Version of Record: https://www.sciencedirect.

com/science/article/pii/S002228522030062X
Manuscript_ae0067fbb377ae60016fe8378557c67d

April 14, 2020

J. Mol. Spectrosc.
Revised

A New Program for the Assignment and Fitting of Dense

Rotational Spectra Based on Spectral Progressions:
Application to the Microwave Spectrum of Pivalic
Anhydride

Nathan Love, Anna K. Huff, and Kenneth R. Leopold*

Department of Chemistry
University of Minnesota
207 Pleasant St., SE
Minneapolis, MN 55455

* Corresponding Author: kleopold@umn.edu

© 2020 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
 Abstract

A new computerized package for the rapid processing and analysis of dense rotational spectra is
described. The package is based on the automated identification of user-
specified spectral progressions and interacts with the operator through a simple graphical user
interface. In addition to containing an algorithm for obtaining spectral assignments, the package
includes a peak-finder with adjustable baseline drift compensation, seamless interfacing with
Pickett’s SPFIT and SPCAT programs, and a number of visualization features. The utility of the
program is illustrated through its application to the analysis of new spectra of pivalic anhydride,
(CH3)3CCOOCOC(CH3)3. Spectra of the parent, as well as all isotopologues with single heavy-
atom substitution, are reported, as are calculations for the parent species at the M06-2X/6-
311++G(3df,3pd) level of theory. The central oxygen atom is poorly located due to its proximity
to the center of mass of the molecule, but a Kraitchman analysis of the fitted rotational constants
otherwise provides a detailed structural characterization of the heavy-atom frame. The two
carbonyl groups are not coplanar, but rather form a dihedral angle of 53.9(39) deg.

Keywords: Autofitting; Pivalic Anhydride; Rotational Spectra; Spectral Progressions; Molecular

Structure

2
Introduction
In recent years, technological advances in the acquisition of molecular rotational spectra have led
to a dramatic increase in the size and complexity of species that can be studied [1,2]. The
concomitant complexity of the resulting spectra is often compounded by factors such as multi-
component samples, the presence of more than one molecular conformation, the occurrence of
naturally abundant isotopologues, and the population of excited vibrational states. Thus, spectra
may contain tens of thousands of transitions, and it has become increasingly unfeasible to
generate spectral assignments by hand. Automated algorithms that aid in the assigning and fitting
of such spectra have been developed over a period of many years [3-11], with powerful programs
such as Autofit [12], PGOPHER [13], JB95 [14], the AABS package [15], and SPFIT/SPCAT
[16] emerging as some of the most important and widely used tools today. Many additional
programs exist, however, and can be found on the Programs for ROtational SPEctroscopy
website (http://www.ifpan.edu.pl/~kisiel/prospe.htm).

Dense spectra of large molecules typically feature large ranges of J quantum numbers.
Accordingly, spectra can be logically organized into progressions of distinct transition types, as
discussed in detail by Cooke and Ohring [17]. Complex spectra, which result from the overlay of
multiple progressions, can then be readily understood in terms of these simple sequences. This
paper describes a new program, “DAPPERS” (Data Analysis Package for Productive and
Enthusiastic Rotational Spectroscopists), which features a dynamic fit searching algorithm that
intelligently assigns spectral progressions embedded in even the most dense spectra with
extremely rapid runtimes (a few seconds). The algorithm accurately identifies members of a
series and then fits them together as a single progression or ultimately combines them in a single
fit with other identified progressions or individual transitions. All fits are done using a built-in
wrapper interface for Pickett’s SPFIT program. DAPPERS also features a number of spectral
processing tools, such as a graphical peak finder with adjustable baseline compensation, that can
greatly aid in the assignment and fitting of rotational spectra.

In addition to describing the basic features of DAPPERS, this paper illustrates its applicability to
new spectra of a moderately large molecule, pivalic anhydride, shown below.

