Rebecca A. Peebles,a Prashansa B. Kannangara,a Brooks H

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Presentation transcript:

Weak Interactions and CO2 Microsolvation in the cis-1,2-difluoroethylene...CO2 Complex Rebecca A. Peebles,a Prashansa B. Kannangara,a Brooks H. Pate,b William C. Trendell,a Sean A. Peeblesa a Department of Chemistry, Eastern Illinois University, Charleston, IL, USA b Department of Chemistry, University of Virginia, Charlottesville, VA, USA

Why CO2? Weak hydrogen bonding Designing approaches to CO2 sequestration Properties of supercritical fluid Microsolvation Trifluoroethylene (TFE) Difluoroethylene (1,1-DFE) Fluoroethylene (FE) VF-CO2: C. L. Christenholz, et al., J. Phys. Chem. A, 118, (2014), 8765. DFE-CO2: A. M. Anderton, et al., J. Phys. Chem. A, 120, (2016), 247. TFE-CO2: R. Dorris, et al, J. Phys. Chem. A, 120, (2016), 7865.

Next Steps… Additional dimers Move towards larger clusters

Predicted 1,2-DFE-CO2 Structure Observed side-bonded structures Initial prediction for 1,2-DFE-CO2 Gaussian 09: MP2/6-311++G(2d,2p)

Oscilloscope (for data collection) Tektronix TDS5054B 500 MHz Oscilloscope AFG3251 Function Generator (0-240 MHz) HP8673G MW Synthesizer 2-26.5 GHz Molecular Expansion Vacuum Chamber 10 W Solid State Amp Picoammeter Gas sample injected Electron gun power Diffusion pump Supersonic nozzle Oscilloscope (for data collection) Reduced Bandwidth Chirped-Pulse Fourier-Transform Microwave (CP-FTMW) Spectrometer 480 MHz bandwidth, scan in 240 MHz steps Calculate absolute frequencies and assemble into full 11 GHz spectrum using LabVIEW Scan a full (10k average) spectrum in 1 day D. A. Obenchain, A. A. Elliott, A.L. Steber, R. A. Peebles, S. A. Peebles, C. J. Wurrey, G. A. Guirgis, J. Mol. Spectrosc., 261, (2010), 35.

Assignment Process Observed “Stacked” prediction “Side” prediction

Observed a c a c Predicted a c 10000 9000 8000 Fitted

Fitted Constants 0+ 0- A / MHz 3810.154(14) 3809.984(14) B / MHz 0+ 0- A / MHz 3810.154(14) 3809.984(14) B / MHz 1614.4404(25) 1614.4991(21) C / MHz 1456.786(14) 1456.867(14) DJ / kHz 3.490(10) 3.451(10) DJK / kHz 14.940(67) 15.216(60) DK / kHz -12.02(41) dJ / kHz 0.3322(70) dK / kHz -12.72(32) Fac / MHz 167.828(97) DE / MHz 333.2433(19) N 51 Durms / kHz 2.2

Fitted Constants 0+ 0- A / MHz 3810.154(14) 3809.984(14) B / MHz 0+ 0- A / MHz 3810.154(14) 3809.984(14) B / MHz 1614.4404(25) 1614.4991(21) C / MHz 1456.786(14) 1456.867(14) DJ / kHz 3.490(10) 3.451(10) DJK / kHz 14.940(67) 15.216(60) DK / kHz -12.02(41) dJ / kHz 0.3322(70) dK / kHz -12.72(32) Fac / MHz 167.828(97) DE / MHz 333.2433(19) N 51 Durms / kHz 2.2

(Very) preliminary barrier = 42 cm-1 Fitted Constants 0+ 0- A / MHz 3810.154(14) 3809.984(14) B / MHz 1614.4404(25) 1614.4991(21) C / MHz 1456.786(14) 1456.867(14) DJ / kHz 3.490(10) 3.451(10) DJK / kHz 14.940(67) 15.216(60) DK / kHz -12.02(41) dJ / kHz 0.3322(70) dK / kHz -12.72(32) Fac / MHz 167.828(97) DE / MHz 333.2433(19) N 51 Durms / kHz 2.2 (Very) preliminary barrier = 42 cm-1

Structure 0+ 0- A / MHz 3810.154(14) 3809.984(14) 3734.7 8002.3 0+ 0- A / MHz 3810.154(14) 3809.984(14) 3734.7 8002.3 B / MHz 1614.4404(25) 1614.4991(21) 1559.1 868.2 C / MHz 1456.786(14) 1456.867(14) 1403.4 783.2 Paa / u Å2 263.655(2) 263.637(2) 274.5 582.1 Pbb / u Å2 83.259(2) 83.258(2) 85.6 63.2 Pcc / u Å2 49.382(2) 49.388(2) 49.7 0.0 ma / D 2.13(3) 2.2 0.02 mb / D 0.00 2.4 mc / D 1.13(4) 1.4 Gaussian 09: MP2/6-311++G(2d,2p)

