the slight blue-shift of the PQO
mental vibrational modes of TBP predicts three distinct PQO mode and the reduced amplitude of the CH2 stretch.
modes in this region: n66 (1250 cm1) and n69 (1265 cm1), both
assignable to the PQO stretch plus different CH2 wags, as well B. Perturbing influence of dipole–dipole interactions:
as n71 (1280 cm1) which is assignable to the PQO stretch plus mixtures of tributyl phosphate and 1-butanol
CH2 rocking motions (see S3 in ESI† for more detail). In this The neat liquids of TPB and 1-butanol provide opportunities to
spectral region, the residuals for the k-values in the 55 : 45 examine systems of increased complexity. In addition to the
mixture are primarily negative (Fig. 2b) indicating the mixtures dispersion and dipole–induced dipole interactions present in
of TBP and n-dodecane are interacting (if only slightly). The the TBP:n-dodecane mixtures examined above, TBP:1-butanol is
deviation from ideal behavior provides a measure of the degree also capable of hydrogen bonding (dipole–dipole) interactions
of interaction between the two liquids. In addition, a slight and is thus expected to demonstrate a greater propensity for non-
blue-shift for the PQO peak for TBP at 1282 cm1 is observed ideal spectral behavior. Specifically, due to the anisotropic nature
as the fraction of n-dodecane increases, e.g., the PQO peak of dipole–dipole interactions (i.e., the interaction preferentially
is shifted to 1287 cm1 for the 10 : 90 mixture. For TBP: involves specific functional groups in each molecule), the pre-
n-dodecane, the mixture with the largest concentration of dicted n and k spectra are expected to deviate from the measured

Fig. 3 The k-spectra for the binary mixtures of TBP:n-dodecane in the region of the (a) PQO stretching region from 1310–1220 cm1 (7.6–8.2 mm) and
(b) C–H stretching region from 3000–2817 cm1 (3.3–3.55 mm). The experimental data are plotted as solid lines, and the theoretical predictions (based
on eqn (2)) are plotted as dashed lines.

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Fig. 4 The measured (a) real part of the index of refraction n and (b) imaginary part of the index of refraction k as the percent volume mixture ratio
progresses from 100 : 0 to 0 : 100 for TBP : 1-butanol mixtures. The spectra are offset for clarity.

spectra in these mixtures (particularly in the O–H and PQO in Fig. 4. Fig. 5 shows the measured and computed values for
stretching modes). Volume mixture ratios of 100 : 0, 88 : 12, the 56 : 44 mixture of TBP : 1-butanol along with the residuals
75 : 25, 56 : 44, 25 : 75, 10 : 90 and 0 : 100 were prepared and for both n and k values, respectively. The model mostly over-
measured for mixtures of TBP:1-butanol. The real and imaginary predicts the n-values and a negative offset of 0.01 is observed.
parts of the refractive index are stack-plotted in Fig. 4 in which the The residuals for the n-values (Fig. 5a) vary from 0.077 to
mixture ratio varies from neat TBP (black trace) to neat 1-butanol 0.042, and the RMSE between the measured and calculated
(purple trace). For 1-butanol, the strongest absorption features n-values is 0.012, which is a factor of six larger than the RMSE
correspond to the broad O–H stretching band centered at of 0.002 observed for 55 : 45 mixture of TBP : n-dodecane and
3329 cm1 (3.0 mm), multiple bands in the 2950–2850 cm1 well outside of the measurement variability (2s o 0.001). The
(3.4–3.5 mm) domain assigned to C–H stretching modes, and multi- measured and modeled n-values at 10 000 cm1 for the five
ple bands around 1080–1025 cm1 (9.3–9.8 mm) assigned to C–C and mixtures and the neat components are also provided in Fig. S4
C–O stretching modes along with CH3 rocking motion.56,57 of the ESI.† Fig. 5b shows the model both over and under-
For each of the mixtures, the n and k values were also predicts the k-values, and the residuals range from 0.066 to
computed using the expressions in eqn (2) through eqn (4) 0.057 with an RMSE of 0.005, compared to an RMSE of 0.001 for
and compared to the measured n and k values presented the 55 : 45 mixture of TBP : n-dodecane. The largest differences

Fig. 5 Plots showing (a) the real part (n) and (b) imaginary part (k) of the complex refractive index for both the experimentally measured and calculated
values (using eqn (2)) for a 56 : 44 mixture of TBP and 1-butanol. Bottom panels show the residual error between the experimental and calculated index
values.

