1D Chains of [Pt(CN)4]2-

The naked 1D [Pt(CN)4]2- chain (left)

shows unique electrical behavior
compared to a similar chain
coordinated by macrocyclic ligands.

1
 Metal-Semiconductor Transition
Peierls Distortion and Charge Density Waves

Rudolf Peierls

Peierls
Energy
Gap
EF

2
 Charge Density Waves and the Peierls Transition

Left: when the electron and the phonon systems are not coupled - ions are equally spaced and the charge
density - represented by the red line - is uniform
Right: when the electron and phonon systems are allowed to interact, this leads to a static lattice deformation
and periodically modulated charge density
This distortion is called the Peierls instability. The temperature at which this transition takes place is called the 3
Peierls temperature (TP).
 Krogmann’s Salt: K2Pt(CN)4·nH2O

• 1D chain of d8 square planar Pt(II) complexes

2- dPt–Pt
NC CN
Pt
NC CN

• s  5x10-7 -1 cm-1

• dPt–Pt is sensitive to cation size and number of
water molecules of crystallization (n)
– dPt–Pt ranges from 3.1 to 3.6 Å
• Slightly staggered (almost eclipsed) conformation

4
 Synthesizing Krogmann’s Salt: K2Pt(CN)4·3H2O
2-
N

Pt(NO3)2(aq) + 4 KCN 2 K+ N Pt N
+ KNO3

• [Pt(CN)42-]n 1D chain
• Almost eclipsed conformation of Pt(CN)42-
• dPt–Pt 3.48 Å suggests M–M bonding
(metallic Pt–Pt = 2.77 Å), but is insulating
N
C
K 5
Pt
 Chemical Oxidation of Krogmann’s Salt
Br2
K2Pt(CN)4·3H2O K2Pt(CN)4Br0.3·3H2O

Br
K
N
C
P

• Pt(CN)42- are now staggered by 45° – Why???

• Pt–Pt distance shrinks to 2.88 Å (metallic Pt–Pt = 2.77 Å)
6
• Compound is a good conductor (s = 200 -1 cm-1).
Structure of K2Pt(CN)4Cl0.32·3H2O

• K and Cl ions located in

between the Pt chains space
filling
• dPt–Pt varies by up to 0.6 Å
with different cations

7
 Molecules to Materials, Orbitals to Bands:
Structure, Optical, and Electrical Properties of K2Pt(CN)4

px,y
• Electric dipole-allowed optical transition 5dz2
(n+1)p
pz  6pz
dx2-y2
• Electrons filled up to 5dz2
1 2
(n+1)s
dz2

nd dyz,xz,xy Four lone pairs from four cyanide ligands

Ni or Pt 4L

L
L Pt L d8 square planar Pt(II) complex 8
L
Consider Two MX4 Molecules in Eclipsed Conformation:

L L
σ-bonding π-bonding
L L
Pt Pt
L L pz pz
dxz,yz dxz,yz
L L

s(pz)
dz2 dz2 dxy,x2-y2 dxy,x2-y2
d
Observed electronic structure:
• wide, empty pz σ-band
• wide, filled dz2 σ-band
s(dz2) • narrow, filled dxy,xz,yz and dx2-y2 bands
Orbital symmetry and overlap controls:
p
• band width and band gap
d • controls M–M distance
Band filling-width controls conductivity 9
 Polarizing Filter y
x

y E = Electric field component

H = Magnetic field component

A polarizing filter can provide x- or y- polarized light for

polarization optical anisotropy spectroscopy measurements

10
https://photonterrace.net/en/photon/category/
 Optical Properties of Krogmann’s Salt Single Crystals
Large single crystals of Krogmann’s salt are easy to grow from aqueous solution
These crystals have anisotropic optical properties due to their 1D structure

hν E always  to chain

K2Pt(CN)4·3H2O E = Electric field vector

5dz2  6pz dipole
allowed (z-polarized)
hν

E always  to chain z z
H = Magnetic field vector
x
y
• High reflectivity with E ∥ Pt chain
• Low reflectivity with E  Pt chain
• Electric dipole selection rules for μx,y,z!!
11
• Hence, crystal orientation controls optical absorption, transmission, and reflection
 Polarized Optical Reflectance Properties of M2Pt(CN)4·3H2O

hν E

R(Imax)
Dipole-allowed
hν 5dz2  6pz
E (z-polarized)
z

x
y

• Reflectivity high with E ∥ Pt chain

• Reflectivity low with E  Pt chain
• Cation variations M cause shifts of R(Imax)
• R(lmax) red shifts as dPt-Pt gets smaller - better Pt-Pt overlap
12
• Wider dz2 and pz σ-bands  smaller bandgap for (5dz2  6pz) [or (5dz2  pp*(CN))]
 Cation Effects on Optical Reflectance of M2Pt(CN)4·3H2O

For same crystal structure, cations (M)

can be substituted for alkali or alkaline
earth elements, resulting in size and
charge effects of cation on anionic
chains
(EII)

Cations attract charge from anionic

{[Pt(CN)4]2-}n stack, allowing:
• closer approach of {[Pt(CN)4]2-
building blocks
• shorter Pt–Pt distances
• wider σ(dz2) and σ(pz) bands
• smaller σ(dz2 pz) bandgaps
Largest effect for cations with highest
RPt–Pt-3 ionic potential (Z*/r)

• R(Imax) of the s(dz2  pz) optical transition depends on RPt–Pt-3

13
• cations are not innocent, due to their effect on anionic chains
 Partial Oxidation of K2Pt(CN)4·3H2O

dx2–y2 Partially filled dz2

[Br2]
band, but is it
really a metal!
dz2
dxz dyz 1D CHAIN
dxy K2Pt(CN)4 K2Pt(CN)4Brd
s(T)/s(300 K)
• Partially filled dz2 band
• Fully filled dz2 band
K2Pt(CN)4Brd • Conductor
• Insulator
• s ~ 200 -1 cm-1
0 • d(Pt-Pt) = 3.48Å
• dPt–Pt = 2.88 Å
10-2 M
increasing s 

