THE MICROWAVE SPECTRUM AND UNEXPECTED STRUCTURE OF THE BIMOLECULAR COMPLEX FORMED BETWEEN ACETYLENE AND (Z)-1-CHLORO-2-FLUOROETHYLENE Nazir D. Khan, Helen.

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THE MICROWAVE SPECTRUM AND UNEXPECTED STRUCTURE OF THE BIMOLECULAR COMPLEX FORMED BETWEEN ACETYLENE AND (Z)-1-CHLORO-2-FLUOROETHYLENE Nazir D. Khan, Helen O. Leung & Mark D. Marshall Department of Chemistry Amherst College Supported by the National Science Foundation

Leung, Marshall, Amberger, Fluoroethylene---HF Complexes 18.7(15)o 21.65o 29.99o 2.734 Å 1.892(14) Å 2.60952(14) Å 1.910297(68) Å 2.7825(3) Å 1.98833(44) Å Cole & Legon, CPL 400, 419 (2004) Leung, Marshall, Amberger, JCP 131, 204302 (2009) Leung & Marshall et. al, JCP 131, 204301 (2009) 2.7522(40) Å An increase in the number of F substituents has significant effects on the nature of intermolecular interactions. 41.6(51)o 2.020(41) Å Leung & Marshall, JCP 126, 114310 (2007)

1, 1-Difluoroethylene---HX Complexes 3.0762(3) Å 2.3309(4) Å 122.41o 34.22o Kisiel, Fowler, Legon, J. Chem. Soc., Faraday Trans. 88, 3385 (1992) 1.9883(4) Å 2.7825(3) Å 29.99o Leung, Marshall, Drake, Pudlik, Savji, McCune, J. Chem. Phys. 131, 204301 (2009) 2.65(1) Å 3.01(2) Å 122.4(8)o 53.3(2)o Leung, Marshall, J. Chem. Phys. 125, 154301 (2006) H C C F H H Cl H

A Different Structure for the 1, 1, 2-Trifluoroethylene---HF Complex 2.60952(14) Å 1.910297(68) Å 21.65o Leung, Marshall, Amberger, JCP 131, 204302 (2009) 41.6(51)o 2.7522(40) Å 2.020(41) Å Leung & Marshall, JCP 126, 114310 (2007) 122.41o 109.0o “Top binding” “Side binding” Top binding is sterically more favorable, and side binding is electrostatically more favorable.

1,1,2-Trifluoroethylene---HX Complexes 2.8694(9) Å 104.5(2)o 2.75(2) Å 69.2(7)o H C 2.02(4) Å 2.752(4) Å 109(1)o 42(5)o C F H H Leung, Marshall, J. Chem. Phys. 126, 114310 (2007) Leung, Marshall, Cashion, Chen, J. Chem. Phys. 128, 064315 (2008) 2.3416(7) Å 3.0796(5) Å 109.72(4)o 47.73(1)o Cl H Leung, Marshall, Ray, Kang, J. Phys. Chem. 114, 10975 (2010)

Effects of Chlorine Substitution: Chlorofluoroethylenes and chloroethylenes What is the effect of substituting chlorine atoms for fluorine atoms in various fluoroethylenes? Chlorine is less electronegative than fluorine Chlorine is more polarizable Acids were expected to preferentially bind to fluorine in chlorofluoroethylenes The primary interaction was expected to be weakened less by additional chlorine substitution than additional fluorine substitution

Chlorofluoroethylene---HF Complexes 1.9482(10) Å 124.371(70)o 2.7386(19) Å 29.14o 24.93(1)o F F H H 2.4535(2) Å 1.9445(2) Å HF preferentially binds to fluorine over chlorine in chlorofluoroethylenes 118.635o F F H H H H Cl Cl 2.7574(12) Å Leung, Marshall, Bozzi, Cohen, Lam, J. Mol. Spectrosc. 267, 43 (2010) F F Leung, Marshall, Lee, In preparation H 41.5(24)o 109.20(61)o F 2.020(18) Å H Cl Leung, Marshall, Bozzi, In preparation

