Dancing a waltz with C60 anions

Umesh R. Kadhane

Acknowledgement
TIFR, Mumbai: Lokesh C. Tribedi Deepankar Misra Yahspal singh, Aditya Kelkar, K. V. Thulasi Ram, Ajay Kumar University of Aarhus, Denmark: Steen Brndsted Nielsen Preben Hvelplund Jens Ulrik Andersen Kristian Stckhel Anne I. S. Holm Subhasis Panja Henning Zettergren Anneli Eheldrig Lund University, Sweeden: Sofia Canton University of Tennessee, USA: Robert N. Compton Goteborg University, Sweeden: Klavs Hansen Erika Sunden Universit de Montral, Canada: James S. Forster Univ. of New Hampshire, USA: Olaf Echt Universit Paris-Sud, France: Jaqueline Fayeton Michel Barat Bruno Lucas Marie Prot Christophe Jouvet

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Structure of C60

Few examples of Fullerenes:

http://www.photon.t.u-tokyo.ac.jp/~maruyama/fticr/fullerene.gif (Referred on 23rd Nov 2010)

Collective excitation in C60

Predicted by Bertsch et. al. (1991) Measured by Hertel et. al. (1992)

Frequency ~ 1015 Hz Energy ~ 20 eV

Interaction of fast moving heavy ions with C60

600 500 110 MeV S Ly
16+

on C60

110 MeV

Counts

S16+

+ C60

10-17 sec

S15+*

+ C60+*

400 300 200

S15+*

S15+ + hn (X-ray)

Ly
100 0 2.0 2.5 3.0

Ly
3.5 4.0

Energy (KeV)

Ly n=1
Projectile

Ly

I()/I()

n=3 n=2

0.6 0.5 0.4 0.3

16+

Target atomic number

U. Kadhane et al. Phys. Rev. Lett. 90, 093401 (2003) U. Kadhane et al. Nucl. Instrum. Methods Phys. Res. B 205, 661 (2003)

Influence of GDR excitation on C60 ionization

Xq+ + C60 C60*

Xq+ + C60* C60+ + e-

50 MeV O on C60
Relative Ionization Cross Sections of C 60
1+

q+

1.8 1.6 1.4 1.2 1.0 0.8 0.6 0.4 0.2 0.0

Projectile
4+

Relative Ionization Cross Sections of C60

Local Plasma Approx. calculations Plasmon Excitation model 1+ C60

50 MeV O on C60
0.10 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0.00 4 5 6 7 8

q+

Local Plasma Approx. calculations Plasmon Excitation model 4+ C60

Projectile Charge State

Projectile Charge State

U. Kadhane et al. Phys. Rev. A (Rap. Comm.) 75, 041201 (2007) U. Kadhane et al. Rad. Phys. Chem. 75, 2046 (2006)

Experimental development:

Design, planning and drawing of all the vacuum chambers. Planning, assembly and testing of Ultra High Vacuum system (10-8 torr in the main chamber and 10-9 torr in beam line.) Design, fabrication and testing of the mass spectrometer with the detectors. Processing electronics, data acquisition and analysis.

Possible application:
Ion thrusters

Excited state dynamics

1 0 System in ground state

1
0 Photo excited system

1
0 Electron capture

1 0 Unit 1

1 0 Unit 2

1
0 Coupled system

U. Kadhane et al. Phys. Rev. E 77, 021901 (2008) U. Kadhane et al. J. Photochem. Photobio. 197, 110 (2008)

Ion Storage

Storage rings

Ion traps

High energy (MeV and more)

Low energy (Few keVtens keV)

Various systems investigated

C60 and C602

ELISA :

Protoporphyrine IX
NC X X NC CN X X CN ESI NC X CN X

ELectrostatIc Storage ring for ions, Aarhus

Na

X TCNQ dianionsX NC CN

X = H: TCNQ X = F: TCNQ-F 4

protonated Tryptophan DNA building blocks

Doubly charged negative ions

OVER THE BARRIER ELECTRON TRANSFER

r ()
0 2 0 5 10 15 20

Ue (eV)

-2 -4 -6 -8
C60 60

Na Na+

Na ion Free electron + R=100 R=10 R=15 R=20 R=50 Na R=Rc=7.6

Formation of C60 dianion in vacuum.

Bo Liu et. al., Phys. Rev. Lett. 2004

Hckel molecular orbital diagram for C60

Hands et. al. Adv. Quant. Chem. 44, 335 (2003)

Spectroscopy of C60 dianios

Temperature control is essential!!!!!

S. Tomota et. al., J. Chem. Phys. 2006

Nielsen ion source

Ion source and 14 pole RF trap

RF trap schematic

-20V

20V

ELISA
Mirror

E* = E0 + hn
Laser Channeltron, detector for ions

Magnet
Injection 1m Detector for neutrals

Decay of excited molecule

Ion source Na cell

Counts

~100 s

-2 A+ CAB+ C60++B e 60

Detection of charged products after electron detachment

Channeltron detector

C60-

C60-2

Temperature measurement on C60 and C70 dianions

10
1

10

C60
Decay rate (a.u.)
10
-1

2-

C70

2-

10

-2

200 K RT

10

-3

370 K

10

-4

0.1

10

100

Time (ms)

Comparison at longer time scale

C70
10
1

2-

Beam current (a.u.)

10

C60

2-

225 K
10
-1

300 K
10
-2

318 K

355 K
10
-3

200

400

600

800

1000

Time (ms)

Spectroscopy of C60 dianions

14000 12000 10000

930 nm

6000

4000

2000

Counts

8000 6000 4000 2000

3.8

4.0

4.2

4.4

4.6

4.8

5.0

5.2

5.4

Time (ms)

Spectroscopy of C602- states

The similarity between solution based measurements indicate that the ground state is a Singlet due to strong JT coupling to quadrupole deformation.

U. Kadhane et al., J. Chem. Phys. 131, 014301(2009) Hase et. al. Chem. Phys. Lett. 326, 186 (2000)

Conclusion
Near-infrared absorption spectra of C60 dianions in the gas phase leads to electron loss by both direct electron tunneling into the continuum and statistical autodetachment after internal conversion. The Coulomb barrier is more than 1.5 eV. Consistent with the theoretically predicted value of 1.7 eV. The absorption spectra reveal the strong JT interaction in the dianions of C60, and the electronic ground state is determined to be singlet. There is evidence for interpretation of a broad high-energy band as transitions to states with positive JT energy stabilized by pseudorotations cone states, and we suggest a similar assignment for a high-energy absorption band in the monoanion.

As we climb new heights

We become more thoughtful!