3
Our laboratory has recently become interested in acid anhydrides, initially in the form of
carboxylic sulfuric anhydrides (RCOOSO2OH) [18], with the eventual goal of studying their
water complexes as hydrolysis precursor complexes. One such complex, CH3COOSO2OH−H2O,
has already been studied [19]. Recently, however, this interest has been extended to more
familiar analogues derived from the condensation of two carboxylic acids i.e., species of the
form RCOOCOR′. Trifluoroacetic anhydride (TFAA), the first of these carboxylic analogues
investigated in our laboratory, featured a relatively dense b-type spectrum with the presence of
several spectral progressions [20]. Pivalic anhydride was chosen as the example for DAPPERS
because it was predicted to also have a dense spectrum with multiple superimposed sequences.
Although it does not exhibit complicating features such as internal rotation, hyperfine structure,
Coriolis coupling, or multiple conformers, the spectrum consists of multiple progressions that are
so intertwined as to render them difficult to identify by visual inspection. We take this as the
operational definition of a “dense” spectrum for which an autofitting routine has value.
Moreover, beyond its role as a test case for DAPPERS, pivalic anhydride extends the study of
acid anhydrides by replacing the small, electron withdrawing fluorines of TFAA with bulky,
electron releasing methyl groups, thus allowing an exploration of steric and electronic effects on
structure (and ultimately complexation).

Methods and Results

The 6-18 GHz chirped-pulse spectrum of pivalic anhydride was measured in 3 GHz segments
with the tandem chirped-pulse and cavity spectrometer which has been described elsewhere
[21,22]. Pivalic anhydride, obtained from Sigma Aldrich, was introduced into the system by
flowing argon over a ~1 ml sample in a reservoir located a short distance from the pulsed nozzle.
The reservoir was heated to 60° C and the resulting pivalic anhydride-argon mixture was injected
through a 0.020 in I.D. (inner diameter) needle along the axis of a cone nozzle as described
previously [23]. The pressure behind the hypodermic needle was 0.4 atm and the stagnation

4
pressure (behind the nozzle) was 1.3 atm. A 30 MHz segment of the observed spectrum is shown
in Figure 1.

Frequencies from the chirped-pulse spectrum were measured with a typical uncertainty of
~12 kHz. As described in more detail below, DAPPERS was then used to assign and fit 255 b-

Figure 1. A 30 MHz wide segment of the chirped-pulse spectrum of pivalic anhydride. This spectrum represents
the Fourier transform of the average of 60,000 free induction decay signals and includes two Q branch
progressions with Kp = 4 ← 3. The two progressions converge in frequency as J decreases. The J value for each
transition is labeled at the top of the corresponding peak and primes are used to differentiate transitions from the
two progressions. Transitions with J = 4, 5, and 6 are not differentiated due to their small splitting. The stick
spectrum on the bottom shows the frequencies predicted with the fitted spectroscopic constants.

type Q and R branch transitions with a root mean square residual of 3.5 kHz in under four
minutes. Several sets of unresolved transitions in the chirped-pulse spectrum were purposefully
not included at this stage and were subsequently re-measured and resolved on the cavity
spectrometer before being added to the final fit. For these measurements, the typical accuracy
was 1-2 kHz. Six transitions with frequencies greater than 18 GHz were also observed and
measured as sidebands on the chirped-pulse system. The final set of 273 assigned transitions
(226 distinct frequencies) was fit to a Watson A-reduced Hamiltonian in the Ir representation
using Pickett’s SPFIT program [16], again as implemented through its interface with DAPPERS.

5
The rms residual was 4.0 kHz and the resulting spectroscopic constants are given in Table 1. A
listing of fitted transitions, assignments, and residuals appears in the Supplementary Material and
a sample spectrum showing the 5 , ←4 , and 5 , ←4 , transitions, as resolved on the cavity
spectrometer, is shown in Figure 2.

Figure 2. Black trace shows the 542 ← 431 and 541 ← 432 transitions of the parent form of pivalic
anhydride, as observed on the cavity spectrometer. This spectrum represents the average of 24,000 free
induction decays. The calculated splitting is 24 kHz and the observed splitting is 22 kHz. The red trace
shows the same pair of transitions as observed on the chirped-pulse system.

Due to the C2 symmetry of the molecule, there are five singly-substituted 13C isotopologues, and
two singly-substituted 18O isotopologues. Rotational constants were predicted for each species
using the results of the parent fit, and spectra were readily located in natural abundance on the
cavity spectrometer. (A few 13C peaks resulting from pairs of unresolved transitions were
observed on the chirped-pulse system as well.) Due to the equivalence of pairs of atoms on both
sides of the bridging oxygen, spectra from all isotopologues, except those from that bridging
oxygen, were observed at approximately twice the expected intensity based on relative isotope
abundances. The scope of the data sets for the isotopically substituted species was, in each case,
insufficient to determine all of the quartic centrifugal distortion constants and thus, when
6
necessary, these values were constrained to those determined for the parent species. Transition
frequencies, assignments, and residuals for all isotopologues studied are also given in the
Supplementary Material, and the fitted spectroscopic constants are included in Table 1.