Structure Paa for DFE = 85.30534(4) u Å2 m for DFE = 2.42 D 0+ 0- 0+ 0- A / MHz 3810.154(14) 3809.984(14) 3734.7 8002.3 B / MHz 1614.4404(25) 1614.4991(21) 1559.1 868.2 C / MHz 1456.786(14) 1456.867(14) 1403.4 783.2 Paa / u Å2 263.655(2) 263.637(2) 274.5 582.1 Pbb / u Å2 83.259(2) 83.258(2) 85.6 63.2 Pcc / u Å2 49.382(2) 49.388(2) 49.7 0.0 ma / D 2.13(3) 2.2 0.02 mb / D 0.00 2.4 mc / D 1.13(4) 1.4 mtot / D 2.41(5) Paa for DFE = 85.30534(4) u Å2 m for DFE = 2.42 D Monomer rotational constants: N. C. Craig, et al, Int. J. Quantum Chem., 95, (2003), 837. Monomer dipole moment: V. W. Laurie, J. Chem. Phys., 34, (1961), 291. Gaussian 09: MP2/6-311++G(2d,2p)

What’s next? Larger clusters… (d) (e) (a) (b) (c) (i) (h) (f) (g) What’s next? Symmetry adapted perturbation theory (SAPT) Better understanding of energetics Larger clusters… Figure adapted from: R. Dorris, et al, J. Phys. Chem. A, 120, (2016), 7865.

Ees Eind Edisp Eex ESAPT EMP2 (BSSE) X…CO2 [kJ mol-1 ] X = Ees Eind Edisp Eex ESAPT EMP2 (BSSE) FE (side) –8.33 (52.0%) –1.34 (8.3%) –6.36 (39.7%) 8.33 –7.70 –6.41 FE (top) –7.78 (49.7%) –1.30 (8.2%) –6.61 (42.1%) 8.03 –7.66 –6.30 FE (stacked) –6.65 (42.5%) –0.96 (6.1%) –8.02 (51.3%) 8.43 –7.19 –6.44 1,1-DFE (top) –5.69 (44.8%) –1.00 (7.8%) –6.02 (47.4%) 6.49 –6.22 –5.10 1,1-DFE (stacked) –4.43 (34.8%) –0.78 (6.1%) –7.50 (59.1%) 7.35 –5.35 –4.86 cis-1,2-DFE (side) –7.91 (51.0%) –1.34 (8.6%) –6.28 (40.5%) 7.99 –7.54 –6.33 cis-1,2-DFE (stacked) –7.29 (44.6%) –1.11 (6.8%) –7.96 (48.7%) 8.38 –7.97 –6.81 TFE (side) –7.61 (50.2%) –1.30 (8.5%) –6.23 (41.3%) 7.82 –7.32 –6.16 TFE (top) –6.11 (45.7%) –1.21 (9.0%) –6.07 (45.3%) 6.78 –6.61 –5.39 TFE (stacked) –5.84 (41.2%) –0.87 (6.1%) –7.47 (52.7%) 7.52 –6.66 –5.69 Table adapted from: R. Dorris, et al, J. Phys. Chem. A, 120, (2016), 7865.

Building up CO2 solvation shells 387 cm-1 0 cm-1 319 cm-1 24 cm-1 MP2/6-311++G(2d,2p) using Gaussian 09

New Fluoroethylene-CO2 Scan – 1 million FIDs FE-only lines cut

1552.1048(9) 1169.4589(4) 847.2575(3) 351.5135(3) 244.9746(3) 80.6342(3) Strongest Less Strong Weak Top-stack Side-stack Stack Side-top A / MHz 1618.3 1734.3 2933.3 1626.9 B / MHz 1173.9 1107.4 643.5 922.8 C / MHz 881.2 808.4 609.4 588.8 Paa / u Å2 345.9 395.1 721.2 547.6 Pbb / u Å2 227.7 230.1 108.1 310.7 Pcc / u Å2 84.6 61.3 64.2 0.0 ma / D 1.1 0.8 0.03 mb / D 1.0 0.5 1.5 mc / D 0.7 DE / cm-1 24 319 387 1660.3513(1) 1109.7647(1) 785.7773(1) 397.08513(4) 246.07297(4) 58.30781(4) Medium Stronger

Summary and Conclusions cis-1,2-DFE-CO2 is nonplanar CO2 inversion motion Work using Meyer’s 1-dimensional model to determine barrier is in progress Two FE-CO2-CO2 trimers observed Nearly isoenergetic Tetramers?

Acknowledgements National Science Foundation RUI1214070 (2012-2017) RUI1664900 (2017-2020) Pate Group (University of Virginia) Eastern Illinois University spcat 