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in Fig. 5b occur at 1283 cm1 (7.8 mm) and 1246 cm1 (8.0 mm), wavenumber (e.g., shifts to 3446 cm1 for the 88 : 12 mixture),
i.e., the PQO stretching region. Similar to the TBP:n-dodecane with the O–H band vanishing entirely as the volume fraction
mixtures, using molar fractions in eqn (2) through eqn (4) leads moves to that of 100% TBP. The doublet nature of the peak is
to higher errors in the calculated spectra due to the differences seen most clearly in the spectrum for the 56% by volume TBP
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between molar and volume fractions (see Table 1). mixture (light green trace in Fig. 6b). The peak shift to higher
While the TBP and 1-butanol are quite miscible, there is not wavenumber is attributed to hydrogen bonding of the PQO
a linear correlation between simply adding the k vectors of the oxygen atom with the OH moiety in 1-butanol.58 It is blue-
two neat liquids in ratios corresponding to the volume fractions shifted from the OH peak in neat 1-butanol indicating that
for all spectral regions in the infrared. The OH moiety in some of the OH groups begin to associate with the PQO group
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1-butanol enables H-bonding with the phosphoryl oxygen in of TBP versus other OH groups in 1-butanol. The blue-shift
TBP28 causing non-ideal behavior that is not captured by the may indicate the strength of the interaction is weaker as steric
mixing rules. This behavior can be better understood by effects from the bulky butyl groups are forcing the interactions
inspection of Fig. 6 which plots the experimentally derived k between the OH and PQO groups over larger distances. Both
values (solid lines) and calculated k values (dashed lines) using proton-NMR (Fig. S5 in the ESI†) and phosphorus-31 NMR
eqn (2). Fig. 6a highlights the PQO stretching region from (Fig. S6 in the ESI†) data support the notion that the OH and
1310–1220 cm1 (7.6–8.2 mm). With increasing fraction of PQO groups are interacting and causing electron density
1-butanol, the PQO (phosphoryl) peak for TBP at 1282 cm1 perturbations as the 1H NMR data indicate an upfield
(7.8 mm) shows a reduction in predicted amplitude whereas an chemical shift for the OH proton58 with increasing TBP
increase in amplitude and broadening is observed around the concentration, and, in contrast, the 31P NMR data show a
two peaks at 1262 cm1 (7.9 mm) and 1236 cm1 (8.1 mm). The downfield chemical shift for the 31P with increasing TBP
change in the measured spectra indicates an increase in the concentration.59,60
number of chemical environments for the PQO moiety, sug-
gesting some of the TBP molecules continue to interact with C. Comparison of the mixing rules
itself, but some also interact with the 1-butanol molecules To assess if any of the three mixing rules yield better predictive
via hydrogen bonding between the phosphoryl oxygen and capabilities for the n and k values for the binary mixtures, the
the hydroxyl group (see Section III.D). To further assess if root mean square error (RMSE) between the modeled and
hydrogen-bonding is indeed occurring, Fig. 6b is expanded measured data was calculated61 and is plotted in Fig. 7. The
from 3600–3030 cm1 (2.8–3.3 mm) and includes the broad dashed lines show the RMSE values for mixtures of TBP:
band for the O–H stretching frequency at 3333 cm1 for n-dodecane, and the solid lines represent the values for TBP:
1-butanol. As the volume percentage of TBP increases, the 1-butanol. A lower RMSE indicates better agreement between
broad OH peak changes to a doublet and shifts to higher the simulated and measured data, i.e. better accuracy.

Fig. 6 The k-spectra for the binary mixtures of TPB:1-butanol in the region of the (a) PQO stretching region from 1310–1220 cm1 (7.6–8.2 mm) and
(b) O–H stretching region from 3600–3030 cm1 (2.8–3.3 mm). The experimental data are plotted as solid lines, and the theoretical predictions (based on
eqn (2)) are plotted as dashed lines.

