microwave studies of glycerol f.j. lovas, and d.f plusquellic nist and v.v. ilyushin and r.a....
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Microwave Studies of Glycerol
F.J. Lovas, and D.F Plusquellic
NIST
and
V.V. Ilyushin and R.A. Motiyenko
Institute of Radio Astronomy of NASU
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Outline
Background on Studies of Polyols (for astronomy)
MW Study of Glycerol:ab Initio calculations
Prior free jet study (60 - 78 GHz)
FTMW study (9 - 26.5 GHz)
Summary
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Glycerol: CH2OHCHOHCH2OH
Sweet, colorless, viscous liquid
Results from hydrolysis of fats & oils
Many applications:pharmaceuticals & cosmetics
chemical stabilizer
plasticizer coatings
moisturizer
adhesives & lubricants
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Sugars and Polyols in Space
C2 sugar: “Interstellar Glycolaldehyde: The First Sugar” J.M. Hollis, F.J. Lovas, & P.R. Jewell, Ap. J. 540, L107 (2000)“Green Bank Telescope Observation of Glycolaldehyde”Hollis, Jewell, Lovas & Remijan, ApJ 613, L45 (2004)
C2 sugar alcohol: “Interstellar Antifreeze: Ethylene Glycol” Hollis, Lovas, Jewell, & Coudert, Ap. J. 571, L59 (2002)
“Ethylene glycol in comet C/1995 O1 (Hale-Bopp)” Crovisier, et al. Astron. Astrophys. 418, L35 (2004).
C3 sugars: “GBT Detection of New Interstellar Aldehydes: Propenal andPropanal” Hollis, Jewell, Lovas, Remijan & Møllendal, Ap. J.610, L21 (2004). Negative result on glyceraldehyde, C3H6O3
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Sugars and Polyols in Space
C3 sugars: “1,3-Dihydroxyacetone in Sgr B2(N-LMH): The First Interstellar Ketose” S.L. Widicus Weaver & G.A. BlakeAp. J. 624, L33 (2005); erratum Ap. J. 632, Li63 (2005)
“Investigating the Limits of Chemical Complexity in Sagittarius B2(N): A Rigorous Attempt to confirm 1,3-dihydroxyacetone” Apponi, Halfen, Ziurys, Hollis, Remijan & Lovas Ap. J. 643, L29 (2006)
63 new transitions of DHA were sought but noplausible emission was observed for 97% of these
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Murchison and Murray Meteorite Studies
Polyols in Meteorites by GC-MS
Carbonaceous meteorites as a source of sugar-related organic compounds for the early Earth“ Cooper, Kimmich, Belisle, Sarinana, Brabham & Garrel, Nature 414, 879 (2001).
“Murchison meteorite is generally used as the standard reference for organic compounds in Extraterrestrial material.”
Carbons Sugars Sugar Alcohols Sugar Acids
C2 --- ethylene glycol ----
C3 dihydroxyacetone glycerol glyceric acid
C4 --- Erythritol &Threitol
erythronic acid &threonic acid
C5 --- ribitol & isomers
ribonic acid &isomers
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Prior Lab and Theoretical Studies
Ab Initio study of ethylene glycol and glycerol:Teppen et al. J. Mol. Struct. 314, 169 (1994).
Found 11 stable conformers for glycerol
“Free jet investigation of the rotational spectrum of glycerol” G. Maccaferri, W. Caminati, & P.G. Favero, J. Chem. Soc. FaradayTrans. 93, 4115 (1997).
Identified the 2 lowest energy conformers in the 60 – 78 GHz rangefor the normal and tri-OD species
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(1) G'Gg'gg' E = 0.0 cm-1
(2) GGtg'g' E = 34.4 cm-1
(3) GGgg'g' E = 207.6 cm-1
(4) G'Gg'gt E = 240.4 cm-1
(5) GG'tg'gE = 245.9 cm-1
Five lowest energy conformers of glycerol and their relative energies from ab initio MP2 aug-cc-pVTZ basis set with zero point corrections
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NIST
Mini-FTMW
Spectrometer
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O p tica l Tech n o lo g y D iv is io n
Mirror-MountedHeated Reservoir Nozzle
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9000 10000 11000 12000 13000 14000 15000 16000 17000 180002
3
4
5
6
7
8
9
10
Glycerol
Frequency (MHz)
Inte
nsit
y
A1
A1
A1
A1
A1A1
A2
A2
A2
A2
A2
A2
A2
A2Conformer 1
Conformer 2
Conformer 5a-type
*
*
*
C1C1
C1
B1 B1B2
B2
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Parameter G'Gg'gg' (1)ab initio
MP2GGtg'g' (2)
ab initio MP2
Another Conformer like
(2)?