• σ(T): @ RT  Metal, @ LT  Non-Metal

10-4
NM • M NM at low T
10-6 s vs T
• d = 0.3, crystal structure shows long-short-long-short Pt-Pt—Pt-
10-8 Pt—Pt-Pt bonds in chain with periodicity l = 2.35a
• “Incommensurate charge density wave” – does not match the
0 10 20 103/T (K-1) lattice periodicity, lattice becomes distorted (Peierls distortion)
Decreasing T 
14
 Materials Food for Thought
Polarized optical reflectivity
spectra showing diagnostic
plasmon edge of conduction
How will this optical reflectance electrons for oxidized
spectrum change as the sample is (metallic) form of Krogmann’s
cooled below 100 K?
salt K2Pt(CN)4Br0.3·3H2O

Remember:
• Metallic reflectivity with EII – along chain axis excites conduction e-’s
• Insulating with E – orthogonal to chain axis does not excite conduction e-’s
• Conduction electron resonance of intra-band 5dz2 electrons
• Shows polarization behaviour commensurate with 1D chain 15
• Diagnostic plasma edge of a metal - plasmon resonance of conduction electrons
 Materials Food for Thought

(RII)
Same crystal structure
Explain how and why particular cation (M) but with cation M
variations for alkali,
variations for M2Pt(CN)4·3H2O cause the 5dz2  alkaline earth, size,
6pz optical transition to shift linearly with RPtPt-3 charge effects
(as shown in the accompanying figure).

RPtPt-3

16
 Materials Food for Thought

• Using clearly labeled diagrams and concise explanations, explain how the molecular
orbital scheme and optical reflectance spectrum for K2Pt(CN)4 transforms into the
electronic band diagram and optical spectrum for solid phase K2Pt(CN)4 and these
change on oxidation to K2Pt(CN)4Br0.3
• Why does the metallic form of K2Pt(CN)4Br0.3 reflect light only in one particular
direction?

17
 Materials Food for Thought

Using clearly labeled diagrams and concise explanations, explain the origin of the
significant differences between polarized optical spectra of non-oxidized and
oxidizedand forms of Krogmann’s salt (K2Pt(CN)4 and K2Pt(CN)4Br0.3) in both single-
crystal and powder forms. How do these spectra change on cooling the material?

18
Orbitals and Bands of the Eclipsed PtL4 chain
Undistorted (T >TP) Peierls-distorted (T < TP)
a 2a

AB s pz B

B d dxy AB

AB p dxz,yz
B

B s dz2 AB

k = 2π/λ = 2π/ = 0 k = 2π/2a = π/a

19
 Orbitals and Bands of the Eclipsed PtL4 chain
AB s B
Bonds and bands of an
B d AB eclipsed PtL4 chain –
relationship with dispersion
AB p B
plot and density of states
B s AB
k=0 k = π/a

Plot E(k) vs. k

E(k)
ab  b
Bands running down σ(pz and dxz):
anti-bonding  bonding
Bands running up σ(dz2 and dxy):
bonding  anti-bonding
b  ab
20
0 p/a k
Band Structure and Density of States for an Eclipsed [PtH4]2- 1D Stack
E(k) vs. k Dispersion E(k) vs. N(E) DOS

Note the wide

pz band

Note the wide dz2

band

21
• Unit cell a = 2a’ (a’)
• band folding

22
• DOS for staggered and eclipsed [PtH4]2- very similar
• dz2 band to pz band transition

23
 Materials Food for Thought

• Using clearly labeled diagrams, explain how the electronic bands,

dispersion curves and densities of states for a 1D chain of eclipsed square
planar [PtH4]2- anions evolve from the molecular orbitals of the isolated
[PtH4]2- anion

• Using clearly labeled diagrams, illustrate these diagrams will change on

passing from the eclipsed to the staggered conformation of the chain

• What techniques could be used to distinguish between these two

configurations of the chains?

24
 Molecules to Materials

Bonds  Bands
Molecules  Solids
Jahn-Teller  Peierls
Structure: High-symmetry linear chain (1D), sheet (2D), or cubic close packed
(3D) lattice
Orbitals: Highly symmetrical ordered structures often do not correspond to
situations of maximum bonding/stability

Asymmetric vibrational deformation modes: couple with electronic states and

reduce symmetry – vibronic coupling (e x v)

25
Case Study: Molecular Jahn-Teller Distortion in Cyclobutadiene (C4H4)

D4h
a-2b B2g
Vibronic Coupling

Eu
e*ve  0
a

a+2b A1g

• Two electrons in degenerate orbitals

• Jahn-Teller Effect: coupling of vibrational and electronic motion (“vibronic coupling”)
• Vibrational mode breaks electronic degeneracy, lowering energy of system 26
 v

hν

Temperature, pressure, or light can

convert distorted to undistorted form
• Symmetry-lowering vibrational deformation mode occurs
– Stabilizes one molecular orbital while destabilizing another
– D4h square molecule deforms to D2h rectangular molecule
• Oxidized form ([C4H4]2+) not distorted
• First-order Jahn-Teller effect in C4H4 creates long and short C–C bonds 27
 The three-dimensional form of the potential energy
surface for a Jahn–Teller molecule like C4H4

Q: What would this PES look like for Ag3 ? 28

The Jahn-Teller Effect

29
Steric Stabilization of Cyclobutadiene

30
 Steric Stabilization of Cyclobutadiene
Stabilizing cyclobutadienes (CBDs) and
the heaver congeners Si, Ge with
sterically demanding organic
substituents
• A common view is the polar J–T
distortion stabilizes the cyclic 4p-
electron anti-aromaticity in heavy
CBDs, producing a planar rhombic-
shaped charge-separated singlet
state.
• Explains difference in the bonding and
structure between the carbon CBDs
and the heavy CBDs
• Ascribed to the weaker p-bonds
originating from the less effective p-
orbital overlap, due to larger inter-
atomic distances between heavier
Group 14 elements.
31
Projection of “Sombrero” Potential Energy Surface for the
(A1 + E) Electronic Structure of H3 or Ag3

D3h C2v +
+
+ - + -
B2
- E EJT -
+ + A1
+ +
+ A1 A1 +
(??)
+ +
+ +

Equilateral Isosceles
Triangle Triangle
JT vibrational
distortion mode

32
 Materials Food for Thought

• Draw in detail all possible structures and molecular orbital diagrams for molecular
Ag3. Which of these geometries for Ag3 is Jahn-Teller active? Describe in detail the
effects of temperature, light and pressure on the geometric and electronic
structure of this Ag3 geometry.

