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Ionic liquids

Polarity and Solvation in Ionic


Liquids
Prof. Tom Welton
Imperial College

Polarity
Polarity of a liquid is defined as:
The sum of all possible specific and nonspecific interactions between the solvent and
a potential solute, except for those that lead to
a chemical reaction

When you heat a salt it will melt (e.g.,


NaCl, 801C).
The melt is composed of mobile ions (ionic
liquid).

Ionic liquids
Ionic liquid solutions
Make cation-solute and/or anion solute
interactions
Break solute-solute and cation-anion
interactions

These include:
Coulombic, dipolar, inductive and dispersive
forces, hydrogen-bonding etc..

Polarity

Polarity

Solvent-solute interactions are how liquids


change the behaviours of solutes.

There is no available measure of polarity.


All polarity scales are estimates.

Polarity is understood in qualitative terms.


The test of a polarity scale is usefulness.
Good quantitative understandings have
proved elusive.

Polarity

There is no concept of right and wrong

Polarity

There is no simple relationship


between different measures of
polarity.

There is no simple relationship


between different measures of
polarity.

"Polarities"
20

dipole moment(x 10 exp 30 / C m)

18
16
14
12
10
8
6
4
2
0
0

50

100

150

200

250

dielectric constant

Ionic liquid polarity


Ionic liquids have only moderate r
liquid

PC
DMSO
Acetonitrile
Acetone
[emim][OTf]
[emim][N(Tf)2]
[bmim][OTf]
[bmim][N(Tf)2]
Dichloromethane
THF

64.92
46.45
35.94
20.56
15.1
12.3
13.2
11.6
8.93
7.58

Ionic liquid polarity


Ionic liquids have a wide range of dielectric constants.
Anion effect:
r is proportional to H-bond basicity
[HCO2]- > [C2OSO4]- [NO3]- >> [OTf]- > [BF4]- > [NTf2]- [PF6]-

Cation effect:
r is proportional to H-bond acidity
[(HO)C2NH3]+ > [C2NH3]+ > [CnCm im]+

Alkyl chain effect:


r is proportional to 1/chain length

Trends similar to those in molecular solvents

H. Weingrtner, Angew. Chem. Int. Ed., 2008, 47, 654.

Ionic liquid polarity


r assumes that a liquid is
smooth and isotropic.
ILs are heterogeneous on
the nanoscale.*
Emission spectra of 2amino-7-nitrofluorene shows
the dye molecules occupying
distinct non-exchanging
environments.**
* Jos N. A. Canongia Lopes; Aglio A. H. Pdua; J.
Phys. Chem. B 2006, 110, 3330-3335.
** Mandal, P.; Sarkar, M.; Samanta, A. J. Phys. Chem. A
2004, 108, 9048.

Ionic liquid polarity


r from dielectric spectroscopy fails to capture
the defining feature of ionic liquids the
translation of ions.
r from dielectric spectroscopy shows poor
agreement with:
Lack of kinetically active ion pairs in SN2 reactions
(see later).
Ionic association of Kosowers dye at equilibrium (see
later).

red/green (charged/nonpolar)

Ionic liquid polarity

Empirical Polarity Scales

r from dielectric spectroscopy shows good


agreement with:
These have no solvent reorganisation on
timescale of measurement.
r from speed of sound together with densities and
heats of vapourization.*
Emission spectra of pyrene and PRODAN.

Timescales are important

Empirical polarity scales are based upon


measurements of some solvent dependent
property(ies)
e.g. spectra, rates or selectivities of reactions.

The property is selected to:


Be sensitive to as many solvent-solute interactions as
possible;
Have a wide range, so that a reasonable resolution of
results can be achieved.

Multiparameter scales are more helpful.