The minimum energy structure of pivalic anhydride was obtained at the M06-2X/6-
311++G(3df,3pd) level of theory using the Gaussian16 suite [24] of programs. The optimized
geometry is shown in Figure 3 and calculated structural parameters are summarized in Table 2.
The structure is similar to that predicted for trifluoroacetic anhydride [20], with a C2 axis of

Figure 3. The structure of pivalic anhydride calculated at the M06-2X/6-311++G(3df,3pd) level/basis. Note that
the b-axis is the C2 symmetry axis.

symmetry and non-coplanar arrangement of the carbonyl groups. However, the 59 deg O2-C1-
C4-O5 dihedral angle calculated at this level of theory is 25 deg larger than that in the
trifluoroacetic analog at the same level of theory. In principle, the resulting double well potential
associated with a scissoring motion of the two C=O groups gives rise to a pair of tunneling
states. However, the calculated barrier, obtained by re-optimizing the geometry with the dihedral
angle constrained to zero, has a rather large value of 1.7 kcal/mol. Indeed, no second state was

7
observed and, as mentioned previously, the observed spectrum was adequately fit to a semi-rigid
rotor Hamiltonian. The predicted rotational constants for the parent isotopologue, A, B, and C,
are 1537, 459, and 438 MHz respectively, and agree with their experimentally determined values
to within 1.3%, 0.5%, and 0.8%, respectively. The predicted dipole moment is 3.6 D and lies
entirely along the b-inertial axis, consistent with the observation of only b-type rotational
transitions. Cartesian coordinates for the predicted structure are provided in the Supplementary
Material.

Structure Analysis
With isotopic substitution on each of the heavy atoms of the molecule, Kraitchman’s equations
[25] can be used to determine the structure of the heavy atom frame. The analysis was
implemented using Kisiel’s KRA program [26] and the resulting atomic coordinates are given in
Table 3. The signs of the coordinates are not determined experimentally, but have been inferred
based on the theoretical structure. Quoted uncertainties include the Costain correction, as
described in the KRA documentation. Note that O3 is excluded from this tabulation as, in the
theoretical structure, it lies within 0.25 Å of the center of mass of the molecule, rendering the
Kraitchman analysis unreliable. Indeed, the bond distance between either carbonyl carbon and
the bridging oxygen was calculated to be 1.78 Å with Kraitchman’s equations, quite different
from the more realistic value of 1.38 Å predicted by theory. A comparison of the experimentally
determined structural parameters and those predicted by M06-2X/6-311++G(3df,3pd) theory is
included in Table 2. As indicated in the table, bond lengths and bond angles are duplicated on
two sides of the molecule due to symmetry.

The DAPPERS Package

As noted above, chirped-pulse spectral data were processed using the DAPPERS package. The
package is coded in LabVIEW, but has been complied into an executable file, therefore
eliminating the need to have LabVIEW installed by the user. A single installer for the DAPPERS
package, as well as extensive documentation, test files, and installation instructions, can be
downloaded at www.chem.umn.edu/groups/kleopold. The program features an intuitive and
dynamic graphical user interface that requires no prior programming experience and

8
automatically formats and executes Pickett SPFIT and SPCAT files. This section outlines some
of the basic features of the package.

Graphical Peak Finder: Peak finding programs are widely used to identify and catalogue
transitions in a raw spectral file that have intensities greater than a user selected threshold. While
many programs utilize a global threshold for this purpose, spectra with drifting baselines are
better served by more refined methods. One solution is to apply a baseline correction to the
spectrum, but this involves the modification of raw experimental data. DAPPERS handles the
problem by allowing the calculation of local thresholds within a user-defined window. For
example, for a 50 MHz window, a separate baseline value is calculated for every 50 MHz
segment of the spectrum. The windows can be as small as 1 MHz or as large as the entire
spectrum. The local thresholds determined within each windowed segment are then stitched
together to form a piece-wise threshold function that can be uniformly raised or lowered to a user
selected intensity level. A traditional, global threshold (without calculation of a baseline value) is
also available.

