1. Chris Medcraft Dror Bittner, Nick Walker, Tony Legon
Microwave spectroscopy and structure determination of H2S MI (M=Cu, Ag, Au)
Chris Medcraft
Dror Bittner, Nick Walker, Tony Legon

2. Chirped-pulse Fourier transform microwave spectrometer (CP-FTMW)
Nd:Yag 532 nm laser
~25 mJ/pulse
N. R. Walker et al., Phys. Chem. Chem. Phys., 16, 2014, 25221

4. CP-FTMW Spectrometer
S. L. Stephens, N. R. Walker, J. Mol. Spectr., 263, 27 (2010).

5. Newcastle Ablation Sources
13mm

6. Small ablation source

7. Metal Complexes PdCCC M + CF3I  MI XMY M + CCl4  MCl
X=C2H2, H2S, H2O, NH3,c-C3H6, TMA….
M + SF6  MF
M = Cu, Ag, Au, Pb, Sn,Pt, Pd
M + CF3I Ar---MI
MI Ar---MI
Ag + CCl4  AgCCCl
Cu + CCl4  CuCCCl
Zaleski et al. J. Phys. Chem. A 2015, 119, 2919
H2CCCH2
HCCH
H2CCH2
CH4
C4H4O (furan)
PdCCC
Palladium Rod
Bittner et al. Angew. Chem. Int. Ed. 2016, 55, 3768

8. H2SMI (M = Cu, Ag, Au) Ablation target: solid Cu or Ag rod or Au foil
Gas mixture: CF3I and H2S in argon (≈1%)
>10 species identified in MW spectra
Intensity / μV

9. H2S63CuI 0.8 Intensity / μV 0.0 63Cu/65Cu = 0.69/0.31 0.7
1.3 M FIDs
0.0
63Cu/65Cu = 0.69/0.31
D2S63CuI
0.7
17220
17224
17228
Intensity / μV
2.1 M FIDs
Frequency [MHz]
0.0
0.4
HDS63CuI
1.4 M FIDs
Intensity / μV
0.0
18080
18100
Frequency [MHz]
18428
18430
18432
18434
Frequency [MHz]

10. H2SAgI K-1=1 transitions detected for D2S109AgI and D2S107AgI
K-1=1 transitions overlap K-1=0 at lower J’s
B-C ≈ 500 kHz
107Ag/109Ag = 0.52/0.48
D2S109AgI
D2S107AgI
D2S109AgI
D2S107AgI
0.5
0.7
J = 98
J = 1514
Intensity / μV
Intensity / μV
0.0
0.0
00000
Frequency [MHz]
Frequency [MHz]

11. D2SAuI No K-1 = 1 transitions identified B-C ≈ 250 kHz
K-1 = 1 transitions would overlap with K-1 = 0 transitions
J = 1413
J = 1514
16815
16820
18016
18020
18024
Frequency [MHz]
Frequency [MHz]

12. H2SMI (M=Cu, Ag, Au)
Only K-1=0 transitions found for H2S and HDS species
K-1=1 transitions found for D2S---CuI and D2S---AgI (not Au)
H2S---HX, H2S---XY and H2S---MX
K-1=1 transitions usually absent
H2O---HX, H2O---XY and H2O---MX
K-1=1 transitions usually stronger than K-1=0
Intensity / μV

13. H2SMI (M=Cu, Ag, Au) H2OHX, XY or MX H2SHX, XY or MX
Low, narrow barrier
Rapid tunnelling
Effective C2v symmetry
H2SHX, XY or MX
High, wide barrier
No tunnelling
Cs Symmetry

14. H2SMI (M=Cu, Ag, Au)
In H2O complexes, protons are equivalent for a C2 rotation
Cooling from 110/111 to 101 forbidden
Higher effective rotational temperature
Protons not equivalent in H2S complexes
Collisions cool rotational states
Less population in K-1=1 levels

15. D2SMI (M=Cu, Ag, Au) K-1=0/K-1=1 separation H2SCuI D2SCuI
∆𝐸 ≈(𝐴−𝐵)ℎ
H2SCuI
A ≈ 150 GHz
D2SCuI
A ≈ 75 GHz
K-1=1 levels more populated in D2S complexes c.f H2S complexes

16. Molecular Geometry re = CCSD(T)(F12*)/cc-pVTZ+def2-QZVPP
H2S---63/65CuI HDS---63/65CuI D2S---63/65CuI
H2S---107/109AgI HDS---107/109AgI D2S---107/109AgI
H2S---AuI HDS---AuI D2S---AuI   
H2S···CuI
H2S···AgI
H2S···AuI r0
(exp.) re
r(MI) / Å
2.3603(83)
2.3668
2.5484(94)
[2.5220]
2.5203
r(MS) / Å
2.175(14)
2.1624
2.409(18)
(19)
2.3038
φ /  a
75.00(47)
74.513
78.43(76)
77.559
71.216(13)
72.951
re = CCSD(T)(F12*)/cc-pVTZ+def2-QZVPP

17. Acknowledgements
Newcastle University Nick Walker John Mullaney Dror Bittner Argonne National Laboratory Daniel Zaleski University of Bristol Tony Legon Colin Western