*Singh, T.; Kumar, A. J. Phys. Chem. B, 2008, 112, 12968.
**Baker, S. N.; Baker, G. A.; Kane M. A.; Bright, F. V. J. Phys. Chem. B, 2001, 105, 9663

Kamlet-Taft dyes
NH2

Kamlet-Taft Parameters
Et

Et
N

NO2

Reichardt's dye

4-nitroaniline

a = the hydrogen bond acidity of the


solvent: {-0.186(10.91-nR)-0.72p*}
b = the hydrogen bond basicity of the
solvent: {(1.035nNN+2.64-nNA)/2.80}

O-

A. R. Katritsky et al., Chem. Rev. 2004, 104, 175-198

NO2

N,N-diethyl-4-nitroaniline

p* = dipolarity/polarizability etc.:
{0.314(27.52-nNN)}

Ionic liquid polarity

Ionic liquid polarity

Solvent

p*

Solvent

p*

[bmpy] [OTf]

1.017

0.396

0.461

[bmpy] [OTf]

1.017

0.396

0.461

[bmpy] [N(Tf)2]

0.954

0.427

0.252

[bmpy] [N(Tf)2]

0.954

0.427

0.252

[bmim] [OTf]

1.006

0.625

0.464

[bmim] [OTf]

1.006

0.625

0.464

[bmim] [N(Tf)2]

0.984

0.617

0.243

[bmim] [N(Tf)2]

0.984

0.617

0.243

Acetone

0.704

0.202

0.539

Acetone

0.704

0.202

0.539

Methanol

0.730

1.050

0.610

Methanol

0.730

1.050

0.610

Dichloromethane

0.791

0.042

-0.014

Dichloromethane

0.791

0.042

-0.014

DMSO

1.000

0.000

0.760

DMSO

1.000

0.000

0.760

L. Crowhurst, P. R. Mawdsley, J. M. Perez-Arlandis, P. A. Salter and T. Welton, PCCP., 2003, 5, 2790 - 2794

L. Crowhurst, P. R. Mawdsley, J. M. Perez-Arlandis, P. A. Salter and T. Welton, PCCP., 2003, 5, 2790 - 2794

Effect of the anions on a


The cation can H-bond to the anion

bmim + An

K1

bmim + solute

[bmpy] [OTf]

1.017

0.396

0.461

0.427

0.252

1.006

0.625

0.464

[bmim] [N(Tf)2]

0.984

0.617

0.243

Acetone

0.704

0.202

0.539

Methanol

0.730

1.050

0.610

[bmim ...solute]

Dichloromethane

0.791

0.042

-0.014

[bmim+][solute]

DMSO

1.000

0.000

0.760

bmim+..solute
K2 =

0.954

[bmim ][An ]
K2

p*

[bmpy] [N(Tf)2]

[bmim+...An-]

The cation can H-bond to the solute


+

Solvent

[bmim] [OTf]

bmim ...An
K1 =

Ionic liquid polarity

L. Crowhurst, P. R. Mawdsley, J. M. Perez-Arlandis, P. A. Salter and T. Welton, PCCP., 2003, 5, 2790 - 2794

Abraham model
The model is based on a theory of solvation that
describes the process in 3 steps
A cavity is generated in the solvent
The solvent reorganises around the cavity
The solute is introduced to the cavity and any solutesolvent interactions take place.

By studying a wide variety of solutes with known


properties a set of solvent parameters can be
generated.

The Abraham GC experiment


17 different ionic liquids, 8 from the same samples
used for the Kamlet-Taft experiment.
Prepared GC columns
Ran 36 probe solutes whose Abraham parameters are
known
Measured retention times at 40, 70 and 100 oC.
Multiple linear regression analysis was used to derive
the Abraham solvent parameters

Abraham Parameters
Log k = c+rR2+sp2H+aa2H+bb2H+l log L16
k = the property observed
c = constant
r = interactions with p- and n-electrons of the solute
s = dipolarity/polarizability
a = H-bond basicity
b = H-bond acidity
l = dispersion interactions

The Abraham parameters for


ionic liquids
a (hydrogen bond basicity) generally high and
depends mainly on anion.
b (hydrogen bond acidity) generally low and depends
on both cation and anion.
s (dipolarity/polarizability) values are high, showing
the influence of Coulombic interactions
s depends on both anion and cation, but no obvious
trend has been elucidated so far.
l (dispersion) nearly constant for all ionic liquids
studied

Do the Kamlet-Taft and Abraham


parameters agree?

