Solvation of Cs+ ions inside helium droplets has been investigated both experimentally and theoretically. On the one hand, mass spectra of doped helium clusters ionized with a crossed electron beam, HeNCs+, have been recorded for sizes up to N = 60. The analysis of the ratio between the observed peaks for each size N reveals evidences of the closure of the first solvation shell when 17 He atoms surround the alkali ion. On the other hand, we have obtained energies and geometrical structures of the title clusters by means of basin-hopping, diffusion Monte Carlo (DMC), and path integral Monte Carlo (PIMC) methods. The analytical He–Cs+ interaction potential employed in our calculations is represented by the improved Lennard-Jones expression optimized on high level ab initio energies. The weakness of the existing interaction between helium and Cs+ in comparison with some other alkali ions such as Li+ is found to play a crucial role. Our theoretical findings confirm that the first solvation layer is completed at N = 17 and both evaporation and second difference energies obtained with the PIMC calculation seem to reproduce a feature observed at N = 12 for the experimental ion abundance. The analysis of the DMC probability distributions reveals the important contribution from the icosahedral structure to the overall configuration for He12Cs+.

1.
M.
Hartmann
,
R. E.
Miller
,
J. P.
Toennies
, and
A. F.
Vilesov
,
Science
272
,
1631
(
1996
).
2.
J. P.
Toennies
and
A. F.
Vilesov
,
Annu. Rev. Phys. Chem.
49
,
1
(
1998
).
3.
S.
Yang
and
A. M.
Ellis
,
Chem. Soc. Rev.
42
,
472
(
2013
).
4.
C.
Callegari
,
K. K.
Lehmann
,
R.
Schmied
, and
G.
Scoles
,
J. Chem. Phys.
115
,
10090
(
2001
).
5.
F.
Stienkemeier
and
K. K.
Lehmann
,
J. Phys. B: At., Mol. Opt. Phys.
39
,
R127
(
2006
).
6.
M. Y.
Choi
,
G. E.
Douberly
,
T. M.
Falconer
,
W. K.
Lewis
,
C. M.
Lindsay
,
J. M.
Merritt
,
P. L.
Stiles
, and
R. E.
Miller
,
Int. Rev. Phys. Chem.
25
,
15
(
2006
).
7.
K.
Szalewicz
,
Int. Rev. Phys. Chem.
27
,
273
(
2008
).
8.
E.
Coccia
,
E.
Bodo
,
F.
Marinetti
,
F. A.
Gianturco
,
E.
Yildrim
,
M.
Yurtsever
, and
E.
Yurtsever
,
J. Chem. Phys.
126
,
124319
(
2007
).
9.
L.
An der Lan
,
P.
Bartl
,
C.
Leidlmair
,
R.
Jochum
,
S.
Denifl
,
O.
Echt
, and
P.
Scheier
,
Chem. - Eur. J.
18
,
4411
(
2012
).
10.
P.
Bartl
,
C.
Leidlmair
,
S.
Denifl
,
P.
Scheier
, and
O.
Echt
,
J. Phys. Chem. A
118
,
8050
(
2013
).
11.
C.
Di Paola
,
F.
Sebastianelli
,
E.
Bodo
,
I.
Baccarelli
, and
F. A.
Gianturco
,
J. Chem. Theory Comput.
1
,
1045
(
2005
).
12.
D. E.
Galli
,
M.
Buzzacchi
, and
L.
Reatto
,
J. Chem. Phys.
115
,
10239
(
2001
).
13.
N.
Issaoui
,
K.
Abdessalem
,
H.
Ghalla
,
S. J.
Yaghmour
,
F.
Calvo
, and
B.
Oujia
,
J. Chem. Phys.
141
,
174316
(
2014
).
14.
J. H.
Kim
,
D. S.
Peterka
,
C. C.
Wang
, and
D. M.
Neumark
,
J. Chem. Phys.
124
,
214301
(
2006
).
15.
A.
Nakayama
and
K.
Yamashita
,
J. Chem. Phys.
112
,
10966
(
2000
).
16.
A.
Nakayama
and
K.
Yamashita
,
J. Chem. Phys.
114
,
780
(
2001
).
17.
J. V.
Pototschnig
,
F.
Lackner
,
A. W.
Hauser
, and
W. E.
Ernst
,
Phys. Chem. Chem. Phys.
19
,
14718
(
2017
).
18.
F.
Sebastianelli
,
E.
Bodo
,
I.
Baccarelli
,
C.
Di Paola
,
F. A.
Gianturco
, and
M.
Yurtsever
,
Comput. Mater. Sci.
35
,
261
(
2006
).
19.
M.
Theisen
,
F.