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Fig. 7 The RMSE values between the measured and calculated index values using the three methods for binary mixtures of TBP:n-dodecane (dashed
lines) and TBP:1-butanol (solid lines) are shown as a function of volume percent for the (a) n-values and (b) k-values.

For both binary mixtures, all three approaches show similar A binary mixture of liquids, composed of components x1 and
agreement although Fig. 7b shows a slight edge in accuracy for x2, can be modeled by a simple equilibrium expression, x1 +
the k-values using the L–L method for TBP:1-butanol and the x2 ! x1::x2. This modest description suggests that there exist
Arago–Biot method for TBP:n-dodecane (except for the 92 : 8 discrete populations of each component that can be assigned
mixture). As seen in Fig. 7, the RMSEs for n and k are lower for as being effectively isolated (i.e., x1 and x2, which behave like
TBP:n-dodecane with RMSE values below 0.003 and 0.002, the neat liquid samples), as well as a population for which the
respectively, for all mixtures except for the mixture with the two components are interacting with one another (i.e., x1::x2).
highest percentage of n-dodecane. The RMSE generally increases Note that this simple model ignores self-interactions (i.e.,
as the volume percentage of dodecane increases. On the other consisting of two or more of the same molecules interacting
hand, for TBP:1-butanol mixtures, the RMSE for both n and k is with each other), as the primary interest here is in distinguish-
highest for the 56 : 44 mixture peaking at 0.012 and 0.005 for n ing binary mixtures from neat samples. This is not to suggest
and k, respectively. that self-interactions are not occurring in these mixtures.
Rather, for the interacting population, we are solely concerned
D. Spectral deconvolution of the isolated and interacting with cross-component interactions as these lead to spectral
components in a binary mixture perturbations relative to the neat samples. Self-interactions, on
In this section, we seek to quantify the influence of intermolecular the other hand, are already contained within the neat spectra
interactions on the measured k-spectra of the various binary and are hence already accounted for in each of the three
mixtures considered in this study. Such interactions can influence models. We first consider the hydrogen bonding interaction
a variety of molecular properties (e.g., bond lengths, reduced in the PQO stretch of TBP for binary mixtures with 1-butanol.
masses, effective charges, force constants),62 which can manifest Based upon the above equilibrium model, the k-spectra
in the measured spectra as variations in transition frequencies depicted in Fig. 6a can be described as a convolution of two
and absorption intensities. In order to quantify these interactions, distinct vibrational bands: (1) a band resembling the PQO
the observed spectral bands were partitioned into discrete popula- stretch of neat TBP and (2) a frequency and intensity perturbed
tions assignable as either isolated or interacting liquids. The band that is characteristic of the intermolecular interactions
utility of this approach is that the population of isolated liquids between TBP and 1-butanol. Note that neat 1-butanol (Fig. 6a,
represents the fraction of the measured spectra most consistent purple trace) does not exhibit measurable vibrational transi-
with the simulations generated by the three models (eqn (2)–(4)), tions over this wavelength range. Consequently, the TBP::
which do not explicitly account for intermolecular interactions. 1-butanol intermolecular interaction band can be deduced as
Conversely, the population of interacting liquids represents the a perturbation to the PQO spectrum of neat TBP.
portion of the measured spectra that should deviate from model Specifically, it is feasible to deconvolute the measured
predictions. To simplify this process, the analysis was limited to k-spectra and isolate the individual components by subtracting
bands unique to either of the two binary components (i.e., present out an intensity scaled copy of the neat TBP PQO stretch band.
in the neat spectra of one but not the other). The ratio of each This analysis was done iteratively with the constraints that the
population can then be deduced as a function of the volume scaled TBP fraction is maximized, and the intensity profile
fraction of the reference component (i.e., the component produ- of the resulting difference spectrum remains positive over
cing the absorption band). To undertake this approach, we first the entire wavelength range. The rationale for maximizing the
develop a simple physical model. TBP fraction is two-fold: (1) the spectral band predominantly