• What would you predict the structure of the cationic form of triangular Ag3+ to be?

• Using clear and well-labeled diagrams, explain the effects of temperature, pressure
and light on the structure of cyclobutadiene (C4H4).

• How would you expect the molecular orbital diagram and geometric shape of C4H4
to change following oxidation to form C4H42+, C4H4+, C4H4-, and C4H42- ?
33
 Important Information

Midterm Exam (in class): April 2nd, 5:00 pm, 1 hr

Covid-19 Preparedness Plan

34
 Formalism of Band Folding

Undistorted H chain Distorted H chain (H2)

a 2a

Distortion doubles the unit cell: a’ = 2a E

k now varies between -π/2a and π /2a

Undistorted Distorted
Bandgap M
SC

0 π/2a
k
Band structure
Two atoms in unit cell bands “fold back” after distortion 35
 Move to 1D Solid: Chain of H Atoms (1s1)

EF

a
0 π/a
k
E

EF Band Folding

2a 0 π/2a π/a
k

Phononic or vibrational
mode that couples most
effectively with e- motions 36
 Move to 1D Solid: Chain of H Atoms (1s1)
Examine the orbitals below and above EF:
E

EF

0 π/2a
k
E
• Peierls distortion
• Alternating long-short bonds EF
anti-bonding
• Removal of degeneracy bonding
• Stabilization of system
0 π /2a
k
37
 Peierls Distortion (Vibronic Coupling) in a 1D Metal
Causes M  NM Transition

E E

EF Peierls Gap EF

0 π /2a 0 π /2a
k k
Metal Non-Metal or
Semiconductor

Chain of H atoms  Chain of hydrogen molecules

Suggests metallic hydrogen under high pressure!!! 38

 Origin of Charge Density Waves:
Thinking More Deeply About Krogmann’s Salt K2Pt(CN)4Br0.3

E 2.0 e-
1.7 e-

k = 0 band (dz2)
1.0 e-

k = π/a band (dz2)

0 p/a
k
Vibronic coupling of electron wave at EF (with wavevector k = 2π/λ) with a lattice
distortion vibrational mode stabilizes the system by creates a Peierls energy gap
 Metal-to-Semiconductor transition! 39
Thinking More Deeply About Krogmann’s Salt K2Pt(CN)4Br0.3:
Electron Wavelength at EF

• Fully filled band: 2e- per Pt(II) 2π 2π

λF    2a
k π a
Undistorted

• Half-filled band: 1e- per Pt(II) 2π 2π

λF    4a
k π 2a
 Distorted commensurate CDW

• Part-filled band: 1.7 to 2.0 e- per Pt(II) 2π 2π

λF    2.35a
k 1.7π 2a
 Distorted incommensurate CDW
40
 Throwing Light on the Peierls Gap: Close the Gap!

E E

EF EF

0 π/2a 0 π/2a
k k

Peierls gap excitation promotes electron from bonding to anti-bonding band

 Short bond lengthen and long bonds shorten
 Renders all bonds equal and closes the Peierls gap
41
 Peierls Distortion:
Dynamic Effects of Temperature, Light, Pressure
Examples
Photo-excitation (across Peierls gap)
• H2
• Bonding to anti-bonding band transition
• K2Pt(CN)4Br0.3
• Short bonds lengthen
• NbI4 kT DEp hν • Long bonds shorten
• VO2
• Short and long bonds averaged
• (CH)x
• Decrease and close DEp
• (SN)x ???

Thermal excitation of electrons

• Overcomes distortion barrier
Δ
hν • Short and long bonds averaged
• Decrease and close DEp

External pressure
• Long, weaker bonds become shorter and stronger
P DEp • Short, stronger bonds become longer and weaker
• Short and long bonds averaged
• Decrease and close DEp
42
Materials Food
for Thought

43
 Materials Food for Thought

• Using clearly labeled diagrams and precise statements, explain why a cubic close-
packed lattice of H atoms is unstable (with respect to H2 molecules) under ambient
temperature and pressure conditions. Why is the opposite true at lower
temperatures and higher pressures?

• Given this information, rationalize why the aforementioned H-atom lattice is a metal
whereas a similar H--ion lattice is an insulator.

44
 Materials Food for Thought

• Using clearly labeled diagrams and precise statements, explain why the oxidized
form of Krogmann’s salt (K2Pt(CN)4Br0.3) has a distorted, yet periodic, structure
at low temperatures.
[Note: In this material, long-short-long-short (—Pt-Pt—Pt-Pt—Pt-Pt—) bonds form a 1D
chain with a periodicity of l = 2.35a.
Here, a is the Pt–Pt bond length in the undistorted room temperature structure of
K2Pt(CN)4Br0.3 where all the Pt–Pt bond lengths are found to be the same.]

• Given this information, explain the effects of temperature, pressure and light on
the structural and conductive properties of K2Pt(CN)4Br0.3.

45
 Materials Food for Thought

For what application(s) would it be beneficial to avoid the M-NM transition in 1D

metals made of organic, inorganic, or organometallic building blocks? What
physicochemical property is most important in this scenario?

46
 Example:
The 1D Molecular Metal Ni(Pc)I Does Not Show a Peierls M-NM Transition

• The conductivity of the linear-chain molecular-metal phthalocyanatonickel(II)

iodide [Ni(Pc)I] remains metallic down to near 0 K.

• The full characterization of this compound included a Pauli-like magnetic

susceptibility, as well as single-crystal reflectivity spectra that exhibited a
characteristic plasma edge for light polarized parallel to the conducting axis.

• The results confirm that this compound possesses all the characteristics of
molecular metal and retains a metallic band structure down to a temperature
below 2 K.
47
Ni(Pc)I – 1D Molecular Metal with No Peierls M-NM Transition

• Ni(Pc)I does not possess any strong inter-stack interactions of the type
necessary to suppress a Peierls M-NM transition via an increase in the
dimensionality, and is classified as one of the most one-dimensional molecular
metals studied to date.

• A structurally imposed weakening of the inter-stack Coulombic interactions,

coupled with weak random potentials from structurally disordered triiodide
chains, is apparently sufficient to suppress the transition normally associated
with the tendency of an anisotropic conductor to undergo a Peierls distortion.