Vinyl Chloride---HX Complexes 2.319(6) Å 2.59(1) Å 19.8(3)o 102.4(2)o 3.02(1) Å 88.6(2)o 58.5(6)o 2.93(1) Å F H Cl Cl H Cl C H C 2.409 Å 3.386 Å H Leung, Marshall, J. Phys. Chem. 118, 9783 (2014) Leung, Marshall, Bozzi, Cohen, Lam, J. Phys. Chem. 117, 13419 (2013) Cl Acid identity determines the structure of the vinyl chloride---HX complex Minimum energy structure predicted by ab initio calculations for the vinyl chloride---HCl dimer

(Z)-1-Chloro-2-fluoroethylene---HCCH Complex How does HCCH bind to (Z)-1-chloro-2-fluoroethylene? How do the geometric parameters compare to previous results? ?

Ab Initio Calculations 2.57958 Å 2.89827 Å 61.44o 104.33o Fluorine bound minimum 3.04148 Å 2.77504 Å 61.74o 85.67o Chlorine bound minimum θZE r θHCCH A = 11551.2790012 MHz B = 806.4824631 MHz C = 753.8504419 MHz 75 cm-1 A = 4768.7499746 MHz B = 1086.3100008 MHz C = 884.7630614 MHz 0 cm-1

Chirped-Pulse FTMW Spectroscopy Studied in the 5.5-18.1 GHz region 1% CHFCHCl, 1% HCCH in Ar at ~2 atm backing pressure Two isotopologues CHFCH35Cl---HCCH CHFCH37Cl---HCCH Nozzle is mounted perpendicular to microwave horns CHFCH35Cl---HCCH 313-202 Ar---CHFCH35Cl * CHFCH37Cl

Balle-Flygare FTMW Spectroscopy Studied in the 5.5-20.7 GHz region 1% CHFCHCl, 1% HCCH in Ar at ~2 atm backing pressure Six isotopologues CHFCH35Cl---HCCH, CHFCH37Cl---HCCH, CHFCH35Cl---H13C13CH, CHFCH37Cl---H13C13CH, CHFCH35Cl---H13CCH, 13CHFCH35Cl---HCCH Nozzle is mounted parallel to mirror axis, leading to Doppler doubling in each transition.

Representative Transition CHFCH35Cl---HCCH 313-202 F’ = 4.5 F” = 3.5 F’ = 1.5 F” = 1.5

(Z)-1-chloro-2-fluoroethylene---HCCH Transitions CHFCH35Cl---HCCH CHFCH37Cl---HCCH CHFCH35Cl---H13C13CH CHFCH37Cl---H13C13CH 13CHFCH35Cl---HCCH CHFCH35Cl---H13CCH Total # of transitions 101 104 88 76 6 7 # of a-type transitions 43 50 42 36 2 3 # of b-type transitions 58 54 46 40 4 Hyperfine components 587 533 476 372 16 21 J range 0-10 2-5 Ka range 0-4 0-3 0-1

Spectroscopic Constants (MHz) CHFCH35Cl---HCCH A 4885.649238(85) B 1057.174079(35) C 869.413173(32) ΔJ / 10-3 1.16322(23) ΔK / 10-3 0.0698551(82) ΔJK / 10-3 -0.8450(19) δJ / 10-3 0.25182(11) δK / 10-3 5.2715(12) χaa 39.83616(66) χbb -72.66307(83) χcc 32.82691(79) RMS 0.0018 Fluorine bound minimum A = 11551.2790012 MHz B = 806.4824631 MHz C = 753.8504419 MHz Chlorine bound minimum A = 4768.7499746 MHz B = 1086.3100008 MHz C = 884.7630614 MHz