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Fig. 8 Spectral deconvolution of measured k-spectra into separate populations assignable to either isolated or interacting liquids. The insets depict the
relative fraction of the deconvoluted populations plotted as a function of the volume fraction of the reference component. (a) PQO stretch of TBP in a
75 : 25 TBP : 1-butanol mixture. (b) O–H stretch of 1-butanol in a 56 : 44 TBP : 1-butanol mixture. (c) PQO stretch of TBP in a 55 : 45 TBP : n-dodecane
mixture. (See Fig. S3 in ESI† for plots of the other volume fractions.)

originates from TBP (i.e., it is not present in the neat 1-butanol Similar analysis was performed on the O–H stretch of
spectrum) and (2) without some constraint, there exists an 1-butanol for the TBP:1-butanol mixtures depicted in Fig. 6b.
infinite combination of band shapes which could sum together Whereas the PQO stretch acts as a reporter for TBP, the O–H
to produce the measured signal. The remaining spectral stretch provides a complementary measure of the hydrogen
features can then be assigned as the vibrational band of the bonding interaction from the perspective of 1-butanol.
TBP::1-butanol intermolecular interaction complex. Fig. 8a As stipulated above, neat TBP (Fig. 6b, black line) does not
depicts a representative deconvolution of the measured k-spectrum exhibit measurable vibrational transitions over this wavelength
for the 75 : 25 mixture of TBP : 1-butanol (solid orange line) into range. Consequently, the TBP::1-butanol intermolecular inter-
an isolated TBP band (dashed black line) and a TBP::1-butanol action band can likewise be deduced as a perturbation to the
complex band (dashed green line). O–H band of neat 1-butanol. Fig. 8b depicts a representative
The deconvoluted spectral bands (Fig. 8a) are useful in that deconvolution of the O–H stretch of 1-butanol in the 56 : 44
they permit an assessment of the concentration dependence mixture of TBP:1-butanol (solid green line) into an isolated
(volume fraction) for which the deduced populations transition 1-butanol band (dashed black line) and a TBP::1-butanol
between isolated (neat) liquids and interacting liquids. Speci- complex band (dashed blue line). Similar deconvolution analy-
fically, deconvolution analysis was performed for each of the sis was performed for each of the binary mixtures in Fig. 6b (see
binary mixtures in Fig. 6a (Fig. S3a in ESI†) and the relative Fig. S3b in ESI†). The relative fractions of the isolated (black
fractions of the isolated (black dots) and interacting popula- dots) and interacting populations (blue dots) were then plotted
tions (green dots) were plotted as a function of the TBP volume as a function of the 1-butanol volume fraction (Fig. 8b, inset).
fraction (Fig. 8a, inset). These trends were then fit to power The trends were fit to power functions and G50 for the O–H
functions in order to estimate continuous trends. As a basis for stretch of 1-butanol (in a TBP:1-butanol binary mixture) was
comparison, we then defined the quantity G50 as the volume deduced as 47%. As noted above, this suggests that, except for
fraction of the reference component for which the intensity of high volume ratios of 1-butanol (Z47%), the O–H stretch
the measured absorption band is composed of equal parts of absorption is dominated by the hydrogen bonding interaction
the isolated and interacting populations. For mixture ratios with the PQO group in TBP. Given the complementary nature
above G50, the absorption band is dominated by the isolated of these interactions (i.e., both TBP and 1-butanol contribute to
population and should be reasonably well described by the the intermolecular interaction), it is initially surprising that
three mixing rules. Conversely, for mixture ratios below G50, the the G50 values are not more similar. This disparity could stem
absorption band will be dominated by the interacting population from several possibilities, including differences in hydrogen
and will have a greater propensity to deviate from model predic- bonding-induced changes in absorption cross sections (which
tions. As depicted in the inset of Fig. 8a, for the binary mixture of may well differ for phosphates and hydroxyl groups) or even
TBP:1-butanol, the PQO stretch of TBP can be characterized with different stoichiometric ratios of the components involved in
a G50 of 78%. This suggests that, except for high volume ratios of the interaction. Thermodynamically, this could result from the
TBP (Z78%), the measured TBP PQO stretch absorption will be fact that unlike TBP, 1-butanol is capable of self-hydrogen
dominated by the hydrogen bonding interaction and will there- bonding. Consequently, while mixing of TBP and 1-butanol is
fore tend to deviate from model predictions. certainly going to be entropically favorable, the process of

