444trifluorobutyric acid and its complex with Formic acid Yoon Jeong Choi Alex Trevi ñ o Susanna L Stephens Stephen A Cooke Stewart E Novick Wei Lin WD04 Clusters and Complexes ID: 641990
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Slide1
The
rotational spectra of 4,4,4-trifluorobutyric acid and its complex with Formic acid
Yoon Jeong
Choi,
Alex Treviño, Susanna L. Stephens, Stephen A. Cooke, Stewart E. Novick, Wei Lin
WD04 Clusters and Complexes
Wednesday 21th June
2017 09:21 – 09:36 AMSlide2
Chirp Pulse Experiment
To Diff. Pump
G.S. Grubbs
,
C.T.
Dewberry,
K.C.
Etchison
,
K.E.
Kerr,
S.A. Cooke;
Rev
. Sci.
Instrum
.
,
78
,
096106 (2007)
Center Frequency,
ν
, between 8-18 GHzLinear Frequency Sweep 0 – x - “Chirp”ν +/- x is amplified, pulsed and broadcastExcitation interacts with the moleculesFree Induction Decay Collected, Amplified and Digitized on a 40 GS/s oscilloscopeSlide3
Trifluoroacetic acid
S. Antolinez, J.L. Alonso, H. Dreizler
, E. Hentrop, D.H
. Sutter; Z.
Naturforsch. 54a, 524, (1999) B. Ouyang, T.G. Starkey, B.J. Howard; J. Phys. Chem. A., 111, 6165 (2007)Perfluoropropanoic acid
G.S. Grubbs II, A. Serrato III, D. A
. Obenchain, S.A. Cooke, S.E. Novick, W. Lin;
J. Mol. Spec., 275, 1(2012).G.S. Grubbs II
, D.A. Obenchain, D.S. Frank, S.E.
Novick, S.A. Cooke, A. Serrato III, W. Lin;
J
. Phys. Chem.
A.,
119,
10475 (2015
)
Perfluorobutyric
acid
(& its monohydrate)
J. Thomas, A. Serrato III, W Lin, W. Jäger, Y. Xu; Chem. Eur. J., 20,
6148, (2014)Perfluoropentanoic acidA.M. Pejlovas, W. Lin, S.G.
Kukolich; J. Chem. Phys., 143, 124311 (2015)
One lower energy conformer
detected for
perfluorocarboxylic
acids
Difluoroacetic
acid
B.P. van Eijck
, A.A.J
. Maagdenberg, G. Janssen, T.J. van Goethem-Wiersma;
J. Mol. Spec., 98, 282 (1983
)
F
luoroacetic
acidB.P. van Eijck, P. Brandts, P.M. Maas; J. Mol. Strc., 44, 1 (1978)B.P. van Eijck, G. Van der Plaats, P.H. Van Roon; J. Mol. Spec., 11, 67 (1971)
Two conformers detected for short partially fluorinated carboxylic acidsSlide4
PES’ partially fluorinated carboxylic acids chains multiple conformers
3,3,3-trifluoro-2-(trifluoromethyl)propanoic acidJ. Thomas,
M.J. Carrillo, A.
Serrato III, E.G. Schnitzler, W.
Jäger, Y. Xu, W. Lin; Chem. Phys. Lett., 661, 210 (2016)Two lower energy conformers observed2,3,3,3-tetrafluoropropanoic acidLin et al. Investigation ongoingThree conformers observed
3,3,3-trifluoropropanoic acidL.
Evangelisti, J. van Wijngaarden;
J. Mol. Spec., 290, 1 (2013)One lower
energy conformer observedSlide5
Conformer I
C1
C2
C3
C4Original B3LYP / aug-cc-pVTZ to expected major conformerDihedral τ(OO=C-C1-C
2-C3
) in 5° increments @ B3LYP / aug-cc-pVTZMinima structures further optimized @ MP2 /
aug-cc-pVTZHigher energy conformers with dihedrals of 124° and -124°
4,4,4-Trifluorobutyric acid conformational landscape
C1
C2
C3
C4
C1
C2
C3
C4
Conformer I
Conformer II
Conformer II
0.48 kJ mol
-1Slide6
4,4,4-Trifluorobutyric acid
C1
C2
C3
C4Conformer 1
C1
C2
C3C4
Conformer 2
6 ← 5
7 ← 6
8 ← 7
5 ← 4
9 ← 8
Frequency /MHz
Intensity /V
Dimer?
1.5 bar
Ar
bubbled through sample 7200 averagesSlide7
4,4,4-Trifluorobutyric acidConformer 1
6 ← 5
7 ← 6
8 ← 7
5 ← 49 ← 8
Frequency /MHz
Intensity /V
Dimer?
“New”
1.5 bar
Ar
bubbled through sample 7200 averagesSlide8
4,4,4-Trifluorobutyric acid
Conformer 2?
Conformer 1
Conformer 2
MP2
aug
-TZ
Experiment
MP2 aug
-TZ
Speculation*
Bbar
/MHz
728.9
724.5
743.75
743.12
Experimental
Conformer 1:
Spectral Fit
Conformer 2:
Spectral prediction
Conformer 2: Fit of 3 possible transitions, to be verified*Preliminary results based on 3 transitions at 2:1 intensity
Frequency /MHzSlide9
4,4,4-Trifluorobutyric acid Spectroscopic constants
B3LYP/
aug
-cc-pVTZMP2/aug-cc-pVTZ
Experimental
A
0 /MHz
3628.3
3640.3
3649.20(33)
B
0
/MHz
739.15
751.87
746.74870(64)
C
0
/MHz
694.90
706.02
702.21650(64)
J
/kHz
-
-
0.0200(44)
JK /kHz
-
-
0.384(13)
P
aa/(uǺ2)
635.86
624.57
628.99
P
bb
/(uǺ
2
)
91.42
91.24
90.71
P
cc
/(uǺ
2
)
47.88
47.59
47.79
N
-
-
33
/kHz
-
-
7
Planar
moment of
inertia:
P
aa
= (
I
b
+
I
c
–
I
a
)/2,
P
bb
= (
I
a
+
I
c
–
I
b
)/2, and
P
cc
= (
I
a
+
I
b
-
I
c
)/2
.