Lackner
, and
W. E.
Ernst
,
Phys. Chem. Chem. Phys.
12
,
14861
(
2010
).
20.
M.
Theisen
,
F.
Lackner
, and
W. E.
Ernst
,
J. Chem. Phys.
135
,
074306
(
2011
).
21.
J.
Tiggesbaumker
and
F.
Stienkemeier
,
Phys. Chem. Chem. Phys.
9
,
4748
(
2007
).
22.
E.
Yurtsever
,
E.
Yildirim
,
M.
Yurtsever
,
E.
Bodo
, and
F. A.
Gianturco
,
Eur. Phys. J. D
43
,
105
(
2007
).
23.
A.
Mauracher
,
O.
Echt
,
A. M.
Ellis
,
S.
Yang
,
D. K.
Bohme
,
J.
Postler
,
S.
Kaiser
,
S.
Denifl
, and
P.
Scheier
,
Phys. Rep.
751
,
1
(
2018
).
24.
M.
Mudrich
and
F.
Stienkemeier
,
Int. Rev. Phys. Chem.
33
,
301
(
2014
).
25.
S.
Müller
,
M.
Mudrich
, and
F.
Stienkemeier
,
J. Chem. Phys.
131
,
044319
(
2009
).
26.
M.
Rossi
,
M.
Verona
,
D. E.
Galli
, and
L.
Reatto
,
Phys. Rev. B
69
,
212510
(
2004
).
27.
F.
Marinetti
,
E.
Coccia
,
F. A.
Gianturco
,
E.
Yurtsever
,
M.
Yurtsever
, and
E.
Yildirim
,
Theor. Chem. Acc.
118
,
53
(
2007
).
28.
M.
Buzzacchi
,
D. E.
Galli
, and
L.
Reatto
,
Phys. Rev. B
64
,
094512
(
2001
).
29.
D. E.
Galli
,
D. M.
Ceperley
, and
L.
Reatto
,
J. Phys. Chem. A
115
,
7300
(
2011
).
30.
L.
Kranabetter
,
M.
Goulart
,
A.
Aleem
,
T.
Kurzthaler
,
M.
Kuhn
,
E.
Barwa
,
M.
Renzler
,
L.
Grubweiser
,
M.
Schwärzler
,
A.
Kaiser
 et al,
J. Phys. Chem. C
121
,
10887
(
2017
).
31.
M.
Rastogi
,
C.
Leidlmair
,
L.
An der Lan
,
J.
Ortiz de Zárate
,
R.
Pérez de Tudela
,
M.
Bartolomei
,
M. I.
Hernández
,
J.
Campos-Martínez
,
T.
González-Lezana
,
J.
Hernández-Rojas
 et al,
Phys. Chem. Chem. Phys.
20
,
25569
(
2018
).
32.
L. F.
Gomez
,
E.
Loginov
,
R.
Sliter
, and
A. F.
Vilesov
,
J. Chem. Phys.
135
,
154201
(
2011
).
33.
L.
An der Lan
,
P.
Bartl
,
C.
Leidlmair
,
H.
Schöbel
,
R.
Jochum
,
S.
Denifl
,
T. D.
Märk
,
A. M.
Ellis
, and
P.
Scheier
,
J. Chem. Phys.
135
,
044309
(
2011
).
34.
S.
Ralser
,
J.
Postler
,
M.
Harnisch
,
A. M.
Ellis
, and
P.
Scheier
,
Int. J. Mass Spectrom.
379
,
194
(
2015
).
35.
R. A.
Aziz
and
M. J.
Slaman
,
J. Chem. Phys.
94
,
8047
(
1991
).
36.
R. A.
Kendall
,
T. H.
Dunning
, and
R. J.
Harrison
,
J. Chem. Phys.
96
,
6796
(
1992
).
37.
F.
Weigend
,
Phys. Chem. Chem. Phys.
8
,
1057
(
2006
).
38.
H. J.
Werner
,
P. J.
Knowles
,
R.
Lindh
,
F. R.
Manby
,
M.
Schütz
 et al, molpro, version 2012.1, a package of ab initio programs,
2012
, see http://www.molpro.net/.
39.
F.
Pirani
,
S.
Brizi
,
L.
Roncaratti
,
P.
Casavecchia
,
D.
Cappelletti
, and
F.
Vecchiocattivi
,
Phys. Chem. Chem. Phys.
10
,
5489
(
2008
).
40.
D. J.
Wales
and
J. P. K.
Doye
,
J. Phys. Chem. A
101
,
5111
(
1997
).
41.
Z.
Li
and
H. A.
Scheraga
,
Proc. Natl. Acad. Sci. U. S. A
84
,
6611
(
1987
).