Do the Kamlet-Taft and Abraham


parameters agree?

a and b are high in both models and depend mainly on the anion

b is low whereas a is high contradiction of the two scales


0.5
0.4

3.5

0.3

[N(Tf)2N]- ionic liquids

3
0.2

2.5

y = 3.7995x + 1.0823
R2 = 0.8578

[bmim]+ ionic liquids

0.1
0
0.25
-0.1

2
a
1.5
1

-0.2

0.5

-0.3

0.3

0.35

0.4

0.45

0.5

0.55

0.6

0.65

0.7

0.75

-0.4

0
0.2

0.25

0.3

0.35

0.4

0.45

0.5

-0.5

Ionic liquid polarity


Reichardts dye agrees with solvatochromism of
merocyanine dyes.

Ionic liquid polarity


Polarities derived from Reichardts dye agree
with:
Nucleophilic substitution reactions.

Byrne, R.; et al.. Phys. Chem. Chem. Phys. 2008, 10, 5919

Reichardts dye agrees with Kosowers z-scale.

Nu + CR3X

[NuCR3]+ + X-

Nu- + CR3X

NuCR3 + X-

Nu + [CR3X]+

[NuCR3]+ + X

Ionic liquid polarity

Empirical Polarity Scales

Polarities derived from Reichardts dye do not


agree with:
GC measurements
solvatochromism of Fe(phen)2(CN)2 (phen = 1, 10phenanthroline);
fluorescence spectra of PRODAN and coumarin 153
Raman spectra of diphenylcyclopropane

the derived values were lower, and the relative


effects of changing cations or anions were
different
All of these are neutral probes!

Hydrogen bonding in ionic


liquids
H

The second assumption does not always hold:


it is important to consider the nature of the solute as
well as the solvent.

The effect of transferring a solute from a


molecular solvent to an ionic liquid depends
upon the charge on the solute.
Ionic liquids have a greater effect on charged solutes
than neutral solutes.

manifold of
C-H * MOs
C

if the response of the probe solute is the same as that


in some known solvent, then the polarities of the two
solvents are the same.
the effect of transferring from one solvent to another
is the same for all probes.

Empirical Polarity Scales for


ionic liquids

Theoretical investigations have shown the


importance of the Coulombic component of the
hydrogen bond.
C

Assumptions

filled
Cl p-AO

Therefore:
polarity scales based upon charged solutes correlate
well with the behaviours of other charged solutes
polarity scales based upon neutral solutes to correlate
well with the behaviours of other neutral solutes

P. A. Hunt,* B. Kirchner, T. Welton, Chem. Eur. J., 2006, 12, 6762-6775.

Nucleophilic substitutions
Bimolecular nucleophilic substitutions
have been used historically to investigate
solvent effects on the rates of reactions.

E. D. Hughes and C. K. Ingold, J. Chem. Soc., 1935, 244-255.

Nucleophilic substitutions
Bimolecular nucleophilic substitutions
have been used historically to investigate
solvent effects on the rates of reactions.

E. D. Hughes and C. K. Ingold, J. Chem. Soc., 1935, 244-255.

Nucleophilic substitutions
We have investigated the reaction of various
nucleophiles with methyl p-nitrobenzenesulfonate.

Nucleophilic substitutions
It can be followed by u.v. spectroscopy under
pseudo-first order conditions to give kobs.
1.7

1.5

Nu:

Me O S

NO2

O
253 nm
O
NuMe

(+)

O S

NO2

O
275 nm

Absorbance/ Arbitrary Units

O
(-)

1.3

1.1

0.9

0.7

0.5

0.3

0.1
-0.1240

250

260

270

280

290

300

wavelength/ nm

N. L. Lancaster and T. Welton J. Org. Chem., 2004, 69, 5986; J. Am. Chem. Soc., 2004,
126, 11549; N. L. Lancaster, P. A. Salter, T. Welton and G. B. Young, J. Org. Chem., 2002,
67, 8855; L. Crowhurst, R. Falcone, N. L. Lancaster, V. Llopis-Mestre and T. Welton, J. Org.
Chem., 2006, 71, 8847-8853 .

