2nd edition.

All rights reserved © October 2015

The gold electronic enigma, 1, 2 or 3, a look inside the electronic shell of noble metals
Preface:
Noble metals of the light and heavy groups, behave as 'darlings', keeping well their
electrons from being taken, or being oxidized. Only strong oxidizers, e.g. chlorine can
provide the high energy needed to react those electrons.
One day I asked myself “why noble metals, are noble?” for example, why it is hard for
electrons to enter reactions, like oxidation, dissolution, why precipitation is easy. This
provides “a look inside the electronic shell”, as well as how electrons interact in adsorption
of gases, 1st stage in catalysis, where noble metals play a big role. Why at all, we do not
use other transition metals, much cheaper? Then I asked myself why some noble metals
have high electric conductivities, the highest among metals, while some have low
conductivity like palladium and especially mercury, is there any connection between its
being a liquid, to having low conductivity. Then I learned about relativistic contraction,
what causes both fluidity and low conductivity, for mercury. So, I asked myself, how gold
is so different, if being such a close neighbor to mercury. Interestingly, both have similar
earth crust abundances, mercury about twice only that of gold. Then I learned, that some
researchers say gold and platinum concentrated in the earth core, since they are heavier
than nickel and iron. So why not lead, mercury and osmium too? My guess - the reason
they said that is simply because gold and platinum light the imagination, the others, not.
The questions continued, if the relativistic contraction works well for 2 outer electrons,
gold has but one, isn't that? so, how gold is monovalent or trivalent and not divalent.
Enigma? Add to this the colors gold makes in different sizes, and learn the enigma is just
beginning. Add to this the fact that elements' nth s-shell, fills before (n-1)th d-shell. Does
that imply that d-electrons will react before s-electrons? Add to this that 2 of the ten 5d-
electrons of gold join the lonely 6s electron to make the trivalent gold. Similarly with
rhodium. Add the fact that ionization potential of gold lonely electron is 9.2ev, while silver
ionization takes place with 7.6ev only (mercury – 10.4!). Add the fact that the “sea of
electrons” in gold consists of molecular orbitals that may contain a couple of electrons
each – does that imply gold dimer existence? And why gold, silver do not make good
super conductors, being such good conductors. Well, here we come to Enrico Fermi, a
great scientist which has made so many postulates (axioms), covering the whole issues,
but use his ideas for noble metals which is the issue here. We'll see what are phonons and
photons, we'll give a look to the nucleus, holding the inner electronic shells, see how it
agglomerated from helium, through iron, to noble metals (preceding helium - hydrogen,
protons, electrons and more were the building bricks). The section dealing with creation
will answer 1. Is it possible that asteroid, or another planet, has different concentrations
of elements than earth's? 2. Is nobleness or inertness implies higher abundance? Another
issue is that of electron transitions, a cause to colors, in other words light absorbance, we
shall meet many such transitions, sometimes speaking only about the colors, taking in
account that the reader has enough information to guess the transition involved. While
doing all this and more, we pass from one metal to another, lighting some features which,
are less known......
The compilation of all said issues, plus others, trying to cover the main electronic picture
of noble metals and what inside and behind it., that is what created this booklet.
Lastly, notes and corrections will be greatly appreciated.
Arik Lin, Ph.D. Lino_1406@yahoo.com
Contents
1.The creation of noble metals. 1
2.Why they are noble? 3
3.Copper 7
4.Hydrogen adsorption 7
5.Fermi level, conductivity and superconductivity 9
6.Colors of gold, copper and silver metals 15
7.What are the 5 shiniest metals – explanation 20
8.Mercury 21
9.Ruthenium 25
10.Adsorption of oxygen on Ru 25
11.Rhodium 27
12.NO, NO2 adsorption on Rh 27
13.Palladium 28
14.CO adsorption on Pd, Pt 28
15.Silver 29
16.Platinum 30
17.Gold 31
18.Gold electronic enigma, 1, 2 or 3 31
19.Nano-gold and noble metals, crystal sizes and colors 33
20.Rhenium, osmium, iridium 35
 1
1. The creation of noble metals
The story of noble metals...is in fact the story of creation. Where it all started ?
In the beginning.. the universe was a hot, circling 'soup' of 4-Helium, 1-Hydrogen,
protons, neutrons, electrons, positrons, neutrinos, anti neutrinos, γ-rays (photons)....
4-He consists of 2n, 2p+ and 2e-. When three 4-He atoms combine 12-C is formed, in