48
 Transition Metal Monoxide Rock Salt Crystal Structure

e.g., MnO, FeO, CoO

Face-centered cubic (fcc) B anions (GREEN) with A cations (BLUE) in every octahedral site
 Coordination number = 6 for both A and B. Hence, stoichiometry is 1:1.
49
Rock Salt Transition Metal Monoxide Electronic Properties

50
 Bands in Transition Metal Oxides

3d orbitals of Ti less diffuse than 4s and 4p:

• Provide poor shielding against nuclear charge (Z)
Ti 4s • 3d penetrates closer to core
• Less 3d orbital overlap creates narrower 3d bands
Ti 3d (eg) • 3d bands stabilize, contract, and narrow with Z*
Ti 3d (t2g) • Orbital degeneracy: 3d > 4p > 4s
• 3d electron occupancy and DOS near EF important
for optical, electrical, and magnetic properties
O 2p
Z = nuclear charge
Z* = effective nuclear change

51
Electronic Properties of Rock Salt Transition Metal Monoxides

Why not Why not

metallic? metallic?

Ca Sc/Ti/V/Cr/Mn Fe Co/Ni/Cu Zn 52
 Why No Metallic Behaviour?

Mott-Hubbard Insulators
• The d-levels in most transition metal oxides are
partially filled; band theory predicts delocalized
electrons and metallic properties.
• Thus, fully half of known binary compounds should
be conductors.
• However, many such monoxides show insulating
behaviour; d-electrons must be localized.
• Explanation? Short-range Coulomb repulsion of
electrons prevents formation of band states, resulting
in stabilization of localized electron states.
53
 Mott-Hubbard Insulators

• Coulomb repulsion is described in terms of a

correlation energy (Hubbard – U), which is
the energy penalty for transferring an
electron between two adjacent atomic sites.

UI–A

Ionization Energy Electron Affinity

(a few eV)

54
 Mott-Hubbard Insulators

Mott-Hubbard Insulator
• If U > W, the d-band of the transition metal is split into
sub-bands.
• For electron transfer to occur, the energy barrier U
must be overcome and the material is insulating.
• At the point where W  U, the d-bands begin to
overlap.
• Beyond this point there is no bandgap and the
material is metallic.

Thus, the effects of Coulombic repulsion make even the half-filled d-bands insulating when
55
the interaction between adjacent atoms (represented by the bandwidth, W) is small.
Materials Food
for Thought

56
 Materials Food for Thought

Using clearly labeled diagrams and precise statements, explain

how the electronic structures, band diagrams, and electronic
properties of rock salt metal monoxides (MO) would be expected
to change on progressing from M = Ca to M = Zn.
(Note: Beware certain electronic effects that might fool you into thinking
what is really an insulator should be a metal.)

57
 Rutile Crystal Structure (Tetragonal)

y
x 58
 What About Rutile Type MO2?

V/Nb/Mo/
Ti
W/Ru

eg

t2g

59
Assumes Oh symmetry around M(IV)
 John Goodenough’s Electronic Band Diagram
of Tetragonal Rutile (TiO2)
Wide bandgap semiconductor!
• Tetragonal symmetry
E dπ* – empty dxy, xz
CB t2g • Split t2g
dσ – empty dyz
• dσ/dπ bands overlap

VB π(Ti-O) – p-type lone pairs of O filled

σ(Ti-O) – [s p3 dx2-y2 dz2] orbitals filled

LHS of transition
metals d-orbitals less Constructed from Oh TiO6 “building blocks”
contracted making
wider d-bands 60
 M-SC Peierls Transition - Electronic Bands of VO2

M Phase SC Phase
CB t2g
dπ*
dπ* – empty dxy, xz
dσ – empty dyz
• Tetragonal symmetry
dπ*
dσ
• Split t2g
V 3d O 2p
• dσ/dπ bands overlap
dσ 0.7 eV

Fermi Level

dσ

O 2p 61
Bonding and Peierls Distortion in Low-dimensional,
Rutile-type Metal Oxides
O O O O
O O O O O
M M M M t2g dyz σ-band (M–M)
x O O O O O
y O O O O

z O O O O
O O O O O
t2g dxy, dxz π*-bands
M M M M
O O O O O
(M–O, doubly degenerate)
O O O O

• Tetragonal rutile structure comprises edge-sharing chains of Oh M(IV)O6

• Goodenough picture of t2g-based, filled σ- and π-bands (from MO6 building blocks)
• Leaves two d-bands: M–M σ-band and M-O π*-band
• 2 e- on each M for σ-band filling, and extra 4 e- for π*-band filling
• Different band fillings may or may not give Peierls distortion
• Structure and electronic properties a compromise of M–M s and M–O π* effects 62
• Change with temperature, pressure, and light
 Peierls Distortion in Low Dimensional Rutile Metal Oxides
Oxide d-electrons M–M separation

TiO2 0 2.96 (SC)

VO2 (tetra) 1 2.85 (M) HT

VO2 (mono) 1 2.62 (SC) LT 3.17 (SC) LT

NbO2 (tetra) 1 3.00 (M) HT

NbO2 (mono) 1 2.71 (SC) LT 3.30 (SC) LT

MoO2 2 2.51 (M) 3.10 (M)

WO2 2 2.48 (M) 3.10 (M)

RuO2 4 3.11 (M)

OsO2 4 3.18 (M)

• Electronic and structural changes related to dn configuration and temperature

• Electrical conductivity varies from SC to M depending on balance between σ(M–M),
σ*(M–M) and π*(M–O) bonding 63
 Electronic-Structural RelationshipTrends in Rutile Metal Oxides
Regular Form (tetragonal) Peierls-distorted (monoclinic)

M–O π* d1 M–O π*
VO2, NbO2 M–M σ*
M–M σ (HT regular M,
M–M σ
LT distorted SC)

d2 MoO2
(distorted M)

Compromise between
M–M σ and M–O π* d4 RuO2
bonding interactions (regular M)

d1+x
VO2-xFx ??? 64
 Example of Doping Effects on Optical Properties
For “smart” windows, Hysteresis and Contrast are critical

65

ZR Zou, ZH Zhang, J Xu, ZY Yu, M Cheng, R Xiong, ZH Lu, Y Liu, and J Shi. Journal of Alloys and Compounds 2019, 806, 310
 Materials Food for Thought

For rutile-type metal dioxides (MO2), provide geometric and

electronic band structure details that explain why MoO2 behaves
as a distorted metal while NbO2 is a distorted semiconductor at
low temperatures and a regular metal at high temperatures.