The isosbestic point shows that it is a simple


A to B reaction

Nucleophilic substitutions in
ionic liquids

Nucleophilic substitutions
It can be followed by u.v. spectroscopy under
pseudo-first order conditions.

kobs

We have used Linear Solvation Energy


Relationships (LSERs) used to analyse
the rates of nucleophilic substitution
reactions:
lnk2 = c + aa + bb + sp*

[Nu] / mol dm-3

k2 is derived from the linear plot of kobs vs [Nu]

Nucleophilic substitutions in
ionic liquids
O

O
R3N +

Me

MeBu3N++ O2N

NO2

O-

X- + Me

LSER

R2

BuNH2 lnk2 = -8.77 + 4.57b + 6.32p* 0.93


Bu2NH lnk2 = -8.57 + 2.23b + 7.30p* 0.92
Bu3N lnk2 = 0.87 - 2.56a + 12.80p* 0.70
(solvents used: [bmim][Tf2N], [bmpy][Tf2N], [bmpy][TfO], DCM, MeCN)

The change in the rate of the reaction is controlled by both


hydrogen bonding effects and generalised polarity effects.

MeBr + O2N

NO2

O-

R3N

Nucleophilic substitutions in
ionic liquids
O
O
X-

LSER

R2

ClBrI-

lnk2 = 0.21 - 7.56a


lnk2 = 0.87 - 5.83a
lnk2 = 0.87 - 3.05a + 1.16b

0.99
0.97
0.95

(solvents used: [bmim][Tf2N], [bmpy][Tf2N], [bmpy][TfO], DMSO, DCM, MeOH)

The change in the rate of the reaction is


dominated by specific hydrogen bonding effects.

10

Nucleophilic substitutions in
ionic liquids
H3C

H3C

R3N +

Nucleophilic substitutions in
ionic liquids

[CH3NR3]+

NO2

H3C

Cl- +

NO2

CH3Cl +

NO2

H3C

H3C

R3N

R2

LSER

NO2

R2
0.99

LSER
lnk2 = -2.74 6.54a

Cl-

BuNH2 lnk2 = -2.38 - 3.59a - 4.16b + 2.10p* 0.96


Bu2NH lnk2 = -2.66 - 2.79a - 5.01b + 2.89p* 0.99
Bu3N
lnk2 = -5.62 - 6.46b + 4.26p*
0.87

S
H3C

([bmim][Tf2N], [bm2im][Tf2N], [bmpy][Tf2N], [bmim][TfO], [bmpy][TfO], [Hbim][TfO])

(solvents used: [bmim][Tf2N], [bmpy][Tf2N], [bmim][TfO], [bmpy][TfO], DCM,


MeCN, THF, MeOH)

Only ionic liquids appear in the LSER, because it is only in


ionic liquids that k2 can be derived.

The change in the rate of the reaction is controlled by both


hydrogen bonding effects and generalised polarity effects.

In molecular solvents the


reaction is not second order

Nucleophilic substitutions
[bm 2im+][Cl-] + [S+][NTf2-] in [bm2im][NTf2]

H3C
Cl- +

0.00025

CH3Cl +

NO2

0.0002

0.06

0.00015

0.05

0.0001
0.00005

THF
DCM
Propylene Carbonate
CH3CN

0.05

0.07

-1

K2 = 0.00363

0.03
0.02

0
0

0.01

0.02

0.03

0.04

0.06

[Cl ] (M)

k2 is derived from the linear plot of kobs vs [Nu]

0.01
0
0

NO2

H3C

0.04

M-1S-1

kobs (s )

kobs (s-1)

H3C

0.1

0.2
-

[Cl ] (M)

0.3

0.4

No reaction:
water
methanol
Negative order:
acetone
THF
DCM
Positive but not second order:
Propylene carbonate
Acetonitrile
DMSO
Second order:
Ionic liquids

11

In molecular solvents the


mechanism is via ion pairs

H3C

H3C
Cl- +

In molecular solvents the


mechanism is via ion pairs

CH3Cl +

NO2

DMSO
Acetonitrile
Propylene carbonate

H3C
S+

[R4N][Cl] + [S+][NTf2]

NO2

H3C
S

[R4N][NTf2] + [S+][Cl]
fast
metathesis

[S+][Cl]
+
[R4N][Cl]

slow
substitution

CH3Cl + S

Ionic liquids are highly dissociating


solvents.
{[A]+[B]-}
ionisation
molecule

CH3Cl +

NO2

acetone
THF
DCM

H3C
+

[R4N][Cl] + [S+][NTf2]

NO2

H3C
S

[R4N][NTf2] + [S+][Cl]

fast
metathesis

precipitation

The ionic liquid effect

A-B

Cl- +

ion pair

dissociation
association

[A]+ + [B]free solvated ions

Ion pairing is dominated by Coulombic


interactions and is usually highly
correlated with dielectric constants.