The Algorithm: The core feature of the package is the algorithm that intelligently identifies
experimental spectral progressions with user-specified quantum number identities. Examples of
these “quantum filtered” series would be the a-type R branch progression 202 ← 101, 303 ← 202,
etc., or the b-type Q branch progression 1046 ← 1037, 1147 ← 1138, etc. The identification is
based on the relationships between different transitions from a corresponding progression in a
predicted spectrum. (Using the industry standard of Pickett’s SPCAT program, this would be a
.cat file.) The searching algorithm selects experimental frequencies that may belong to a given
spectral progression, starting with the lowest (user specific) J, and then applies successively
refined criteria to identify additional members of the series. The criteria are summarized in
Table 4.

The first test (the starter test) provides initial assignments, and utilizes a “starter window”, which
represents the maximum anticipated discrepancy between the observed and predicted frequencies
for the lowest J member of the series. Depending on a number of factors including molecular
size, prediction accuracy, and experimental frequency range, reasonable starter window values

9
can range from 10 to 10,000 MHz. Fortunately, larger starter windows do not drastically affect
the efficiency of the algorithm (within reason). This means that, although well-predicted
rotational constants are helpful, one does not necessarily need highly accurate information about
the molecule in order to assign its spectrum.

Once candidates for the lowest J member of the series are identified, a “ratio test” is applied.
This test identifies experimental transitions that may be candidates for the next member of the
series, based on their predicted ratio as determined in the .cat file (within a generally smaller
window). Finally, the “derivative ratio test” utilizes ratios of the predicted and observed
differences between previous members of the series (rather than the frequencies themselves) to
select candidates for the next member of the series.

Experimental peaks are only assigned if their frequencies lie within the appropriate user-
specified windows. With dense spectra and liberal window sizes, more than one set of transitions
may initially be identified as belonging to a particular quantum filtered progression. However,
once fit individually, these may be combined with other quantum filtered progressions and fit
simultaneously using Pickett’s SPFIT program to test their compatibility. Once a good fit is
obtained, the spectrum can be further scoured to locate, assign, and fit transitions that were not
contained in the spectral progressions. DAPPERS seamlessly integrates with Pickett’s programs
at each stage of the process, allowing properly formatted input files to be created via an easy-to-
use graphical user interface.

For pivalic anhydride, three distinct R branch progressions involving = 0 (8 , ←7 , ,

9 , ← 8 , , etc.), = 1 (6 , ←5 , ,7 , ←6 , , etc.), and = 3 (3 , ←2 , ,4 , ←3 , ,
etc.) were readily identified. Based on these progressions, the full spectrum was scoured,
yielding the identification and fitting of a total of 255 b-type transitions in four minutes.
Remaining transitions that appeared as sidebands in the chirped-pulse spectrum were then readily
assigned, and a number of predicted lines were observed on the cavity spectrometer before
generating the final fit.

10
Performance: In addition to its application to pivalic anhydride, DAPPERS has been tested on a
number of published spectra whose density arises from the presence of conformers [27], excited
vibrational states [28,29], and isotopologues [28-30]. For example, in 21 minutes, a proficient
user was able to correctly assign and fit well over 4,000 millimeter wave transitions to the
ground vibrational state of 2-chloropyridine [29] in a spectrum containing over 10,000 lines
35/37
(arising from 23 vibrationally excited states and the Cl isotopologues). DAPPERS has also
been used to fit several other sets of published, dense rotational spectra in the microwave
frequency region including trifluoroacetic anhydride [20], perillyl alcohol [27], 3,3,3-trifluoro-
1,2-epoxypropane [30], and 1-hexanal [12]. In these tests, the fitting algorithm has effectively
handled dense rotational spectra with different types (a-, b-, and c-), branches (P, Q, and R),
frequency regions (microwave and millimeter wave), and molecular sizes and asymmetry
parameters. It is easy to learn and has been successfully used by college sophomores with only
several weeks of spectroscopic experience. The extensive documentation noted above guides the
user through operation and “best practices”.

Among the spectra we have tested so far, significant variation in approach has not been required.
Typically, one obtains initial assignments by looking for several intense R branch progressions
with low Kp values from one or more types of spectra (a-, b-, or c-), and then combining these
progressions to produce a fit with centrifugal distortion that is predictive of remaining transitions
from different types and branches. To date, once a full spectrum has been assigned, we have not
encountered any instances of misassignments or erroneous alternate fits.