66
 Synthesis of VO2-xFx

Au tube, 600 C/133kbar

V2 O5  V  6% HF/H 2 O    VO 2 x Fx

V5++ V0  V(4-x)+
Extent of isomorphous substitution (x, F- for O2-)in
VO2-xFx controlled by concentration of HF/H2O

67
 Statistical Isomorphous Substitution in VO2
Vegard’s Law-type behavior observed for lattice parameters
(from PXRD) for VO2-xFx in range x = 0 to 0.2

Vegard’s Law
4.58 • Unit cell parameters vary
Å 4.56
ao linearly with x
4.54
• Solid solution behaviour
2.88
(low-level substitution)
Å co
2.86 O

60.5
V F
Å3 60.0
59.5
Vo
0.05 0.10 0.15 0.20
x
68
Solid-solution VO2-xFx

69
 Solid Solution VO2-xFx
• Isomorphous fluorine substitution into rutile VO2 structure
• What effect on bonding and electronic properties of VO2?
• 0 < x < 0.2  Isomorphous substitution of F- for O2- in rutile lattice
• V4+ reduces to V3+  longer V–O and V–F bonds  weaker V–V bond
• Extra electrons go to M-O π* band
• De-stabilized Peierls distorted state!
Tp • Tuning transition temperature (Tp) for high-
symmetry metallic (tetragonal) to distorted
300
metallic (monoclinic) phase
• Tp with xF- substitution – linear Vegard’s law
200
behavior
• Less-favoured Peierls distortion,high
100
temperature tetragonal metallic phase becomes
more stable
0.05 0.10 0.15 0.20 70
x
 Physical Properties of VO2-xFx

Compound Cell parameter (ao) co Eact (eV) Tp (K)

T-dependent resistivity

VO2 4.530 2.869 0.5 340

VO1.97F0.03 4.552 2.853 0.07 298

VO1.96F0.04 4.554 2.854 0.06 282

VO1.86F0.14 4.562 2.876 <0.01 155

VO1.79F0.21 4.569 2.886 <0.01 65

• Tp as xF-
• Monoclinic (low-T form) to tetragonal (high-T form) transition
• F- substitution  V4+reduces to V3+  longer, weaker V–O/V–F bonds
• Longer V–V bond and weaker V–V interaction energy
• Additional unpaired e- go into π* M–O band
• De-stabilization of Peierls-distorted monoclinic SC state 71
• Favours lower-resistivity, higher-conductivity tetragonal σ-band M state!
 Physical Properties of VO2-xFx

d1+x
VO2-xFx
(regular M)

• Tp as xF-
• Monoclinic (low-T form) to tetragonal (high-T form) transition
• F- substitution  V4+reduces to V3+  longer, weaker V–O/V–F bonds
• Longer V–V bond and weaker V–V interaction energy
• Additional unpaired e- go into π* M–O band
• De-stabilization of Peierls-distorted monoclinic SC state
• Favours lower-resistivity, higher-conductivity tetragonal σ-band M state! 72
Materials Food
for Thought

73
 Materials Food for Thought

• Using clearly labeled diagrams and precise statements, explain

how you would expect the electronic structure, band diagram,
and properties of the rutile-type metal dioxide VxNb1-xO2
change as the value of x increases from 0 to 1.
• How would the electronic structure, band diagram, and
properties change as a function of T?

74
 Materials Food for Thought

• How would you synthesize VxMo1-xO2?

• Using clearly labeled diagrams and precise statements, explain
how would you expect its electronic band diagram, structure
and electronic properties to change as the value of x increases
from 0 to 1.
• How would the electronic structure, band diagram, and
properties change as a function of T?

75
 Materials Food for Thought

• Devise a synthesis of VxNb1-xO2 for values of x between 0

and 1. Describe the different ways in which V and Nb could
be distributed in the Rutile lattice. How could you
distinguish between these different arrangements?
• What are the oxidation states of V and W in VxW1-xO2,
where 0  x  1? What methods could you use to prove it?
• Explain in detail why the Peierls temperature decreases as
the fluorine content in VO2-xFx increases.

76
Photoinduced M-NM Transition in Single Crystal VO2 Nanowires:
A Nanoscale Optical Switch

V2O5(s)(in Al2O3 crucible) + H2(g)  2VO2 (nw, Si substrate) + H2O(g)

Nanowires grown on silicon substrate and characterized by PXRD, XPS, and TEM

77
78
 Nano-VO2 Optical Switch
hν
ON (UV) OFF
M Phase SC Phase

dπ*

dπ*
dσ
V 3d
O 2p
dσ
Fermi Level 0.7 eV

dσ

O 2p 79
 Thermal versus Ultraviolet Driven M-NM Transition in nwVO2
hν
ON (UV) OFF
M Phase SC Phase

dπ*

dπ*
dσ
V 3d O 2p
dσ

Fermi Level 0.7 eV

dσ

O 2p

Note hysteresis in heating and cooling curves.

What is the origin of this effect? 80
 Origin of Hysteresis in Heating-Cooling Cycle
through the M-NM Transition of VO2

Dh
M

NM
Dc

D h > Dc
ΔEp, Lattice Strain ??? 81
Direct Visualization and Electrical Resistance Observation of the M-NM
Peierls Phase Transition in VO2 Nanowires
• The M-NM transition in VO2 is subject to strong lattice coupling, which brings about the unique one-dimensional alignment
of alternating metal and insulator domains along nanowires.
• These conductivity differences can be seen as different color domains on joule heating in a thermoreflectance microscopy
image

82
nwVO2 M-NM RT Optical Switch
hν
ON (U
V) OFF
M Phase SC Phase
50 °C
RT dπ
*

dπ
*
dσ

d
σ
0.7 eV
Fermi Level
d
σ

O 2p

Photocurrent increases in the light!