[S ][Cl]
+
[R4N][Cl]

CH3Cl + S

slow
substitution

Ionic liquid polarity


Ionic liquids are far more dissociating than expected
from :
liquid

PC
DMSO
Acetonitrile
Acetone
[emim][OTf]
[emim][N(Tf)2]
[bmim][OTf]
[bmim][N(Tf)2]
Dichloromethane
THF

64.92
46.45
35.94
20.56
15.1
12.3
13.2
11.6
8.93
7.58

H. Weingrtner, Angew. Chem. Int. Ed., 2008, 47, 654.

12

In molecular solvents the


reaction is not second order
H3C
Cl- +

CH3Cl +

NO2

H3C

NO2

H3C

0.06
0.05

THF
DCM
Propylene Carbonate
CH3CN

-1

kobs (s )

0.04
0.03
0.02
0.01
0
0

0.1

0.2

0.3

0.4

[Cl ] (M)

No reaction:
water
methanol
Negative order:
acetone
THF
DCM
Positive but not second order:
Propylene carbonate
Acetonitrile
DMSO
Second order:
Ionic liquids

Ion pairs
Solvent shared
(loose) ion pair

When you heat a salt it will melt (e.g.,


NaCl, 801C).
The melt is composed of mobile ions (ionic
liquid).

The ionic liquid effect

In a molecular solvent:
Solvent separated
ion pair

Ionic liquids

Contact (tight) ion


pair

Ionic liquids are super dissociating


solvents.
+
_

+
_

+
+ _
_
+
+ _
_

In an ionic liquid all ions are surrounded by


other ions.

+
_
+
_

+
_

+ _

_
+

+
_

+
+

+
_

Decreasing Ion Separation

_
+

+
_

+
_

_
+
_

+
_

+
_

+
_
+
_

_
+
_

+
_

_ +

+ _
_

+
+ _

+
+
_
+ _
+
+ _
_
_
_
+
+
+
+
_
_ +
+ _ + _
_
_
_
+
+
+
+
_
_
+ _
+ _
+
_
_
+
+
+ _
+
+
_

_ +
_
+
+
+ _ + _
_ + _
_
+
+
_ + _ + _
_ + _
_
+
+
_
+ _
+ _
_
+ _
+ _ +
_ + _ + _
_
+ _ + _ +
_
_
_
+
+
_
_ +
+
+
_
+ _ +
_

+ _
_ +

+
_

+
_

13

Charge screening of ion pairs in


ionic liquids (MD simulation)

Ionic liquid polarity


Ionic liquids are super dissociating
solvents.

9 100% screening

Ion pairing in molecular solvents is dominated


by Coulombic interactions.
In an ionic liquid there is little difference
between these of the solute-solute and of the
solute-solvent interactions (highly screened).
Ion contacts that do form are rapidly disrupted
by the constant motion of the ions of the
solution (both solute and solvent).

3 55% screening

R. M. Lynden-Bell, Phys. Chem. Chem. Phys., 2010, 12, 1733.

Kosowers Dye

Kosowers Dye

1-butanol
3

2.5

2.5

Absorbance

Absorbance

MeCN
3

1.5
1
0.5

2
1.5
1
0.5

0
300

320

340

360

380

400

420

Wavelength / nm

440

460

480

500

300

320

340

360

380

400

420

440

460

480

500

Wavelength / nm

14

Kosowers Dye

Kosowers Z-scale
First comprehensive polarity scale
solvents using a solvatochromic dye.
Z-values of selective solvents

[C4C1im]NTf2
3

Liquid

Liquid

Water

94.6

MeCN

71.3

Methanol

83.6

DMSO

71.1

Ethanol

79.6

Acetone

65.5

[bmim][OTf]

76.0

DCM

64.7

0.5

[bmim][NTf2]

74.3

Ethyl acetate

59.4

[bmpy][NTf2]

73.3

Benzene

54.0

Absorbance

2.5
2
1.5

300

400

500

Wavelength / nm

Kosowers Dye

Kosowers dye

Z correlates well with ETN for both ionic


liquids and molecular solvents.

For the spectrum to be seen some [py]+


and I- ions must be in contact.