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breaking 1-butanol hydrogen bonds and forming TBP:1-butanol complex index of refraction data along with accurate optical
hydrogen bonds may be enthalpically hindered. We plan to further models to describe the phenomena can be used to successfully
explore this possibility in future temperature dependent studies. In identify unknown liquids on various substrates. Using the
general, this observation suggests that the influence of hydrogen derived n and k vectors, for example, the reflectance spectra
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bonding on an absorption feature is likely dependent upon the of thin films of liquids on a substrate such as aluminum can be
specifics of the intermolecular interaction, including the strength computed.19 In this section, we have made initial attempts at
of the interaction and the fraction of molecules involved in the modeling more complex systems such as binary mixtures in
interaction complex. Further, it is worth emphasizing that both which these synthetic spectra could be used to populate the
TBP and 1-butanol exhibit reasonably high G50 values (Z47%), members of a spectral library using a range of mixing ratios,
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indicating that hydrogen bonding significantly alters absorption layer thicknesses and substrates to account for various combi-
bands that are susceptible to these types of interactions. nations that may be present in the experimental data.
Finally, in addition to hydrogen bonding, other van der To examine how the differences in the computed optical
Waals based interactions in binary mixtures of TBP and constants will impact the synthetic reflectance spectra, ray
n-dodecane were also analyzed. Due to the concurrent presence tracing models of both binary mixtures were constructed and
of C–H bonds in both TBP and n-dodecane, we chose not to reflectance versus wavelength (wavenumber) computed using
analyze the C–H stretch bands (Fig. 3b) and instead focused on the simplest model, i.e., eqn (2) (Arago–Biot). These computed
the PQO stretch of TBP (Fig. 3a). Similar to the hydrogen results were compared to reflectance spectra generated using
bonding interaction discussed above, the k-spectra depicted the experimentally measured n and k values for the binary
in Fig. 3a can be described as a convolution of vibrational mixture, and the RMSE was calculated to determine the pre-
bands: (1) a band resembling the PQO stretch of neat TBP and dictive capability for the computed spectra using just the
(2) a perturbed band that is characteristic of the various van der optical constants for the neat liquids. For this work,
Waals interactions between TBP and n-dodecane. Similar to TracePro63 was used to model the mixture(s) on a substrate of
1-butanol, n-dodecane (Fig. 3a, purple line) does not exhibit aluminum. A profile view of a 1 mm layer of a binary liquid
measurable vibrational transitions over this wavelength range. mixture is given below in Fig. 9 to illustrate the cumulative
Consequently, the TBP::n-dodecane intermolecular interaction effect of absorption in the thin film as well as reflective losses at
band can be deduced as a perturbation to the PQO spectrum of each film interface.
neat TBP. Fig. 8c depicts a representative deconvolution of the The reflectance spectra were modeled for both (a) a 55 : 45
PQO stretch of TBP in the 55 : 45 mixture of TBP : n-dodecane mixture of TBP : n-dodecane and (b) a 56 : 44 mixture of TBP :
(solid green line) into an isolated TBP band (dashed black line) 1-butanol applied to an aluminum substrate with a 1 mm layer
and a TBP::n-dodecane complex band (dashed blue line). thickness. Fig. 10 shows the results of the modeled reflectance
Deconvolution analysis was performed for each of the binary spectra using the complex index of refraction values that were
mixtures in Fig. 3a (see Fig. S3c in ESI†). The relative fractions either measured (black trace) or mathematically computed
of the isolated (black dots) and interacting populations (blue using the Arago–Biot method of eqn (2) (red trace). As illustrated
dots) were then plotted as a function of the TBP volume fraction by the residuals in the bottom panels of Fig. 10a, excellent
(Fig. 8c, inset). The trends were fit to power functions and G50 agreement is observed for the thin film of TBP:n-dodecane using
for the PQO stretch of TBP (in the TBP:n-dodecane binary calculated n and k values when compared to measured index of
mixture) was deduced as 1.5%. As detailed above, this suggests
that the PQO stretch of TBP will almost always resemble the
neat liquid. It is only for extremely low volume ratios of TBP
(r1.5%) that van der Waals interactions between the binary
components dominate the absorption band. This is in stark
contrast to the influence of the hydrogen bonding interactions
(Fig. 8a and b), for which the intermolecular interaction
complex dominates the measured spectra for TBP (1-butanol)
volume fractions below ca. 50%. These observations nicely
account for the fact that the three mixing rules (eqn (2)–(4))
do an excellent job of predicting the k-spectra of binary mix-
tures exhibiting only isotropic interactions (e.g., dispersion),
but a less satisfactory job for binary mixtures capable of
anisotropic interactions (e.g., hydrogen bonding) as they have
a greater propensity to perturb the spectra.
Fig. 9 Side view of the model illustrating light propagation through a 1 mm
E. Modeling the reflectance spectra using calculated index layer of a binary mixture atop an aluminum substrate illuminated at 301
values of mixtures angle of incidence at a wavelength of 10 mm. The ray colors denote
relative intensity of the light as it traverses the thin film structure, with red
In situations where liquid layers are optically thin enough that symbolizing the most intense, green, intermediate intensity, and blue, the
light interacts with both the liquid layer and substrate, the weakest intensity. The arrows denote the direction of light propagation.