Watson
Ir
in PickettSlide10
4,4,4-Trifluorobutyric acid
··· f
ormic acid
8-12 GHzTwo conformers
86 a-type transitions No splitting's associated with hydrogen exchangeFrequency /MHzSlide11
4,4,4-Trifluorobutyric acid ··· formic acid
Conformer A
Conformer B
4,4,4-Trifluorobutyric
acid monomer conformers
Conformer 1
Conformer 2Slide12
Conformer
A
Conformer
B
B3LYP
MP2
Experimental
B3LYP
MP2
ΔD
/kJ
mol
-1
0
0
-
4.0
4.0
ΔD
0
/kJ
mol
-1
0
0
-
3.6
3.9
A
0
/MHz
2523.1
2514.7
2517.80(17)
2666.4
2673.0
B
0
/MHz
285.09
289.58
287.49357(12)
281.48
285.48
C
0
/MHz
269.21
273.03
271.34761(12)
267.50
271.11
Δ
J
/kHz
-
-
0.00510(22)
-
-
Δ
JK
/kHz
-
-
0.0380(17)
-
-
Δ
K
/kHz
-
-
120(52)
-
-
µ
a
/D
1.7
1.7
-
1.7
1.7
µ
b
/D
0.3
0.3
-
0.4
0.4
µ
c
/D
0.0
0.0
-
0.0
0.0
4,4,4-Trifluorobutyric
acid-formic
acidSlide13
Formic acid dimerO.
Birer, M. Havenith;
Annu.
Rev. Phys. Chem., 60
, 263 (2009) & refs.MalonaldehydeW.F. Rowe, R.W. Duerst, E.B. Wilson; J. Am. Chem. Soc., 98, 4021 (1976)S.L. Baughcum, R.W.
Duerst, W.F. Rowe, Z. Smith, E.B Wilson;
J. Am. Chem. Soc., 103, 6296 (1981)
S.L. Baughcum, Z. Smith, E.B. Wilson, R.W. Duerst;
J. Am. Chem. Soc.,
106, 2260 (1984)P. Turner, S.L.
Baughcum
, S. L. Coy, Z. Smith;
J. Am. Chem. Soc
.
106
, 2265 (1984)
Tropolone
K
. Tanaka, H.
Honjo
, T. Tanaka, H.
Kohguchi, Y. Ohshima, Y. Endo; J. Chem. Phys., 110, 1969 (1999)
J.C. Keske, W. Lin, W.C. Pringle, S.E. Novick, T.A. Blake, D.F. Plusquellic; J. Chem. Phys., 124
, 074309 (2006)Propriolic acid ··· Formic AcidA.M. Daly, P.R. Bunker, S.G. Kukolich;
J. Chem. Phys
.,
132(20)
, 201101/1 (2010)
A.M. Daly, P.R. Bunker, S.G. Kukolich
; J. Chem. Phys., 133(7)
, 079903/1 (2010)
A.M. Daly, K.O. Douglass, L.C. Sarkozy, J.L. Neill, M.T. Muckle, D.P. Zaleski, B.H. Pate, S.G
.
Kukolich; J. Chem. Phys
., 135, 154304/1 (2011)Benzoic Acid ··· Formic Acid
L
. Evangelisti, P. Ecija
, E.J.
Cocibero, F. Castano, A. Lessarri, W. Caminati, R. Meyer; J. Phys. Chem. Lett., 3, 3770 (2012)Manifestation of proton tunneling
1/2Slide14
2
/2Manifestation of proton tunneling
Formic acid
··· acetic acid M.C.D. Tayler, B. Ouyang, B.J. Howard;
J. Chem. Phys., 134, 054316/1 (2011)Acrylic acid ··· Trifluoroacetic acid(cis & trans)Q. Gou, G. Feng, L. Evangelisti, W.
Caminati,;
J. Phys. Chem. A., 117
, 13500 (2013)Acrylic acid ··· Difluoroacetic acid
G. Feng, Q. Gou, L.
Evangelisti, W. Caminati
;
Angew
. Chem. Int. Ed.,
53
, 530 (2014)
Perfluorobutyric
acid
···
formic
acid
J. Thomas, A. Serrato III, M.J. Carrillo, W. Lin, W. Jäger, Y. Xu; J. Mol.
Spectrosc., 335, 88 (2017)
2.759 MHz1.203 MHz3
03
3
1
3
1.877 MHz
2.806 MHz
12 kHz
No Tunneling
No TunnelingSlide15
1
L.
Evangelisti
, J. van
Wijngaarden; J. Mol. Spec.
, 290, 1 (2013)
4,4,4-Trifluorobutyric acid-formic acid
complex
No
splittings
associated with hydrogen exchange
Two conformers calculated
2
nd
conformer that would be formed by proton exchange not observed
4,4,4-Trifluorobutyric
acid
PES landscape determined
One conformer observed
Analogous
to 3,3,3-trifluoropropionic acid
1Slide16
Wei Lin
Stewart Novick
Steve Cooke
Karen Peterson
Pete PringleWilman OrellanaYoon ChoiAngela ChungEric ArsenaultRobert MelchreitNational Science FoundationWesleyan Chemistry Department
FB06
FB02
TI11
Not pictured
:
Robert Melchreit TC02
Karen
Peterson: RH07
WE10