1
0.9
0.8
0.7

E TN

0.6
0.5
0.4
0.3
0.2
0.1
0
50

55

60

65

70

75

80

85

90

95

100

15

Kosowers Dye Absorbance

Kosowers Dye Absorbance

1-butanol

MeCN
30
20
25
Absorbance/Pathlength (cm-1)

Absorbance/Pathlength (cm-1)

18
16
14
12
10
8
6

20

15

10

4
2

0
0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.005

0.01

0.015

0.02

0.025

0.03

0.035

0.04

0.045

0.05

Concentration / M

Concentration / M

Kosowers Dye Absorbance

Kosowers Dye

[C4C1im]NTf2

[C4C1im]OTf

30

20
18
Absorbance/Pathlength (cm-1)

Absorbance/Pathlength (cm-1)

25

20

15

10

16
14
12
10
8
6
4
2

0
0

0.02

0.04

0.06

0.08

0.1
Concentration / M

0.12

0.14

0.16

0.18

0.2

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

Concentration / M

16

Kosowers Dye Equilibrium


Model

Beer-Lambert Law
A = cl

Consider the simple equilibrium of ion


association:

= molar absorptivity (constant)


c = concentration
l = path length

Non-linear A vs c indicates that there is an


equilibrium.

the following equilibrium model was


derived:
CIP = (CT - 0.5/K) 0.5*SQRT{4*CT/K + 1/(K2)}

Kosowers Dye

1400

1400

1200

1200

1000

1000

800

K=1000
K=100
K=50

600

K=10
K=1

400

200

Extinction coefficient

Extinction coefficient

Kosowers Dye Equilibrium


Model

800
DCE
1-butanol

600

MeCN
400

200

0
0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

Concentration, M

0.04

0.045

0.05

0.005

0.01

0.015

0.02

0.025

0.03

0.035

0.04

0.045

0.05

Concentration / M

= A/cTl
CIP = (CT - 0.5/K) 0.5*SQRT{4*CT/K + 1/(K2)}

17

Kosowers Dye in ionic liquids

Kosowers Dye in ionic liquids

140

160

140

120
y = 681.33x + 5.8247

120

100

y = 592.94x + 5.5254
80
[bmim]BF4

60

[bmim]OTf

40

Extinction
coeffcient

Extinction coefficient

100

80
[bmpy]NTf2
[bmim]NTf2

60

40

20

20

0
0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

Concentration / M

Concentration / M

Kosowers Dye

What is the reaction?


This is a metathesis reaction.

60
55
50

Extinction coefficient

45
40
35
30
K=1

25
20
15
10
5
0
0

0.005

0.01

0.015

0.02

0.025

0.03

0.035

0.04

0.045

concentration, M

K=1
G = -RTlnK = 0

18

Kosowers Dye Equilibrium


Model

Kosowers Dye Equilibrium


Model
Two energies per complex Energy of metathesis not unambiguous
AVR: calculated from the average energy per complex
MIN: calculated from the lowest energy per complex
MAX: calculated from the highest energy per complex

Simplest possible model for metathesis

Two lowest energy structures for each complex on B3LYP/6-31++G(d,p)


level of theory with small core ECP for iodide
Singlepoint calculations using zero-point energy (+Z) and basis set
superposition error (+B) correction on B3LYP level
Singlepoint MP2 energies on B3LYP geometry

AVR
MIN
MAX

DFT
22.13
23.09
21.16

DFT+Z
19.60
18.37
20.83

DFT+Z+B
20.02
18.40
21.64

MP2
3.95
-2.83
10.73

MP2+Z
1.42
-4.90
7.75

On highest level of theory: Metathesis energy neutral within simple model


system

Ion solvation
All ions are randomly associated
Dynamic system prevents long-lived ion
contacts
There are no special ion pairs in solutions
of Kosowers dye in ionic liquids.

Acknowledgements

Dr Patricia Hunt (theory)


Dr Lorna Crowhurst (polarity)
Dr Jason P. Hallett (kinetics)
Dr Patricia Hunt (theory)
Dr Juan Perez-Arlandis (polarity and kinetics)
Dr Guiseppe Ranieri (kinetics)
Mr Matthew Lui (polarity)
Mr Heiko Niedermeyer (theory)

Leverhulme Trust, Kodak Foundation, EPSRC, ERC


(funding)

19