Specific tests were conducted to assess the effect of the molecular asymmetry parameter on the
accuracy of guess frequencies derived from the ratio and derivative ratio tests. This is useful for
setting the sizes of the windows utilized in these tests. A graphical representation of the
relationship between the accuracy of guess frequencies and the asymmetry parameters for both
the ratio and derivative ratio tests can be seen in Figure 4. The curves in this figure that
correspond to an asymmetry parameter of −0.95 represent the accuracy of the algorithm guesses
that were obtained for the R branch, b-type progression J′1,J′ ← J″0,J″ of trifluoroacetic anhydride
(TFAA) [20]. The remaining curves were calculated by fixing all experimental constants for
TFAA except for B, which was then varied to produce the range of asymmetry parameters. The

11
 Figure 4. Plots comparing the accuracies of the ratio test (top) and derivative ratio test (bottom) for
varying asymmetry parameters between −0.95 and 0.95. J values are along the horizontal axis and
the deviations of the algorithm’s guess frequencies from their hypothetical experimental values are
on the vertical axis. See text for discussion.

predicted frequencies thus generated were compared against a hypothetical experimental

spectrum obtained by scaling the new A, B, and C according to the ratio of the observed TFAA
constants and those obtained from the DFT calculations. The figure shows that, regardless of
asymmetry parameter, the ratio and derivative ratio tests are reliable to within a few MHz. Other
progressions were tested and, while the shape of the curves were found to vary, similar
accuracies were obtained.

12
The core algorithm uses parallel computing to significantly speed up performance, and
assignment and fitting of spectra are not limited by the runtime of the algorithm itself. Indeed,
with reasonably chosen window sizes for the three test algorithms, runtimes generally take no
longer than a few seconds, even for very dense spectra. These runtimes, however, can be further
minimized, if desired, by using an abridged peak list containing only the most intense
experimental peaks and searching for progressions that are likely to be most intense. A
significant advantage of this approach can be to reduce the number of trial progressions that need
to be evaluated and merged, and may be particularly useful for spectra that contain weak lines
from rare isotopologues in natural abundance or high energy conformers with reduced
population. A built-in spectral “scrubber” facilitates the creation of spectral files containing
subsets of the data, and ensures that they receive different files names so that abridged spectra
cannot be accidentally confused with original, raw data.

The current version of DAPPERS was designed to analyze asymmetric top spectra with quartic
and sextic centrifugal distortion but is currently not capable of handling internal rotation,
Coriolis coupling, or nuclear hyperfine structure (unless it is collapsed to near or within the
experimental resolution). Because DAPPERS’ algorithm searches for spectral progressions, a
minimum of 3 or 4 transitions per progression is required in the experimental data set and thus,
the routine is neither applicable (nor needed) for light molecules with sparse spectra. Finally,
since DAPPERS utilizes SPCAT and SPFIT for the prediction and fitting of spectra, it is subject
to the same limitations as those programs (notably limited to a maximum J value of 369 for
SPCAT and 999 for SPFIT).

Discussion
The experimentally determined structural parameters for pivalic anhydride given in Table 2 are
seen to be in generally quite good agreement with the corresponding values determined at the
M06-2X/6-311++G(3df,3pd) level of theory. Of particular interest is the O2-C1-C4-O5 dihedral
angle of 53.9(39) deg, which measures the degree to which the two carbonyl groups are not
coplanar. This value is in very reasonable agreement with the DFT result of 59 deg. Overall, the
extensive isotopic substitution and the good agreement between experimental and theoretical
values indicates that the reported structural parameters should be quite reliable.

13
The structure of pivalic anhydride may be compared with that of the related compound,
trifluoroacetic anhydride [20], in which the C(CH3)3 is replaced by the more electron
withdrawing CF3 group. For this purpose, we compare only the computational results, since a
complete experimental structure determination for trifluoroacetic anhydride was not reported.
The calculations in that work, however, were performed at the M06-2X/6-311++G(3df) level of
theory and should be comparable to those reported here. (Note that trifluoroacetic anhydride
contains no hydrogen atoms). In the calculated structure of pivalic anhydride, the C=O bond
lengths are 1.187 Å. This value is slightly longer than the 1.175 Å value obtained for
trifluoroacetic anhydride from the coordinates provided in the Supplementary Material of
reference [20]. The expansion of the carbonyl bond is slight in pivalic anhydride and may result,
at least in part, from a stabilization of the C+−O− resonance structure of the carbonyl group by
the more electron releasing substituent.

