Microwave Measurements of Cyclopropanecarboxylic Acid and its Doubly Hydrogen Bonded Dimer with Formic Acid Aaron M. Pejlovas, Kexin Li, Dr. Stephen G.

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Microwave Measurements of Cyclopropanecarboxylic Acid and its Doubly Hydrogen Bonded Dimer with Formic Acid Aaron M. Pejlovas, Kexin Li, Dr. Stephen G. Kukolich Dr. Wei Lin (University of Texas Rio Grande Valley) ISMS June 2016

Earlier Work

Conformers of CPCA B3LYP/aug-cc-pVQZ predicted difference in E of ~ 0.92 kcal/mol (~ 320 cm-1)

Ground State Conformation of CPCA Microwave measurements at 5-15 GHz using pulsed beam FT microwave spectrometer Heat sample to ~50 °C Parent, –OD isotopologue, all unique singly substituted 13C isotopologue Natural abundance (except –OD, synthesized through exchange rxn w/ MeOD)

13C(3&6) 13C(9) 13C(1) -OD Parent A/MHz 7563.3591(16) 7624.9982(19) 13C(3&6) 13C(9) 13C(1) -OD Parent A/MHz 7563.3591(16) 7624.9982(19) 7577.7505(38) 7619.8580(64) 7625.0432(17) B/MHz 2676.47555(90) 2716.6267(19) 2720.6834(22) 2629.4700(14) 2724.7672(8) C/MHZ 2351.02155(96) 2375.8584(19) 2374.3843(28) 2308.5301(14) 2382.0755(5) ΔJ/kHz 0.3845* ΔJK/kHz 3.087* ΔK/kHz -0.447* δJ/kHz 0.04375* -11.972* φJ/Hz 0.005092* N 6 5 9 16 σ/kHz 2 3 *Marstokk, K. -M.; Mollendal, H.; Samdal, S. Acta Chemica Scandinavica 1991, 45, 37-45.

Excited State Conformer Microwave measurements at 5-11 GHz (PBFT) Previously searched for at 26.5-38 GHz, but not observed1 Only parent isotopologue measured Transitions observed at RT 1Marstokk, K. -M.; Mollendal, H.; Samdal, S. Acta Chemica Scandinavica 1991, 45, 37-45.

Experiment B3LYP/aug-cc-pVQZ MP2/6-311+G**1 A/MHz 7452.3132(57) Experiment B3LYP/aug-cc-pVQZ MP2/6-311+G**1 A/MHz 7452.3132(57) 7490.121 7451 B/MHz 2789.8602(43) 2770.327 2786 C/MHZ 2415.0725(40) 2399.7699 2411 DJ/kHz 0.29(53) DJK/kHz 2.5(12) N 10 σ/kHz 5 1Marstokk, K. -M.; Mollendal, H.; Samdal, S. Acta Chemica Scandinavica 1991, 45, 37-45.

101 to 000 transitions, recorded after 230 pulsed-beam cycles. Appeared to be similar intensity as 13C signals of ground state conformer

CPCA – FA Dimer Measured transitions from parent, all unique singly substituted 13C (natural abundance), and D-FA (purchased) Sample of FA cooled to -8 °C, CPCA and valve at 60 °C

Parent 13C(16) 13C(3&6) 13C(1) 13C(9) D(17) A/MHz 4045.4193(16) 4044.16(21) 4021.03(25) 4035.98(22) 4041.76(37) 4035.84(66) B/MHz 740.58380(14) 730.45455(16) 730.44765(18) 735.63679(17) 740.11049(30) 722.3152(32) C/MHz 658.56760(23) 650.51344(17) 650.81382(20) 654.40357(19) 658.09839(33) 643.9651(12) ΔJ/kHz 0.0499(16) 0.0499* ΔJK/kHz 0.108(14) 0.108* N 31 7 σ/kHz 2 1 6 Type B97D/aug-cc-pVTZ MP2/aug-cc-pVTZ Parent (exp.) A/MHz 4068.66 4038.00 4045.42 B/MHz 732.32 747.56 740.58 C/MHz 652.25 663.19 658.57 µa(Debye) 1.7 1.4 µb(Debye) 0.2 µc(Debye) 0.0

CPCA – FA Dimer No concerted proton tunneling observed Singlet a- and b-type transitions Structure fit for dimer to determine H-bond distances Interatomic Distance Microwave Fit Value Calculated (MP2) Value r(H12-O14) 1.36 1.67 r(O11-H13) 2.25 1.62 COM Separation 4.11 4.09

CPCA-FA Dimer

Excited Dimer Conformer? B97D/aug-cc-pVTZ predicted E separation of 210 cm-1 Did not observe excited conformer of dimer after extensive searches

Acknowledgements Dr. Stephen Kukolich Dr. Wei Lin (University of Texas Rio Grande Valley) Kexin Li NSF University of Arizona