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Fig. 10 Results of modeling a 1 mm layer on an aluminum substrate of a (a) 55 : 45 mixture of TBP : n-dodecane and a (b) 56 : 44 mixture of TBP :
1-butanol. Bottom panels show the residual error between the modeled spectra using measured n and k values (black trace) vs. using n and k values
computed (red trace) by the method of Arago–Biot (eqn (2)).

refraction values (RMSE is 0.004). On the other hand, Fig. 10b three models was achieved with TBP:n-dodecane compared to
shows higher residuals for the modeled reflectance for the thin TBP:1-butanol. For example, the RMSE of the k-values for all
film of TBP:1-butanol on aluminum. The RMSE increases by a TBP:n-dodecane mixtures and methods was consistently below
factor of six to 0.024 due to the cross-interactions between TBP 0.002 (Fig. 7b). This low RMSE was only achieved for the TBP:
and 1-butanol, which impact the optical constants as seen in 1-butanol mixture with the highest percentage of TBP (i.e.,
Fig. 5. As expected, the largest errors for TBP:1-butanol appear in 88 : 12, Fig. 7b), indicating that TBP and 1-butanol have inter-
the OH stretching region at 3449 and 3264 cm1 and the PQO molecular interactions that lead to larger deviations, including
stretching region at 1283 and 1246 cm1 due to frequency shifts frequency shifts. Further, it is worth noting that all three
induced by the interaction between the TBP and 1-butanol models (eqn (2)–(4)) produced remarkably similar results
molecules. (Fig. 7), with only slight differences, indicating that any of the
three expressions could be used, as long as intermolecular
interactions do not lead to significant perturbations.
IV. Discussion It is also of interest to note the characteristic trends of the
deduced errors at higher TBP concentrations. For the TBP:
This paper examined the influence of intermolecular inter- n-dodecane mixtures (no cross dipole–dipole interactions), the
actions on the complex refractive index of binary mixtures in RMSE values were shown to increase almost monotonically
the infrared spectral region. Specifically, two representative sets as the percentage of TBP decreased (Fig. 7). In general, this
of binary mixtures were considered: (1) TBP and n-dodecane, appears to suggest that each of the three methods is better at
for which only dispersion and dipole–induced dipole intermo- simulating TBP spectra compared to n-dodecane (i.e., the errors
lecular interactions were possible between the two components increased as the spectra became more characteristic of
and (2) TBP and 1-butanol, for which dipole–dipole interactions, n-dodecane). Lower RMSE values were also observed for the
including hydrogen bonding, were also feasible. In addition to TBP:1-butanol mixtures preferentially enriched with TBP. If we
measured spectral components, the binary mixtures were simu- consider the specific self-intermolecular interactions at play in
lated using three established mixing models (eqn (2)–(4)). It was these systems, n-dodecane which is a non-polar molecule,
reasoned that intermolecular interactions such as hydrogen- exhibits dispersion interactions (i.e., no dipole–dipole) whereas
bonding, in which the geometry of the interaction is restricted 1-butanol is polar and capable of hydrogen bonding (dipole–
by the orientation of the permanent dipoles in the two compo- dipole). Tributyl phosphate is capable of both dipole–dipole
nents, should result in significant perturbations in the measured and dispersion interactions and has the highest boiling point
spectra (particularly for the functional groups involved in the of the three liquids, indicating it has the strongest intermole-
interaction) and hence deviations from the predicted spectra. cular forces. Since higher concentrations of both n-dodecane
Conversely, the geometry of intermolecular interactions result- and 1-butanol lead to larger errors from the models, the
ing from an induced dipole (i.e., dispersion forces) is not limited addition of TBP appears to have a bigger impact on the mixture
and were predicted to have little to no influence on either the properties (and hence the cross-intermolecular interactions)
measured or modeled spectra. than either the addition of n-dodecane or 1-butanol. Due to
Indeed, as evidenced by lower residuals (Fig. 2 and 5) and the strong intermolecular interactions in neat TBP, a larger
lower RMSE values (Fig. 7), overall better agreement with the concentration of 1-butanol is required before most of these