A larger difference between the two compounds is seen in the dihedral angle formed by the two
carbonyl groups (59 deg computed for pivalic anhydride and only 34 deg for trifluoroacetic
anhydride). A plausible explanation for the difference may be increased repulsion between the
two carbonyl oxygens in pivalic anhydride resulting from the replacement of the electron
withdrawing fluorines with electron releasing methyl groups. In this regard, it is interesting to
note that the 1.7 kcal/mol barrier at the coplanar configuration calculated in this work for pivalic
anhydride is about five times larger than the 0.3 kcal/mol barrier obtained for trifluoroacetic
anhydride. Some caution is warranted in applying this argument, however, since the equivalent
angle has been observed to be 180 deg in formic anhydride [31,32] and formic acetic anhydride
[33], where the carbonyl groups are coplanar, but opposed. As is often the case with
conformation, multiple electronic and steric factors may contribute to determining the minimum
energy geometry.

The variety of programs that are now available for automated spectral fitting [5-678916] provides
workers in the field with an array of options for handling increasingly dense rotational spectra.
DAPPERS’ focus on spectral progressions provides an alternative and easy-to-use approach
which should add to the pool of resources that can be harnessed to rapidly process spectra.

14
Further work will be needed to handle spectral features such as hyperfine structure, internal
rotation, and Coriolis coupling, but for a variety of semi-rigid asymmetric top molecules, the
routine has so far proven quite effective at solving dense spectra of the kind that can now be
easily recorded with chirped-pulse methods.

Conclusion
Eight isotopologues of pivalic anhydride have been observed by chirped-pulse and cavity Fourier
transform microwave spectroscopy and the resulting spectroscopic constants provide reliable
information about the structure of the heavy atom frame. The two carbonyl groups are syn to one
another, but are not coplanar. M06-2X/6-311++G(3df,3pd) calculations have provided additional
structural information, as well as a value for the energetic barrier at the planar configuration
(1.7 kcal/mol relative to the equilibrium geometry). The chirped-pulse spectrum provides an
early demonstration of the utility of a new spectral processing program (DAPPERS) which
provides start-to-finish spectral assignment and fitting based on the identification of spectral
progressions. Currently, the program is applicable to semi-rigid asymmetric top molecules with
dense rotational spectra but, in principle, could be adapted to analyze spectra with features such
as internal rotation, Coriolis coupling, and nuclear hyperfine structure.

Acknowledgements
This work was supported by the National Science Foundation (Grant No. CHE 1563324) and the
Minnesota Supercomputing Institute. We are grateful to Brian Esselman (UW Madison), Helen
Leung (Amherst College), Mark Marshall (Amherst College), Fan Xie (University of Alberta),
and Yunji Xu (University of Alberta) for providing their experimental spectral files which were
critical to the development and testing of DAPPERS.

15
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30. M.D. Marshall, H.O. Leung, K. Wang, M.D. Acha, J. Phys. Chem. A 122 (2018) 4670–4680.
31. S. Vaccani, U. Roos, A. Bauder, Hs. H. Günthard, Chem. Phys. 19 (1977) 51–57.
32. S. Vaccani, A. Bauder, Hs. H. Günthard, Chem. Phys. Lett. 35 (1975) 457-460.
33. A. Bauder, Mol. Phys. 111 (2013) 1999-2002.

17
Table 1. Spectroscopic Constants of Pivalic Anhydridea,b
Parent 13C6/13C19 13C15/13C28 13C1/13C4

A [MHz] 1517.933464(96) 1517.59346(31) 1505.57983(24) 1516.44979(27)

B [MHz] 456.765702(84) 454.42018(10) 453.31916(27) 456.19737(11)
C [MHz] 434.61336(10) 432.46251(10) 432.39939(16) 434.05900(10)
∆J [kHz] 0.01240(17) 0.01325(61) 0.0129(15) 0.01197(73)
∆JK [kHz] 0.23806(84) 0.2338(73) 0.2375(39) 0.2382(67)
∆K [kHz] -0.1149(29) -0.109(11) -0.135(11) -0.138(10)
δJ [kHz] -0.000202(92) [-0.000202] [-0.000202] [-0.000202]
δK [kHz] 0.057(22) [0.057] [0.057] [0.057]
Nc 273 (226) 30 (25) 23 (22) 22 (21)
σ [kHz] 4.0 3.3 1.9 1.9

13C7/13C20 13C11/13C24 18O2/18O5 18O3

A [MHz] 1516.11388(48) 1503.80980(41) 1490.29340(67) 1517.3256(12)

