In the rotational spectroscopy community, several popular codes are available to treat multiple internal rotors in a molecule. In terms of the pros and cons of each code, it is often a difficult task to decide which program to apply to a specific internal rotation problem. We faced this issue when dealing with the spectroscopic fingerprint of 4-methylacetophenone (4MAP), recently investigated in the microwave region, which we here extended into the millimeterwave region. The methyl group attached to the phenyl ring in 4MAP undergoes internal rotation with a very low barrier of only 22 cm−1. The acetyl methyl group features a much higher barrier of about 580 cm−1. The performances of a program using the so-called “local” approach in terms of Herschbach’s perturbative treatment, SPFIT, as well as three programs XIAM, ERHAM, and ntop, representing “global” fits, were tested. The results aim at helping spectroscopists in the decision on how to tackle their own internal rotation problems.
REFERENCES
1.
H. V. L.
Nguyen
, I.
Kleiner
, I.
Gulaczyk
, and B.
Tylkowski
, in Theoretical and Computational Chemistry
, edited by B.
Tylkowski
(De Gruyter
, 2021
), pp. 41
–52
.2.
I.
Kleiner
, J. Mol. Spectrosc.
260
, 1
–18
(2010
).3.
C. C.
Lin
and J. D.
Swalen
, Rev. Mod. Phys.
31
, 841
–892
(1959
).4.
Z.
Kisiel
, Spectroscopy from Space
, edited by J.
Demaison
, et al. (Kluwer Academic Publishers
, Dordrecht
, 2001
), pp. 91
–106
, http://info.ifpan.edu.pl/∼kisiel/prospe.htm.5.
H.
Hartwig
and H.
Dreizler
, Z. Naturforsch, A: Phys. Sci.
51a
, 923
–932
(1996
).6.
P.
Groner
, J. Chem. Phys.
107
, 4483
–4498
(1997
).7.
J. T.
Hougen
, I.
Kleiner
, and M.
Godefroid
, J. Mol. Spectrosc.
163
, 559
–586
(1994
).8.
I.
Kleiner
and J. T.
Hougen
, J. Chem. Phys.
119
, 5505
–5509
(2003
).9.
M.
Tudorie
, I.
Kleiner
, J. T.
Hougen
, S.
Melandri
, L. W.
Sutikdja
, and W.
Stahl
, J. Mol. Spectrosc.
269
, 211
–225
(2011
).10.
V. V.
Ilyushin
, Z.
Kisiel
, L.
Pszczólkowski
, H.
Mäder
, and J. T.
Hougen
, J. Mol. Spectrosc.
259
, 26
–38
(2010
).11.
V. V.
Ilyushin
and J. T.
Hougen
, J. Mol. Spectrosc.
289
, 41
–49
(2013
).12.
N.
Ohashi
and J. T.
Hougen
, J. Mol. Spectrosc.
203
, 170
–174
(2000
).13.
L.
Ferres
, W.
Stahl
, and H. V. L.
Nguyen
, J. Chem. Phys.
148
, 124304
(2018
).14.
L.
Ferres
, W.
Stahl
, and H. V. L.
Nguyen
, J. Chem. Phys.
151
, 104310
(2019
).15.
V.
Van
, T.
Nguyen
, W.
Stahl
, H. V. L.
Nguyen
, and I.
Kleiner
, J. Mol. Struct.
1207
, 127787
(2020
).16.
H. M.
Pickett
, J. Chem. Phys.
107
, 6732
–6735
(1997
).17.
H. M.
Pickett
, J. Mol. Spectrosc.
148
, 371
–377
(1991
).18.
R. C.
Woods
, J. Mol. Spectrosc.
21
, 4
–24
(1966
).19.
R. C.
Woods
, J. Mol. Spectrosc.
22
, 49
–59
(1967
).20.
P.
Groner
, J. Mol. Spectrosc.
278
, 52
–67
(2012
).21.
B. J.
Drouin
, J. C.
Pearson
, A.
Walters
, and V.
Lattanzi
, J. Mol. Spectrosc.
240
, 227
–237
(2006
).22.
D. R.
Herschbach
, J. Chem. Phys.
31
, 91
–108
(1959
).23.
S.
Herbers
, S. M.
Fritz
, P.
Mishra
, H. V. L.
Nguyen
, and T. S.
Zwier
, J. Chem. Phys.
152
, 074301
(2020
).24.
L. H.
Xu
and J. T.
Hougen
, J. Mol. Spectrosc.
173
, 540
–551
(1995
).25.
I.
Kleiner
, ACS Earth Space Chem.
3
, 1812
–1842
(2019
).26.
K.
Eibl
, W.
Stahl
, I.
Kleiner
, and H. V. L.
Nguyen
, J. Chem. Phys.
149
, 144306
(2018
).27.
Y.
Zhao
, W.
Stahl
, and H. V. L.
Nguyen
, Chem. Phys. Lett.
545
, 9
–13
(2012
).28.
L.
Ferres
, K. N.
Truong
, W.
Stahl
, and H. V. L.
Nguyen
, ChemPhysChem
19
, 1781
–1788
(2018
).29.
C. J.
Smith
, A. K.
Huff
, H.
Zhang
, Y.
Mo
, and K. R.
Leopold
, J. Chem. Phys.
150
, 134302
(2019
).30.
K. P. R.
Nair
, S.
Herbers
, A.
Lesarri
, and J.-U.
Grabow
, J. Mol. Spectrosc.
361
, 1
–7
(2019
).31.
S.
Herbers
and H. V. L.
Nguyen
, J. Mol. Spectrosc.