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interactions are disrupted. Perhaps more interesting, however, dipole–induced dipole) for extremely dilute volume ratios of
is the behavior of the 56 : 44 mixture of TBP:1-butanol. For this TBP (i.e., below 1.5%).
mixture, which corresponds to when the sample is roughly Finally, Section III.D showed that spectral modeling using
equal parts (by volume) TBP and 1-butanol (Fig. 7), the max- the three mixing rules is a viable approach for materials that
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imum RMSE between the measured and computed n and k are dominated by dispersion (and weak dipole–induced dipole)
spectra is observed. Importantly, for this specific mixture ratio, forces as these interactions only induce minimal perturbations
hydrogen bonding should significantly influence both compo- in the spectra of liquid mixtures. For example, spectral model-
nents in the sample (i.e., the PQO stretch of TBP and the O–H ing of a thin layer of a 55 : 45 TBP : n-dodecane mixture yielded
stretch of 1-butanol). Conceptually, as the mixture ratio is excellent agreement between the reflectance spectrum calcu-
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decreased in either direction, there should be an increased lated using either measured or computed n and k values
propensity for the remaining dominant component to behave (Fig. 10a). Larger perturbations were observed for mixtures of
as an isolated (rather than interacting) liquid. Given that none TBP:1-butanol, particularly in spectral regions where hydrogen-
of the three models explicitly considers intermolecular interac- bonding occurs (Fig. 10b). These results demonstrate the need
tions between the two components, it is therefore reasonable for improved mixing models which implicitly incorporate inter-
that the approximately 50 : 50 mixture (i.e., for which cross- molecular interactions between the binary components. In the
component H-bonding should be maximally occurring) should meantime, one potentially viable approach is to simply exclude
exhibit the greatest RMSE. spectral regions which are strongly influenced by such inter-
As depicted in Fig. 2 and 5, intermolecular interactions are actions from modeled spectra. For example, for stand-off
shown to measurably influence the spectra of binary mixtures. chemical detection, excluding the OH bands is reasonable as
Dispersion forces were shown to have minimal impact on the this spectral region is notoriously problematic due to the
spectra of binary mixtures (Fig. 3), whereas dipole–dipole presence of atmospheric water which hinders detection efforts.
interactions (e.g., hydrogen-bonding) resulted in significant As a result, this spectral region is routinely ignored in such
perturbations in the spectral regions that are impacted by these analysis. However, such an approach is largely impractical for
forces (Fig. 6). For example, in TBP, the phosphoryl oxygen other spectral regions that are characteristic of the distinct
(PQO) is a H-acceptor, so the addition of 1-butanol can lead to functional groups present in the mixture components and are
H-bonding between the phosphoryl oxygen and the hydroxyl therefore necessary to help with material identification, such as
group. Since the OH moiety in 1-butanol can be either a the PQO bands. For these samples, the only viable path
H-donor or H-acceptor, self-association via H-bonding also forward is improved models which consider intermolecular
occurs in neat 1-butanol. Due to disruption of the H-bonding interactions between the mixture components.
between 1-butanol molecules from the addition of TBP, a blue-
shift is observed for the O–H band at 3300 cm1 (Fig. 6b). This
blue-shift may also indicate the interactions between the O–H V. Conclusion
and PQO bond occur over larger distances due to steric