B [MHz] 451.34088(20) 454.36885(39) 455.164(40) 457.20(17)
C [MHz] 429.68330(32) 431.46515(33) 431.944(43) 434.19(17)
∆J [kHz] 0.0133(17) 0.0095(35) [0.01240] [0.01240]
∆JK [kHz] 0.229(13) 0.2249(65) 0.244(30) [0.23806]
∆K [kHz] -0.114(18) -0.152(14) -0.121(41) [-0.1149]
δJ [kHz] [-0.000202] [-0.000202] [-0.000202] [-0.000202]
δK [kHz] [0.057] [0.057] [0.057] [0.057]
Nc 20 (19) 19 (18) 16 (10) 6 (5)
σ [kHz] 1.6 2.1 1.8 3.5
(a) Column headings with more than one atom listed refer to single substitution on either of the
equivalent atoms indicated. Atom numbering refers to Figure 3.
(b) Numbers in square brackets were constrained to the value determined for the parent
isotopologues.
(c) Number in parentheses denotes the number of distinct frequencies in the fit. Number not in
parentheses denotes the number of transitions included.

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Table 2. Structural Parameters for Pivalic Anhydridea
M06-2X/6-
Bond Lengths [Å ] Experimental
311++G(3df,3pd)
C1⋅⋅⋅C4b 2.3847 2.3507(26)
C1-O2 and C4-O5 1.1874 1.20(16)
C1-C6 and C4-C19 1.5156 1.509(11)
C6-C7 and C19-C20 1.5247 1.513(14)
C6-C11 and C19-C24 1.5329 1.529(17)
C6-C15 and C19-C28 1.5352 1.590(45)

Bond Angles [deg]

O2-C1-C6 and O5-C4-C19 126.8 124.0(44)
C1-C6-C7 and C4-C19-C20 108.7 111.6(14)
C1-C6-C11 and C4-C19-C24 109.7 110.9(16)
C1-C6-C15 and C4-C19-C28 107.3 106.2(34)
C7-C6-C11 and C20-C19-C24 110.6 111.7(18)
C7-C6-C15 and C20-C19-C28 110.5 108.8(36)
C11-C6-C15 and C24-C19-C28 109.9 107.3(35)

Dihedral Angles [deg]

O2-C1-C4-O5 59.5 53.9(39)
O2-C1-C6-C7 and O5-C4-C19-C20 5.2 1.72(19)
O2-C1-C6-C11 and O5-C4-C19-C24 126.2 127(10)
O2-C1-C6-C15 and O5-C4-C19-C28 114.3 117(11)
(a) Atom numbering refers to Figure 3.
(b)The C1⋅⋅⋅C4 distance does not correspond to the length of a bond but is quoted here because
the C1-O3-C4 angle and the C1-O3 and O3-C4 bond lengths are not determined.

19
Table 3. Experimental Coordinates for Pivalic Anhydridea,b
a [Å ] b [Å ] c [Å ]
C1 1.1274(13) 0.4654(32) -0.3322(45)
O2 1.108(17) 1.528(12) -0.889(24)
C4 -1.1274(13) 0.4654(32) 0.3322(45)
O5 -1.108(17) 1.528 (12) 0.889(24)
C6 2.39183(63) -0.2724(55) 0.033(45)
C7 3.62498(42) 0.4743(32) -0.4266(36)
C11 2.36346(65) -1.70350(90) -0.5039(31)
C15 2.41031(63) -0.3630(42) 1.62014(94)
C19 -2.39183(63) -0.2724(55) -0.033(45)
C20 -3.62498(42) 0.4743(32) 0.4266(36)
C24 -2.36346(65) -1.70350(90) 0.5039(31)
C28 -2.41031(63) -0.3630(42) -1.62014(94)

(a) Atom numbering refers to Figure 3.

(b) The Kraitchman analysis gives only the absolute values of the coordinates. Signs have been
inferred based on the computed structure (Figure 3).

20
Table 4. The Three Tests Used to Identify Spectral Progressionsa
Test When is it applied? Equationa
When searching for the first
Starter Test =
transition in a progression

When searching for the second

Ratio Test = !"
# $
transition in a progression

% − %'
=& )#
When searching for the Nth
Derivative Ratio Test %
!"
%' − !"
%' $+ !"
%'
transition in a progression (N > 2) %' − %'

(a) νPred is determined from estimated constants, e.g., from a .cat file produced by SPCAT.

21