A (MHz) 4297.81022(11) 4327.5 0.7% 6258.33735(19) 6307.9 0.8% 6255.3793(13)
B (MHz) 3165.445328(94) 3206.1 1.3% 2283.292415(96) 2306.4 1.0% 2266.82639(79)
C (MHz) 2540.440776(96) 2583.4 1.7% 2015.899871(84) 2042.1 1.3% 2002.27853(76)
ΔJ (kHz) 1.4863(18) 0.5251(10) 0.5004(80)
Δ JK (kHz) 1.5133(52) 0.1784(32) 0.172(35)
Δ K (kHz) 2.8869(42) 7.520(16) 7.97(28)
δ J (kHz) 0.34223(93) 0.03254(34) 0.0367(45)
δ K (kHz) 0.9786(57) -0.649(14) -0.97(35)
Nlines 145 136 27
rms (MHz) 0.059 0.051 0.0022
Energy (cm-1) 0.0 34.4
Two Lowest Energy Conformers of Glycerol
C1 C1
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Parameter GGgg'g' (3) ab initio MP2
A (MHz) 6224.6024(16) 6265.16 0.3%
B (MHz) 2270.72466(40) 2292.16 0.9%
C (MHz) 2011.66540(46) 2038.19 1.3%
Δ J (kHz) 0.5208(44)
Δ JK (kHz) 0.138(26)
Δ K (kHz) 8.02(37)
δ J (kHz) 0.0303(17)
δ K (kHz) -0.48(14)
Nlines 30
rms (MHz) 0.0034
Energy (cm-1) 207.6
New Conformer (3) at 207 cm-1
C1
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ParameterGG'tg'g (5)
v=0GG'tg'g (5)
v=1ab initio MP2
A (MHz) 8208.24389(28) 8208.24979(28) 8295.01 1.0%
B (MHz) 1986.495283(71) 1986.495966(72) 2003.02 0.3%
C (MHz) 1712.662887(76) 1712.659143(75) 1728.10 0.9%
Δ J (kHz) 0.18335(74) 0.18249(74)
Δ JK (kHz) 2.4295(34) 2.4354(32)
Δ K (kHz) 8.406(38) 8.415(38)
δJ (kHz) 0.02318(16) 0.02363(16)
δ K (kHz) 1.146(11) 1.109(12)
E (MHz) 41.9254
Nlines 180 180
rms (MHz) 0.0025 0.0025
Energy (cm-1) 245.9
C1
Second New Conformer at 246 cm-1 with OH Tunneling
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Measured and calculated dipole moments for glycerol conformers
G'Gg'gg' (1) Measured MP2 Diff. %
μa 0.780(6) D -0.81 D 3.8
μb 0.30(2) D 0.30 D 0.0
μc 1.134(4) D 1.25 D 10.2
GGtgg' (2) Measured MP2 Diff. %
μa 1.749(3) D -1.86 D 6.3
μb 0.901(2) D -1.04 D 15.5
μc 0.161(2) D -0.13 D 18.7
GGgg'g' (3) Measureda MP2 Diff. %
μa ≈1.7 D -1.61 D 5.3
μb ≈0.2 D -0.20 D 0.0
μc ≈1.7 D 2.22 D 30.3
a Estimated from intensity comparisons
GGtg'g (5) Measured MP2 Diff. %
μa 2.77(5) D -3.02 D 6.9
μb 1.47(7) D -1.20 D 18.4
μc ≈0. D 1.03 D ---
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Summary
• FTMW spectrum yielded 4-5 conformers
• Ab initio calculations aided new conformer identification
• Dipole moments determined & aided assignments
• GBT data covered good candidate lines for conformers 1 & 2, but no signals observed down to 5 – 10 mK noise level