what is called helium burning at 100 million Kelvin degrees. 12-Carbon has equal numbers
of electrons, protons and neutrons. Similarly 16-O, which has 8n, 8p+ and 8e-.
"Carbon burning” and “oxygen burning” bring temperature higher and 28-Si, having 14n,
14p+, 14e-, 20-Ne, 24-Mg, 32-S and 40-Ca are produced. The temperature is then raised
to 2 billion ºK.. Than 56-Ni which is unstable, transforming quickly to unstable 56-Co by a
process called β+ decay. Except for this case β+ decay is a rare decay, caused by passing
a limit to number of protons “held” by a given number of neutrons. Capturing together 4-
He = 2p + 2n, for example, may cause such “deviation”. Another possibility is losing a
neutron by fast² neutrons bombardment. In both cases the situation formed is that the
number of protons per neutrons in a given nucleus is above what can be “absorbed”. To
correct that, A positron is freed, besides neutrino and energy. Proton transforming into
neutron. Atomic number decreased by 1 (νe = neutrino, a particle postulated by Fermi):
56Ni(28) = 56Co(27) + e+ + νe + γ
Then 56-Fe, very stable, from 56-Co by same reaction.. an Iron atom is produced having
26 protons, 26 electrons and 30 neutrons.. which is the most stable atom on earth, having
the largest nuclear binding energy, 8.8 Mev per nucleon (that is either a proton or
neutron). Constitutes most of earth core¹.. From here on, at atomic numbers higher than
26, a cooling takes place and a sequence of neutron captures begins. 4-He cannot join
atoms above z=26, because of coulombic repellence, but neutrons can (what is energy
consuming), so, atoms above 56-Fe are neutron-rich, meaning – over 1 neutron per
proton in the nucleus. The process goes like this: AX(z) + n = (A+1)X(z) + γ, where A is
the atomic weight and z the atomic number (in whole numbers). However, at points the
number of neutrons per proton, in a given nucleus, reaches its limit. For example, Fe
heaviest isotope is 59Fe. Then the more common β- decay may occur, where the atomic
number is raised by one, due to neutron already captured, transforming into a proton
(A+1)X(z) = (A+1)X(z+1) + e- + νe- + γ (νe- = antineutrino)
for example: the formation of a stable 59-Cobalt atom
56Fe + n = 57Fe + γ; 57Fe + n = 58Fe + γ; 58Fe + n = 59Fe + γ
59Fe = 59Co + e- + νe-+ γ. This is not necessarily the lowest isotope of Co, but it is able
to capture further 5n, to 64-Co (in five consecutive stages).
Now let's proceed to stable 58Ni from 57Co received by neutron capture of 56Co
57Co + n = 58Co = 58Ni + e- + νe-+ γ
Note: shown sequences that occur 'regularly' in stellar cores called s- (slow) processes.
But supernova nuclear explosions with r-(rapid) processes occur and add more reactions.
For 63-Copper and 65-Copper we need several neutron captures sequence of 58Ni:
58Ni +3n = 61Ni+ γ (three consecutive stages are written together)
62Ni + n= very stable 63Ni+ γ
63Ni +3n= 66Ni+ γ
63Ni = 63Cu + e- + νe-+ γ, that's β- decay
65Ni = 65Cu + e- + νe-+ γ, that's β- decay too.
¹ The death of stars consists of lighter elements than iron to fuse and heavier to split into
56-Iron.. the most stable, the most “tightly bound nuclei” (together with 62-Ni).
² If not otherwise stated, all neutrons mentioned here as being captured or splitted, are
slow (thermal) neutrons.
 2
Death of stars is out of this text concern (When abnormal heat takes the place...nuclear
reactions again replace chemical reactions). Meanwhile... a process of settling takes place.
stars agglomerated of the circling soup, each carrying, probably a different composition of
elements, among them noble metals. Palladium e.g. is much more abundant than silver in
the sun contrary to earth. (Prioritization of even 46 vs. 47 + a continuing process in
nuclides without melted core). So we got all the elements, including noble metals, all of
which are heavier than iron. Atomic numbers, z=44 to 47 (Ru Rh Pd Ag) and z= 76 to 80
(Os Ir Pt Au Hg). Formed of course by series of neutron capturing, β- decays, β+decays..
Mother nature simply made a round all over the atomic numbers, capturing and decaying,
not giving any preference to noble metals, or any element above z=26, (except a small
one for even numbered, mother nature likes all of them in pairs..) We shall discuss also
Cu(29) and Re(75), because of some linkage with noble metals.
Look at the following graph, showing nuclear binding energies of group Ru Rh Pd Ag :
We see that binding energy per nucleon goes down with growing number of neutrons,
meaning that if protons and neutrons had to decide which nucleus to comprise, they'll
generally go towards lower atomic number, more precisely lower number of neutrons,
thus having the highest binding energy, hence stability
Nuclear binding energy, per nucleon Ruthenium - Silver
Nuclear binding energy, Mev

