Microwave spectra of Ar...AgI and H2O...AgI produced by laser ablation John MullaneyƗ Chris MedcraftƗ, Nick WalkerƗ, Anthony Legonǂ ƗNewcastle University ǂUniversity of Bristol

Generated by laser ablation Linear triatomic Ar .... Ag- X (X = F, Cl, Br) Generated by laser ablation Linear triatomic More strongly bound than Ar ... H-X or Ar ... X-Y complexes X C. J. Evans and M. C. L. Gerry, J. Chem. Phys., 112, 2000, 1321-1329

Sample preparation Target rods prepared from compressed AgI and imidazole powders Laser ablation with Nd:YAG laser (532 nm, ~ 20 mJ/pulse) Rod constantly rotated and translated Supersonic expansion Water reservoir

Chirped-pulse Fourier transform microwave spectrometer (CP-FTMW) Vacuum chamber D. P. Zaleski et al., Phys. Chem. Chem. Phys., 16, 2014, 25221

485k FIDs

Ar...107AgI Ar...109AgI B0/MHz 541.42280(10) 540.71464(10) DJ/ kHz   Ar...107AgI Ar...109AgI B0/MHz 541.42280(10) 540.71464(10) DJ/ kHz 0.05773(24) 0.05686(23) 𝜒aa(I)/MHz -985.411(54) -985.30(14) σRMS/kHz 7.1 6.7 N 68 66 r0(Ag-I) 2.6759 Å r0(Ag...Ar) 2.5356 Å

ic = 1 + χ 𝑎𝑎 (𝑋) 𝑒 𝑄 𝑋 𝑞 (𝑛, 1, 0) 𝑋 Ar...AgF Ar...AgCl Ar...AgBr   Ar...AgF Ar...AgCl Ar...AgBr Ar...AgI r0(Ag...Ar) / Å 2.5581a 2.6124(4)a 2.6366(6)a 2.6759 r0(Ag-X) / Å 1.9861a 2.2683(4)a 2.3825(4)a 2.5356 De / kJmol-1 b 21.8 19.3 18.0 16.7 Ionicity, ic - 0.686 0.638 0.570 F22 / N m-1 29.3(2) 25.8(2) 23.5(6) 20.2(8) ic = 1 + χ 𝑎𝑎 (𝑋) 𝑒 𝑄 𝑋 𝑞 (𝑛, 1, 0) 𝑋 h 𝐷 𝐽 𝑒 = 1 2 ħ 4 (𝐼 𝑏𝑏 𝑒 ) 4 ( 𝑚 1 𝑎 1 ) 2 ( 𝐹 −1 ) 11 +( 𝑚 1 𝑎 1 + 𝑚 2 𝑎 2 ) 2 ( 𝐹 −1 ) 22 F11 = FAg-X F22 = FAr-Ag a C. J. Evans and M. C. L. Gerry, J. Chem. Phys., 112, 2000, 1321-1329 b Calculated at CCSD(T)(F12c)/cc-pVTZ-F12 level of theory D. M. Bittner et al., J. Chem. Phys., 114, 2016, 074308

109AgI...H2O 109AgI...Ar 107AgI...H2O 107AgI...Ar 109AgI H2O...109AgI Frequency / MHz

  H2O...107AgI HDO...107AgI H218O...107AgI (1/2)(B0 + C0)/ MHz 845.09861(14) 824.45945(19) 814.80179(36) DJ/ Hz 0.07072(79) 0.0679(10) 0.0649(17) DJK / kHz 8.642(91) - 8.80(17) 𝜒aa(I)/ MHz -885.54(11) -885.08(24) -884.24(49) 𝜒𝒃𝒃-𝜒𝒄𝒄 (I)/ MHz -12.73(28) -13.6(13) σRMS/ kHz 5.5 5.3 9.6 N 75 28 40   H2O...109AgI HDO...109AgI H218O...109AgI (1/2)(B0 + C0)/MHz 841.64807(14) 821.26461(30) 811.74276(65) DJ/ Hz 0.07111(77) 0.07090(16) 0.0593(28) DJK / kHz 8.626(87) - 8.69(19) 𝜒aa(I)/MHz -885.33(10) -884.42(41) -885.10(71) 𝜒𝒃𝒃-𝜒𝒄𝒄 (I)/MHz -12.79(25) -13.2(17) σRMS/kHz 5.1 7.5 9.3 N 68 26 27

H2O...AgI r0(Ag...O) / Å r0(Ag-X) / Å 𝝋 / o H2O...AgCla H2O...AgFb   H2O...AgI r0(Ag...O) / Å 2.227(7) r0(Ag-X) / Å 2.536(3) 𝝋 / o 36.3(12) H2O...AgCla H2O...AgFb 2.198(10) 2.168(11) 2.273(6) 1.985(11) 37.4(16) 41.9(11) a V. A. Mikhailov et al., J. Chem. Phys., 135, 2011, 014307 b S. L. Stephens et al., J. Chem. Phys., 134, 2011, 134305

Acknowledgements Newcastle University Nick Walker Chris Medcraft Eva Gougoula University of Bristol Tony Legon David Tew University of Valladolid Susana Blanco