1. 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

2. 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,

3. 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

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

5. 485k FIDs

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

7. 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 = χ 𝑎𝑎 (𝑋) 𝑒 𝑄 𝑋 𝑞 (𝑛, 1, 0) 𝑋
h 𝐷 𝐽 𝑒 = 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,
b Calculated at CCSD(T)(F12c)/cc-pVTZ-F12 level of theory
D. M. Bittner et al., J. Chem. Phys., 114, 2016,

8. 109AgI...H2O 109AgI...Ar 107AgI...H2O 107AgI...Ar 109AgI H2O...109AgI
Frequency / MHz

9. H2O...107AgI
HDO...107AgI
H218O...107AgI
(1/2)(B0 + C0)/ MHz
(14)
(19)
(36)
DJ/ Hz
(79)
0.0679(10)
0.0649(17)
DJK / kHz
8.642(91) -
8.80(17)
𝜒aa(I)/ MHz
(11)
(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
(14)
(30)
(65)
DJ/ Hz
(77)
(16)
0.0593(28)
DJK / kHz
8.626(87) -
8.69(19)
𝜒aa(I)/MHz
(10)
(41)
(71)
𝜒𝒃𝒃-𝜒𝒄𝒄 (I)/MHz
-12.79(25)
-13.2(17)
σRMS/kHz
5.1
7.5
9.3 N 68 26 27

10. 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,
b S. L. Stephens et al., J. Chem. Phys., 134, 2011,

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