370
, 111289
(2020
).32.
K. P. R.
Nair
, S.
Herbers
, H. V. L.
Nguyen
, and J.-U.
Grabow
, Spectrochim. Acta, Part A
242
, 118709
(2020
).33.
M.
Hermanns
, N.
Wehres
, F.
Lewen
, H. S. P.
Müller
, and S.
Schlemmer
, J. Mol. Spectrosc.
358
, 25
–36
(2019
).34.
J. U.
Grabow
, W.
Stahl
, and H.
Dreizler
, Rev. Sci. Instrum.
67
, 4072
–4084
(1996
).35.
M. H.
Ordu
, O.
Zingsheim
, A.
Belloche
, F.
Lewen
, R. T.
Garrod
, K. M.
Menten
, S.
Schlemmer
, and H. S. P.
Müller
, Astron. Astrophys.
629
, A72
(2019
).36.
M. A.
Martin-Drumel
, J.
van Wijngaarden
, O.
Zingsheim
, F.
Lewen
, M. E.
Harding
, S.
Schlemmer
, and S.
Thorwirth
, J. Mol. Spectrosc.
307
, 33
–39
(2015
).37.
O.
Zingsheim
, L.
Bonah
, F.
Lewen
, S.
Thorwirth
, H. S. P.
Müller
, and S.
Schlemmer
, J. Mol. Spectrosc.
381
, 111519
(2021
).38.
J.
Mélan
, S.
Khemissi
, and H. V. L.
Nguyen
, Spectrochim. Acta A
253
, 119564
(2021
).39.
S.
Khemissi
and H. V. L.
Nguyen
, ChemPhysChem
21
, 1682
–1687
(2020
).40.
W.
Gordy
and R. L.
Cook
, Microwave Molecular Spectra
, Equations 12.52 and 12.56, 3rd ed. (Wiley
, New York
, 1984
), Vol. 18.41.
C.
Dindić
, A.
Lüchow
, N.
Vogt
, J.
Demaison
, and H. V. L.
Nguyen
, J. Phys. Chem. A
125
, 4986
–4997
(2021
).42.
R. J.
Lavrich
, D. F.
Plusquellic
, R. D.
Suenram
, G. T.
Fraser
, A. R. H.
Walker
, and M. J.
Tubergen
, J. Chem. Phys.
118
, 1253
–1265
(2003
).43.
P.
Stahl
, B. E.
Arenas
, O.
Zingsheim
, M.
Schnell
, L.
Margulès
, R. A.
Motiyenko
, G. W.
Fuchs
, and T. F.
Giesen
, J. Mol. Spectrosc.
378
, 111445
(2021
).44.
T.
Yanai
, D. P.
Tew
, and N. C.
Handy
, Chem. Phys. Lett.
393
, 51
–57
(2004
).45.
S.
Grimme
, J.
Antony
, S.
Ehrlich
, and H.
Krieg
, J. Chem. Phys.
132
, 154104
(2010
).46.
E. R.
Johnson
and A. D.
Becke
, J. Chem. Phys.
123
, 024101
(2005
).47.
M. J.
Frisch
, G. W.
Trucks
, H. B.
Schlegel
, G. E.
Scuseria
, M. A.
Robb
, J. R.
Cheeseman
, G.
Scalmani
, V.
Barone
, G. A.
Petersson
, H.
Nakatsuji
, X.
Li
, M.
Caricato
, A. V.
Marenich
, J.
Bloino
, B. G.
Janesko
, R.
Gomperts
, B.
Mennucci
, H. P.
Hratchian
, J. V.
Ortiz
, A. F.
Izmaylov
, J. L.
Sonnenberg
, D.
Williams-Young
, F.
Ding
, F.
Lipparini
, F.
Egidi
, J.
Goings
, B.
Peng
, A.
Petrone
, T.
Henderson
, D.
Ranasinghe
, V. G.
Zakrzewski
, J.
Gao
, N.
Rega
, G.
Zheng
, W.
Liang
, M.
Hada
, M.
Ehara
, K.
Toyota
, R.
Fukuda
, J.
Hasegawa
, M.
Ishida
, T.
Nakajima
, Y.
Honda
, O.
Kitao
, H.
Nakai
, T.
Vreven
, K.
Throssell
, J. A.
Montgomery
, Jr., J. E.
Peralta
, F.
Ogliaro
, M. J.
Bearpark
, J. J.
Heyd
, E. N.
Brothers
, K. N.
Kudin
, V. N.
Staroverov
, T. A.
Keith
, R.
Kobayashi
, J.
Normand
, K.
Raghavachari
, A. P.
Rendell
, J. C.
Burant
, S. S.
Iyengar
, J.
Tomasi
, M.
Cossi
, J. M.
Millam
, M.
Klene
, C.
Adamo
, R.
Cammi
, J. W.
Ochterski
, R. L.
Martin
, K.
Morokuma
, O.
Farkas
, J. B.
Foresman
, and D. J.
Fox
, GAUSSIAN 16 Revision B.01, Gaussian, Inc.
, Wallingford, CT
, 2017
.48.
S.
Herbers
, P.
Kraus
, and J.-U.
Grabow
, J. Chem. Phys.
150
, 144308
(2019
).49.
V. V.
Ilyushin
, E. A.
Alekseev
, Z.
Kisiel
, and L.
Pszczółkowski
, J. Mol. Spectrosc.
339
, 31
–39
(2017
).50.
D.
Tikhonov
, Struct. Chem.
(published online, 2021
).© 2021 Author(s). Published under an exclusive license by AIP Publishing.
2021
Author(s)
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