42.
J.
Hernández-Rojas
,
F.
Calvo
,
J.
Bretón
, and
J.
Gomez Llorente
,
J. Phys. Chem. C
116
,
17019
(
2012
).
43.
S.
Acosta-Gutiérrez
,
J.
Bretón
,
J.
Hernández-Rojas
, and
J. J.
Gomez Llorente
,
J. Chem. Phys.
137
,
074306
(
2012
).
44.
J.
Hernández-Rojas
,
J.
Bretón
,
J. M.
Gomez Llorente
, and
D. J.
Wales
,
J. Phys. Chem. B
110
,
13357
(
2006
).
45.
J. P. K.
Doye
and
D. J.
Wales
,
Phys. Rev. B
59
,
2292
(
1999
).
46.
J.
Hernández-Rojas
and
D. J.
Wales
,
J. Chem. Phys.
119
,
7800
(
2003
).
47.
T.
James
,
D. J.
Wales
, and
J.
Hernández-Rojas
,
Chem. Phys. Lett.
415
,
302
(
2005
).
48.
J.
Hernández-Rojas
,
J.
Bretón
,
J. M.
Gomez Llorente
, and
D. J.
Wales
,
J. Chem. Phys.
121
,
12315
(
2004
).
49.
J.
Hernández-Rojas
,
F.
Calvo
,
F.
Rabilloud
,
J.
Bretón
, and
J. M.
Gomez Llorente
,
J. Phys. Chem. A
114
,
7267
(
2010
).
50.
D. J.
Wales
,
Energy Landscapes
(
Cambridge University Press
,
Cambridge
,
2003
).
51.
R.
Rodríguez-Cantano
,
R.
Pérez de Tudela
,
M.
Bartolomei
,
M. I.
Hernández
,
J.
Campos-Martínez
,
T.
González-Lezana
,
P.
Villarreal
,
J.
Hernández-Rojas
, and
J.
Bretón
,
J. Chem. Phys.
143
,
224306
(
2015
).
52.
M.
Bartolomei
,
R.
Pérez de Tudela
,
K.
Arteaga
,
T.
González-Lezana
,
M. I.
Hernández
,
J.
Campos-Martínez
,
P.
Villarreal
,
J.
Hernández-Rojas
,
J.
Bretón
, and
F.
Pirani
,
Phys. Chem. Chem. Phys.
19
,
26358
(
2017
).
53.
V.
Buch
,
J. Chem. Phys.
97
,
726
(
1992
).
54.
P.
Sandler
and
V.
Buch
, Prog. QCLUSTER, private communication,
1999
, Vol. 5.
55.
R.
Rodríguez-Cantano
,
T.
González-Lezana
,
P.
Villarreal
,
D.
López-Durán
,
F. A.
Gianturco
, and
G.
Delgado-Barrio
,
Int. J. Quantum Chem.
114
,
1318
(
2014
).
56.
R.
Rodríguez-Cantano
,
T.
González-Lezana
,
P.
Villarreal
, and
F. A.
Gianturco
,
J. Chem. Phys.
142
,
104303
(
2015
).
57.
R.
Rodríguez-Cantano
,
T.
González-Lezana
, and
P.
Villarreal
,
Int. Rev. Phys. Chem.
35
,
37
(
2016
).
58.
R.
Rodríguez-Cantano
,
M.
Bartolomei
,
M. I.
Hernández
,
J.
Campos-Martínez
,
T.
González-Lezana
,
P.
Villarreal
,
R.
Pérez de Tudela
,
F.
Pirani
,
J.
Hernández-Rojas
, and
J.
Bretón
,
J. Chem. Phys.
146
,
034302
(
2017
).
59.
M. F.
Herman
,
E. J.
Bruskin
, and
B. J.
Berne
,
J. Chem. Phys.
76
,
5150
(
1982
).
60.
K. R.
Glaesemann
and
L. E.
Fried
,
J. Chem. Phys.
116
,
5951
(
2002
).
61.
F.
Calvo
,
J. Phys. Chem. A
119
,
5959
(
2015
).
62.
M.
Sprik
,
M. L.
Klein
, and
D.
Chandler
,
Phys. Rev. B
31
,
4234
(
1985
).
63.
U.
Boesl
,
Mass Spectrom. Rev.
36
,
86
(
2017
).
64.
D.
Mateo
and
J.
Eloranta
,
J. Phys. Chem. A
118
,
6407
(
2014
).
65.
J. I.
Martínez
and
J. A.
Alonso
,
Phys. Chem. Chem. Phys.
20
,
27368
(
2018
).
You do not currently have access to this content.