83
• The as-synthesized VO2 nanowires can undergo a photo-induced M-NM phase
transition under UV light at RT
• The nanodevices made from VO2 nanowires exhibited excellent photoresponsive
properties, attributed to photoinduced M-NM phase transition of the VO2
• The ratio of photocurrent-to-dark current is 285 using 7 mW cm-2 UV irradiation.
• Fast response and recovery times of 1.3 and 4.5 ms were determined, respectively.
• VO2 nanowires possess high electron mobility of 29 cm2 V-1 S-1 under UV irradiation.

84
Materials Food
for Thought

85
 nwVO2 M-NM RT Optical Switch

• Given a single-crystal VO2 nanowire with electrical contacts at each end,

what would you expect to observe by turning on and increasing the voltage
between the two terminals in ultraviolet light compared to the dark?
• What technique(s) would you use to measure these effects?
(Use clearly labeled diagrams and precise statements to explain your answer.)

Nanowire

V
86
 Materials Food for Thought

Describe how you would you synthesize, construct and operate a

thermal/optical switching device based on VO2 nanowires.

87
Other Examples of Peierls Distorted Structures

NbI4 consists of d1 (t2g1), edge-sharing Nb4+ Oh in a 1D chain

I I I I
I I I I I
Nb Nb Nb Nb
I I I I I
I I I I

High P and High T

I I I I
I I I I I
Nb Nb Nb Nb
I I I I I
I I I I

• Alternating long/short Nb–Nb bonds (Peierls distortion)

• Semiconductor at low T and low P
88
 Other Examples of Peierls Distorted Structures

BaVS3 consists of d1, face-sharing V4+ Oh 1D chain (extra 1 e- in dz2 orbital)

S S S S
S S S S
V V V V V
S S S S

High P and High T

S S S S
S S S S V
V V V V

S S S S

• Alternating long/short V–V bonds (Peierls distortion)

• Semiconductor at low T and low P
89
Materials Food
for Thought

90
 Materials Food for Thought

Using clearly labeled diagrams and precise statements, using some well-
chosen molecules and materials to explain the the origin of, and
relationship between, the Jahn-Teller effect in molecules and the Peierls
effect in materials.

91
Low-dimensional Layered Structure of Transition Metal Dichalcogenides
MX2, where M = Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, or W, and X = S, Se, or Te

• Group IV, V, VI MS2 compound

• Layered structure (VDW forces) S
• Ti4+ between hcp layers of S2-
S S
• Li insertion into Td sites between the layers Ti
• e- injected into CB S
hcp S2-
S S
S
S
Ti Ti in D3h
Ti
S
S
Li
D3h
Li insertion
S S
Ti Ti dxz, dyz
S S
Li dx2-y2, dxy
S
S
Ti
S
Ti dz2
S
92
 Chemically Tuning Properties of
Transition Metal Dichalcogenide Intercalation Compounds
S, Se, Te in octahedral (Oh) or trigonal prism
(D3h) symmetry sites
Strong M–X bonds hcp S2-
Semiconducting or metallic
S behaviour depends upon:
S
Ti Ti4+ (D3h)
Ti
S
S 1. dn electron configuration of M
Li
S
Li insertion
S 2. D3h/Oh symmetry of M
Ti Ti
S S 3. Degree of band filling  xLi+ + xe-
Li
S 4. S/Se/Te band tuning
S
Ti
Ti 5. p-/n-doping of TiS2 (with P or V)
S
S
Substitution:
Weak interlayer VdW Ti4+, V4+, Cr4+, Zr4+, Nb4+,
forces Electronically tunable MSxSe2-x and
Mo4+, Hf4+, Ta4+, W4+
p/n-doped with P or V in TiS2

Insertion of atoms, ions, clusters, organometallics, and polymers into interlamellar

spaces with minimal perturbation of structure of host
93
 Materials Food for Thought

Oh
D3h

TiS2, ZrS2 VS2 NbS2, TaS2 MoS2

d0 semiconductor d1 metal d1 metal d2 semiconductor

Electronic structure and properties of MX2 depends on M

site symmetry, band type and degree of band filling 94
Electronic Band Structure and Properties of TiO2 versus TiS2
TiO2 – rutile oxide – Oh Ti4+ (d0) TiS2 – layered chalcogenide – Oh Ti4+ (d0)
E E

CB CB
Empty t2g 3d band
Eg(TiS2)
Eg(TiO2)
VB
VB
Fully filled O(2p) and S(3p)
valence band

N(E) N(E)
• TiO2 – rutile oxide is a wide bandgap insulator
• TiS2 – layered chalcogenide is a semiconductor
• Why is Eg(TiS2) < Eg(TiO2)?
• Fully filled lower energy for O(2p) relative to S(3p)
• Empty t2g (3dxz,yz,xy) band (Oh)
• Smaller energy separation, greater orbital overlap 3d–3p Ti-S vs 3d–2p (Ti-O) 95
• Bandwidth of VB larger for S than O; hence, smaller Eg!
 Electronic Band Structure and Properties of TaS2 and TaSe2
Ta Ta Ta Ta Ta Ta Ta Ta

TaS2 and TaSe2

Ta Ta Ta Ta Ta Ta Ta Ta
D3h
Ta Ta Ta Ta
d1 Ta Ta Ta Ta

Ta Ta Ta Ta
Layer Structure Ta Ta Ta Ta

Projection of undistorted MX2 layer 2D CDW Metal array of undistorted MX2 layer
Ta

• D3h Ta4+ d1  half-filled dz2 band

Ta Ta Ta Ta
• Undergoes 2D Peierls distortion
• M–M alternating short-long bonds
Ta Ta Ta • Driven by electron-phonon coupling
• Hexagram-shaped Ta4+ metal-atom-clustering distortion mode
Ta Ta Ta Ta • 2D periodic lattice distortion in hcp chalcogenide sheets

96
Ta
Electronic Band Structure and Properties of TaS2 and TaSe2

Hexagram-shaped Ta
Atom-clustering CDW
in TaS2

97
98
 Ta

Ta Ta Ta Ta

Ta Ta Ta

Ta Ta Ta Ta

Ta

99
 Ta Surface Selenium Atom
Distortion Seen by AFM
Ta Ta Ta Ta (Note: Tantalum Atoms are Buried
Beneath the Selenium Layer)