Spectroscopic Constants (MHz) CHFCH37Cl---HCCH CHFCH35Cl---H13C13CH CHFCH37Cl---H13C13CH 13CHFCH35Cl---HCCH CHFCH35Cl---H13CCH A 4742.466963(66) 4844.133202(90) 4702.44029(10) 4822.9290(22) 4884.4318(18) B 1056.557011(24) 1009.347222(33) 1008.547251(52) 1052.27636(25) 1036.10835(23) C 864.330032(19) 835.57850(28) 830.692854(51) 864.10321(52) 855.08513(48) ΔJ / 10-3 1.15635(14) 1.07935(20) 1.07266(31) 1.1435(81) 1.1037(75) ΔK / 10-3 0.0656266(74) 0.068095(10) 0.063931(12) 0.0698551* ΔJK / 10-3 -0.5415(11) -0.8361(19) -0.5245(36) -0.8450* δJ / 10-3 0.254928(63) 0.22626(10) 0.22909(14) 0.25182* δK / 10-3 5.1913(60) 4.987(11) 4.920(21) 5.2715* χaa 31.40535(60) 39.85329(72) 31.41743(96) 39.819(20) 39.843(16) χbb -57.27402(70) -72.67854(85) -57.2854(10) -72.658(16) -72.6720(58) χcc 25.86868(62) 32.82525(75) 25.86795(96) 32.8387(71) 32.829(12) RMS 0.0014 0.0016 0.0017 0.0018 0.0015

Some Observations κ ranges from -0.92 – -0.90 Δ ranges from -0.21 – -0.18 amu·Å2 typical of a planar molecule in which out-of-plane vibrational contribution is dominant The rotational constants of 3 singly substituted isotopologues are used to locate the positions of 3 atoms.

Substitution Structure CHFCHCl--- HCCH |a|/Å 0.3758(40) 1.4935(10) 3.12697(48) |b|/Å 1.2627(12) 1.1668(13) 0.1631(92) + + - ± + - ± b Cl C C a C C C

Fit to Moments of Inertia Three geometric parameters are required to describe the structure of the complex Fit parameters to Ia and Ic of each of the six isotopologues, assuming the structures of CHFCHCl and HCCH remain unchanged upon complexation. a b 3.076(21) Å 2.8644(23) Å 87.54(34)o Cl C H F 62.4(12)o

Chlorine Quadrupolar Coupling Assuming no efg perturbation upon complexation, one of the principal efg axes should lie more or less along the C-Cl bond. Angle between C-Cl bond and a axis From χ tensor of CHFCH35Cl---HCCH 91.95o From fit to inertial data 89.61o

Chloroethylene---HCCH Complexes 3.076(21) Å 2.8644(23) Å 62.4(12)o 3.02(1) Å 88.6(2)o 58.5(6)o 2.93(1) Å Experimental structures 2.9854 Å 86.50o 57.84o 2.8339 Å 3.0415 Å 2.7750 Å 61.74o 85.67o Ab initio minimum energy structures

Chlorofluoroethylene---HCCH Complexes 3.076(21) Å 2.8644(23) Å 62.4(12)o 124.30(70)o 2.623(11) Å 52.82(28)o 2.977(17) Å HCCH binds to chlorine when only side binding is allowed HCCH binds to fluorine when only top binding is allowed

(Z)-1-Chloro-2-fluoroethylene---HX Complexes 3.076(21) Å 2.8644(23) Å 62.4(12)o 2.88560 Å 1.89650 Å 26.00o 109.99o Red: Most negative electric potential Blue: Most positive electric potential Minimum energy structure predicted by ab initio calculations for the dimer with HF Experimental structure of the dimer with HCCH

Summary The rotational spectra of six isotopologues of (Z)-1-chloro-2-fluoroethylene---HCCH have been observed and analyzed. HCCH interacts with the Cl and H atoms at one end of the double bond instead of the F and H atoms at the other end of the double bond. This bonding motif is different from that observed in all other chlorofluoroethylene---HX dimers. The different binding modes can be explained by different steric requirements for F and Cl in the chlorofluoroethylene dimers

Acknowledgements National Science Foundation for providing funding Thank you