AgI and H 2 O AgI produced by laser ablation John Mullaney Ɨ Chris Medcraft Ɨ Nick Walker Ɨ Anthony Legon ǂ Ɨ Newcastle University ǂ University of Bristol ID: 637321
Download Presentation The PPT/PDF document "Microwave spectra of Ar ..." is the property of its rightful owner. Permission is granted to download and print the materials on this web site for personal, non-commercial use only, and to display it on your personal computer provided you do not modify the materials and that you retain all copyright notices contained in the materials. By downloading content from our website, you accept the terms of this agreement.
Slide1
Microwave spectra of Ar...AgI and H2O...AgI produced by laser ablation
John MullaneyƗChris MedcraftƗ, Nick WalkerƗ, Anthony LegonǂƗNewcastle UniversityǂUniversity of BristolSlide2
X
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
C. J. Evans and M. C. L. Gerry,
J. Chem. Phys.,
112
, 2000, 1321-1329Slide3
Sample preparationTarget rods prepared from compressed AgI and imidazole powdersLaser ablation with Nd:YAG laser (532 nm, ~ 20 mJ/pulse)Rod constantly rotated and translatedSupersonic expansion
Water reservoirSlide4
Chirped-pulse Fourier transform microwave spectrometer (CP-FTMW)D. P. Zaleski et al., Phys. Chem. Chem. Phys., 16, 2014, 25221
Vacuum chamberSlide5
485k FIDsSlide6
Ar...107AgI
Ar
...109
AgI
B
0
/MHz
541.42280(10)
540.71464(10)
D
J
/ kHz
0.05773(24)
0.05686(23)
aa
(I)/MHz
-985.411(54)
-985.30(14)
σ
RMS
/kHz
7.1
6.7N6866
Ar...107AgI Ar...109AgI B0/MHz541.42280(10)540.71464(10)DJ/ kHz0.05773(24)0.05686(23)-985.411(54) -985.30(14) σRMS/kHz7.16.7N6866
r
0
(Ag-I)2.6759 Å
r
0
(Ag
...
Ar)
2.5356 ÅSlide7
Ar
...AgF
Ar
...
AgCl
Ar
...
AgBr
Ar
...
AgI
r
0
(Ag
...
Ar) / Å
2.5581
a
2.6124(4)
a
2.6366(6)
a2.6759r0(Ag-X) / Å 1.9861a2.2683(4)a
2.3825(4)a2.5356De / kJmol-1 b 21.819.318.016.7Ionicity, ic-0.6860.6380.570F22 / N m-129.3(2)25.8(2)23.5(6)
20.2(8)
a
C. J. Evans and M. C. L. Gerry, J. Chem. Phys., 112, 2000, 1321-1329b Calculated at CCSD(T)(F12c)/cc-pVTZ-F12 level of theory
D. M. Bittner
et al.
,
J. Chem. Phys., 114, 2016, 074308
i
c
= 1 +
h =
F11 = FAg-XF22 = FAr-AgSlide8
109AgI107AgI
109AgI...Ar107AgI...
Ar109AgI...
H2
O
107
AgI
...
H2OFrequency / MHz
H
2
O
...109
AgI
H
2
O
...107
AgISlide9
H
2O...107AgI
HDO
...107
AgI
H
2
18
O
...107
AgI
(1/2)(B
0
+
C
0
)
/ MHz
845.09861(14)
824.45945(19)
814.80179(36)
DJ/ Hz0.07072(79)0.0679(10)
0.0649(17)DJK / kHz8.642(91)-8.80(17)aa(I)/ MHz-885.54(11)-885.08(24)-884.24(49)- (I)/ MHz-12.73(28) --13.6(13)σRMS
/ kHz
5.5
5.3
9.6
N
75
28
40
H
2
O
...107AgI HDO...107AgI H218O...107AgI (1/2)(B0 + C0)/ MHz
845.09861(14)
824.45945(19)
814.80179(36)
D
J
/ Hz
0.07072(79)
0.0679(10)
0.0649(17)
D
JK
/ kHz
8.642(91)
-
8.80(17)
-885.54(11)
-885.08(24)
-884.24(49)
-12.73(28)
--13.6(13)σRMS/ kHz5.55.39.6N752840
H2O...109AgI HDO...109AgI H218O...109AgI (1/2)(B0 + C0)/MHz841.64807(14)821.26461(30)811.74276(65)DJ/ Hz0.07111(77)0.07090(16)0.0593(28)DJK / kHz8.626(87)-8.69(19)aa(I)/MHz-885.33(10)-884.42(41)-885.10(71)- (I)/MHz-12.79(25)--13.2(17)σRMS/kHz5.17.59.3N682627
H
2
O
...109
AgI
HDO
...109
AgI
H
2
18
O
...109
AgI
(1/2)(B
0
+
C
0
)
/MHz
841.64807(14)
821.26461(30)
811.74276(65)
D
J
/ Hz
0.07111(77)
0.07090(16)
0.0593(28)
D
JK
/ kHz
8.626(87)
-
8.69(19)
-885.33(10)
-884.42(41)
-885.10(71)
-12.79(25)
-
-13.2(17)
σ
RMS
/kHz
5.1
7.5
9.3
N
68
26
27Slide10
𝝋
H
2
O
...
AgI
r
0
(Ag
...
O) / Å
2.227(7)
r
0
(Ag-X) / Å
2.536(3)
𝝋
/
o
36.3(12)
H
2O...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, 014307b S. L. Stephens et al., J. Chem. Phys., 134, 2011, 134305Slide11
AcknowledgementsNewcastle UniversityNick WalkerChris MedcraftEva GougoulaUniversity of Bristol
Tony LegonDavid TewUniversity of ValladolidSusana Blanco