Ta Ta Ta

Ta Ta Ta Ta

Ta

100
Materials Food
for Thought

101
 Materials Food for Thought

• Using clearly labeled diagrams and precise statements, how would you explain the
origin and mechanism of the transition from semiconductor, to metal, to
semiconductor in the metal disulfide series of materials: ZrS2, NbS2, MoS2?
• Describe different ways you could tune the electronic properties of transition metal
dichalcogenides (MX2) for M = Zr, Nb, or Mo; X = S, Se, or Te.
• Which of these materials would be predicted to exhibit the Peierls effect? How
would you expect it to manifest structurally?
• Using clearly labeled diagrams and precise statements, explain how you would
expect the electronic band-gap of ZrO2 to compare to that of ZrS2

102
 Materials Food for Thought

• Using clearly labeled diagrams and precise statements,

apply chemical bonding and simple electronic band
theory concepts to decide which of the niobium
dichalcogenides (NbS2 or NbSe2) is the better metallic
conductor.
• Based on this choice, rationalize which one is most
likely to undergo a change to a superconductor on
cooling to cryogenic temperatures. Why is this true?

103
DAY AND ROBBINS CLASSIFICATION OF
INTERVALENCE COMPOUNDS

104
CLASSIFICATION OF INTERVALENCE COMPOUNDS

Class I: Finite molecule - very different discrete ion

environments for different oxidation states, GaCl2 =
Ga(I)[Ga(III)Cl4], large Eact, no interaction, localized electrons
Class II: Sufficiently similar environments for different integral
oxidation states, small Eact hopping semiconductors,
intervalence charge transfer IVCT band observed
Class III: Identical fractional oxidation states with delocalized
electrons between them.
Class IIIA: Finite cluster - delocalized intra-cluster electrons
Nb6Cl14 Oh Nb6 cluster core, 6 terminal Cl + 8 face Cl
Class IIIB: Electrons delocalized throughout Extended solid -
metallic conduction 105
 MIXED VALENCE COMPOUNDS – LOCALIZED VS DELOCALIZED

localized delocalized localized

Configuration Activation
coordinate diagram energy
for electron
IVCT hopping
optical transition between MOM
between two sites
different
oxidation state
MOM sites

• Weak interaction MOM - localized electrons and associated lattice distortion

called a small polaron (ion-lattice polarization effect) at left and right
• Large interaction MOM, low Eact activated hopping – delocalized e
• Weak interaction MOM, large Eact trapped or localized e 106
 Class I and Class IIIA

[Nb6Cl14]2-
Mixed Valence Class IIIA
Delocalized Nb(2.33) finite
cluster

GaCl2 = Ga2Cl4 = Ga(I)Ga(III)Cl4

Mixed Valence Class I
Localized Ga(I) and Ga(III)
oxidation states in a finite
molecule

107
Class II Mixed Valence Red Lead
Pb3O4 = Pb(II)2Pb(IV)O4

6 CB Pb(IV)

IVCT
Pb(II)
3
Eg

Provide an electronic band diagram to explain why red lead

is colored red and behaves electricaly as a hopping VB O(-II)

semiconductor? 108
Class II Mixed Valence Perovskites
ABX3 where A = Cs, B = Au, X = Cl
CsAuCl3 = Cs2Au(I)Au(III)Cl6
Au(I)Cl6 octahedral
B(I) building blocks will be
larger than Au(III)Cl6
ones in CsAuCl3
B(III Optical absorption
A(I)) spectrum of CsAuCl3
will show Au(III)Au(I)
X(-I) inter-valence charge
transfer – Class II
109
 Fe3O4 – [Fe(III)][Fe(II)Fe(III)O4]
• Borderline class II/III - inverse Spinel [Fe3+(Td)][Fe2+Fe3+(Oh)]O4
• Note [Mn2+(Td)][Mn3+Mn3+(Oh)]O4 normal Spinel class II
High T - behaves as borderline mixed valence
102 metal -semiconductor Fe(II)-Fe(III) Oh-Oh same
sub-lattice sites - valence delocalized class II/III
1
s(-1cm-1)

Verwey transition
10-2 Low T - behaves as low Eact
Oh-Oh Fe(II)-Fe(III) same
10-4 sub-lattice site valence
localized hopping
semiconductor class II
4 8 12
1/T
temp 
• Mn3O4/Co3O4 – normal Spinel e-hopping - different sub-lattice
110
Td -Oh sites, class II, high Eact low RT conductivity
 Eu(II) Eu(III)
Eu3S4
• [Eu(II)(Td)][Eu(III)2(Oh)] S4 Normal
Spinel

• ccp O(-II), M(III) 1/2Oh, M(II) 1/8Td sites

• Mössbauer – distinct Eu(II)/Eu(III) isomer

shifts at low T – localized class II

• Peaks coalesce at high T

• Electron hopping between Eu(II)/Eu(III) –

delocalized class III

• Reversible – analysis provides Eact(ET)

111
 Wolfram’s Red
• Reihlen and Flohr in 1931

• Synthesis of Wolfram’s Red salt

• React aqueous colorless Pt(II) + yellow Pt(IV) solutions

D4h Square Planar D4h Quasi Octahedral

• [Pt(II)(C2H5NH2)4]Cl2 + [Pt(IV)(C2H5NH2)4Cl2]Cl2

• Product red with double salt formula

• [Pt(II)(C2H5NH2)4][Pt(IV)(C2H5NH2)4Cl2]Cl4
112
Wolfram’s Red salt [PtII(am)4][PtIV(am)4Cl2]Cl4
Another class of 1D Pt chain compound • d8-d6 inter-valence
compound with long-short
Cl
NH2R Pt(am)4Cl3 Pt(IV)-Cl---Pt(II) bonds

RH2N Pt
IV
• Square planar D4h and
NH2R
octahedral Oh building
RH2N blocks in 1D chain
Cl

NH2R
• Electronic spectrum
II
shows 500 nm IVCT band
RH2N Pt NH2R – valence localized NM
RH2N
hv
Pt(IV) Cl Pt(II) Pt(II) Cl Pt(IV)
Cl
NH2R
• Hypothetical Pt(III) valence delocalized
IV
• Symmetric compound would be a metal
RH2N Pt NH2R
• d7 Pt(III) partially filled dz2-band
RH2N • Peierls distortion electron-phonon coupling
Cl • Long-short bond mixed valence Peierls NM favoured
113
• Dissociates to Pt(II) and Pt(IV) complexes rather than transitioning to metal
Franck-Condon Principle
ES