hindrance from the bulky butyl chains. Investigating smaller This paper evaluated the validity of computing the optical
alcohols with TBP would help determine if steric hindrance is a constants of binary mixtures by using the measured optical
contributing factor. In the same way, the introduction of constants of the neat constituents along with the volume ratio
H-bonding between the OH and PQO groups leads to a broad for the various mixtures. By computing the optical constants
peak that is red-shifted for the PQO band at 1282 cm1 of the mixtures, laboratory reference measurements can be
(Fig. 6a). The change in intermolecular interactions upon drastically reduced by using the computed optical constants
mixing causes much more significant spectral alteration for to model the synthetic reference spectra of binary mixtures for
the binary mixtures of TBP and 1-butanol (Fig. 5) compared to populating into a spectral library. In particular, three methods
mixtures of TBP and n-dodecane (Fig. 3). For binary mixtures of of calculating the complex refractive index for binary mixtures
TBP and n-dodecane, only a small blue-shift (up to 5 cm1 for were investigated: the method of Arago–Biot (eqn (2)),40 the
the 10 : 90 mixture) is observed for the PQO band (Fig. 3a), Newton method using relative permittivity (eqn (3))30 and
likely due to dispersion (and possibly dipole–induced dipole) the L–L method (eqn (4)).42 Each method was evaluated by
interactions between TBP and dodecane molecules disrupting calculating the difference between the measured values and the
some of the self-interactions in the neat liquids. These results predicted values for both the real and imaginary parts of the
were supported by the spectral deconvolution analysis pre- index. Using linear combinations of the n and k vectors of
sented in Section III.C, which quantified the influence of the neat substances, the three methods provided similar
cross-component intermolecular interactions on the resulting approximations of the resulting complex index of refraction
spectra. Specifically, as depicted in Fig. 8, hydrogen bonding when compared with measured values of the same mixture
between TBP and 1-butanol was shown to dominate the mea- ratios using volume fractions to determine both n and k.
sured spectra for all volume ratios consisting of less than 78% Additionally, the RMSE between the measured and calculated
TBP. This is in stark contrast to the binary mixtures of TBP index values using the three methods for binary mixtures was
and dodecane which only began to show the influence of cross- calculated and plotted for each mixture and no method was
component van der Waals interactions (e.g., dispersion or found to provide superior results; the simplest method of

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Arago–Biot defined in eqn (2) appears to be adequate to 3 T. D. Brandt and D. S. Spiegel, Prospects for Detecting
estimate the complex index of refraction of binary liquid Oxygen, Water, and Chlorophyll on an Exo-Earth, Proc. Natl.
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anisotropic (dipole–dipole) interactions. Y. Zhuang, N. C. Surawski, B. Organ and E. F. C. Chan,

The largest differences between the calculated and mea- Rapid Detection of High-Emitting Vehicles by On-Road
sured spectra were seen in regions where cross-intermolecular Remote Sensing Technology Improves Urban Air Quality,
interactions, particularly H-bonding, occur. Good agreement is Sci. Adv., 2022, 8(5), eabl7575.
achieved for both mixtures in regions with ideal mixing beha- 5 R. E. C. Pabón, C. R. de Souza Filho and W. J. d de Oliveira,
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vior, but regions that are affected by dipole–dipole interactions, Reflectance and Imaging Spectroscopy Applied to Detection
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There are no conflicts to declare.
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