Vibronic
Progression
GS
Roughly
Equally
Spaced
Vibrational
Components
in Absorption
and Emission
Spectrum

114
 Pt(IV)--ClPt(II)  Pt(II)Cl—Pt(IV)

Resonance Raman spectrum

• Resonance Raman (~500 nm laser excitation into ~ 500 nm

IVCT) – Raman vibration progression in symmetrical intra-chain
(Pt-Cl) stretching mode with regular spacing ~200 cm-1
• Shows importance of Peierls vibronic coupling between (Pt-
Cl) modes and IVCT excited electronic state of 1D chain
• Frank-Condon Principle controls number and intensity distribution
of vibronic states in configuration coordinate diagram 115
 Adv. Mater. 2000,12,1461

Cl- Cl- Cl- Cl- Cl-

Cl- Cl- Cl- Cl- Cl-

CHCl3
solvent

IVCT
colored

NO IVCT
Self Assembling Disassembling
116
Wolfram Chains
 Thermochromic Mixed Valence Material
Coloration and de-coloration through association-dissociation and reversible
activation of inter-valence charge-transfer IVCT band

NOTE - DIFFERENT M DIFFERENT IVCT COLOR

Pd(II)Pt(IV) Ni(II)Pt(IV) Pt(II)Pt(IV) Pd(II)Pd(IV)

117
Wolfram Nanowires in Solution

118
 MIXED VALENCE ORGANOMETALLIC POLYMER
ROP of Strained Silicon-Bridged [1]Ferrocenophanes

Me Me

Si

Me 0
Fe Si Fe
Me

n
Manners 1992
Polyferrocenylsilane (PFS )

amber, film-forming polymer

Mw = 520,000, Mn = 340,000

ROP of a bent back ring strained cyclic ferrocene monomer

Chain growth mechanism, facile access to high MW polymers 119
 Monomer Synthesis
R2 SiCl2
Li non-polar solvent
Fe
BuLi, tmeda Fe . tmeda eg hexanes Fe Si
R
hexanes - 2 LiCl R
Li

red-orange crystals
70 - 90 %
tmeda = Me2 NCH2 CH2 NMe2
R = Me, Ph, Cl
(Osborne, Univ. Exeter, England 1975)

• Possess strained, ring-tilted structures

• Tilt-angle ca. 20.8° (for R = Me)

• Strain energies ca. 70 - 80 kJmol-1

120
 Polyferrocenylsilanes (PFSs)
Me Me
Si

Fe

n
Polyferrocenyldimethylsilane
semicrystalline thermoplastic
Tg m

• PFSs depending on substituent's on Si can be amorphous gums, glassy

materials, semi-crystalline or liquid crystalline.
• PFSs depending on substituent’s on silicon can be soluble in polar or non-
polar organic solvents or even in water

• Chemical (I2, AgPF6) or electrochemical oxidation produces PFS/PFS+ in

which alternate iron sites are oxidized …..Fe(II)-Fe(III)-Fe(II)-Fe(III)…. mixed
valence localized or delocalized ???
• Mossbauer, electrochemistry, electrical conductivity, UV-Vis IVCT shows
behaves as Class II p-type hopping semiconductor for charge transport 121
MO Scheme of Cp2Fe

Oxidation to
ferrocinium
Cp2Fe+

122
 X
R R

Si

R R
Fe Fe
* Si
*

Mossbauer, electrochemistry, electrical

conductivity, UV-Vis IVCT shows behaves as

Class II Fe(II)•••Fe(III) mixed valence localized p-

type hopping semiconductor for charge transport 123
 PFS – Chemical and
Electrochemical Oxidation
 PFS Fe(II)Fe(II) is electroactive
 2 redox peaks in cyclic voltammetry
 Fe(II)Fe(III) and Fe(III)Fe(III)

Chemically and
electrochemcially redox-
-200 0 200 400
tunable electrical conductivity E (mV)

Alternating Fe(II)-Fe(III)
R R X 2X
R R R R

Si
Si Si

R R R R R R
Fe Fe Fe Fe Fe Fe
* Si * Si * Si
* * *

n n n

124
Increasing “polarity” of polymer backbone
 Why is Prussian Blue Blue?

Fe7(CN)18

4Fe3+ + 3[FeII(CN)6]4− → FeIII[FeIIIFeII(CN)6]3

125
 Why is Prussian Blue Blue?
IVCT  Fe(II)/(III)
CN NC Color of Prussian Blue
CN NC

NC FeII C N FeIII NC
NC CN
CN NC

3D cubic open framework – bridging

cyanide ligands - distinct class II
localized Fe(II)/Fe(III) sites

Low spin d6/d5 Oh iron(II)/(III) sites 10000 20000 cm-1

126
Materials Food
for Thought

127
 Me Me

Materials Food Me
Si

for Thought
Fe Si Fe
Me

n
Polyferrocenylsilane (PFS )
• With clearly labeled diagrams and concise and
amber, film-forming polymer
precise statements explainM (i) how Mthe= 340,000
= 520,000,
w n
molecular
orbital diagram of ferrocene would be modified in
the poly-ferrocenyldimethylsilane, (ii) how this
diagram would be modified following half and full
oxidation of the ferrocene sites on the polymer, (iii)
how these oxidation processes determine the
electrical conductivity of the polymer, and (iv) how
you would chemically modify the polymer to tune
its electrical properties? 128
 Materials Food for Thought
• With clearly labeled diagrams and concise
and precise statements explain why Fe3O4
shows a Verwey transition but Mn3O4 and
Co3O4 do not?
• Given CsAuCl3 is a mixed valence
Perovskite deduce the element that exhibits
mixed valence and explain how it will
influence the structure of the Perovskite unit
cell and be manifest optically?
• Why is red lead red? 129
 Materials Food for Thought
• With clearly labeled diagrams and concise and precise
statements explain the reason why “Wolfram’s Red”
formulated Pt(en)4Cl3 is Red and with this knowledge
describe what would you modify by chemical synthesis
in order to tune the color from red through the rest of the
visible spectral range and even into the near infrared?
• How would you make Wolfram’s red into a
thermochromic material ?

130