8.64

8.62

8.6

8.58

8.56

8.54

8.52

8.5
Atomic number
43 44 45 46 47 48

What means, no preference for a particular metal, except neutrons number. So every
metal or elements including noble metals were simply produced from other elements..
Possible scenarios s-(slow process). Bear in mind that β- decay is the common sequence;
1) Abundant iron(26), nickel(28) copper(29) and Zn(30), serve as starting materials
2) A sequence of neutron captures, followed by decays, give Nb(41) and Mo(42)
3) Mo(42) gives unstable Tc(43) and stable Ru(44). A luster is developing..
4) Ru(44) gives Rh(45) by neutron capture and β- decay. Luster now at its climax..
5) Rh(45) gives Pd(46) by neutron capture and β- decay
6) Pd(46) gives Ag(47) by neutron capture and β- decay, (however most Ag captures
neutrons, going to Cd(48) with β- decay). A similar patern for the group Os Ir Pt Au Hg :
7)Re(75) gives Os(76) by neutron capture and β- decay. Mother nature observed at
this point the highest weight - number of neutrons and protons in a given volume. Most
compact material ever produced!
8) Os(76) gives Ir(77) by neutron capture and β- decay. 2 nd most compact
9) Ir(77) gives Pt(78) by neutron capture and β- decay. Again high luster.. let's see
what happens next
10) Pt(78) gives Au(79) by neutron capture and β- decay. Since only one stable gold
isotope (197) exists, the origin must be the 197-Pt isotope. A twinkling yellow star was
 3
received (green in the vapor phase). Let's continue..
11) Au(79) gives Hg(80) by neutron capture and β- decay. Mother nature thought it is a
gas, since it vaporized right away but when condensing outside the core a liquid emerged.
Further neutron captures gave the thallium and lead, more solidified though fusible, soft
metals. We may assume some additional processes for gold:(a) 196-Hg +n + e- capture.
(b)198-Hg + fast neutrons bombardment provides the reverse route – splits a neutron to
become197-Hg going β+decay to, again 197-Au Notes:(1)198Hg has an earth abundance
of 0.0085ppm, similar to gold 0.004ppm. While 196-Hg is far less abundant (0.0001ppm).
This may serve as a clue to how nature produced gold. (2) Heavy isotopes of any element
tend to go β- decay, while lighter isotopes go β+ decay. Additionally, β+ decay is almost
non-existent above z=60. (3) Gold, and rhodium, have only one stable isotope each, as
odd numbered atoms whose abundances are generally lower then even numbered atoms.
Nuclear binding energy per nucleon, Rhenium - Mercury
Nuclear binding energy, Mev

7.98

7.96

7.94

7.92

7.9

7.88

7.86

7.84

7.82 Atomic number

74 75 76 77 78 79 80 81

However, the conclusion remains: only the neutron numbers decide the probability of a
certain noble metal to form. So they align with all other elements' abundance sequence
accordingly (beside what we said about gold and rhodium, which make troughs in the
abundance saw teeth graph). What is still uncertain, is how all noble metals occur
together. Why they always come with Nickel, copper, zinc and iron (the abundant starting
materials) is understood. But how, e.g. gold(79) , platinum(78) etc. will join silver(47),
palladium(46) etc.? probably because in the molten state they dissolve in each other
besides being heavy, enduring chemically so on physical and chemical – and not nuclear-
grounds they may be eluted together by water, gravity and wind. Nuclear sequence was
followed by a physical and chemical processes.. 75 percent of gold, as well as 'platinum
sisters' are found in placer deposits which are the result of elution by water streams
followed by deposition (eluvial deposits) and the rest - residual (alluvial) deposits which
were not carried due to being so heavy (this may be called “panning by nature”).
In that connection we'll remind some more riddles of nature: Rhenium(75) is found
with tantalum(73) and tungsten(74) (what is understandable), niobium(41) and
molybdenum(42) maybe by same reasoning – solubility due to column localization on
periodic table. Seems the answer is same for finding together abundant sulfur(16) with
selenium(34) and tellurium(52), having chemical and physical affinity, solubility in each
other. Platinum bonding with arsenic(PtAs2) and gold with tellurium(AuTe2) is probably by
gold and platinum being oxidized to their ions by I2 and Br2 respectively, periodical table
neighbors to abundant Te and As respectively, before being precipitated by the last two.
2.Why they are noble?
Noble metals are a particular case of transition metals. Those with relativistic contraction
(i.e. full 5d-band), comprising the heavy group, are even more unique.
 4
Gold, silver and copper dimers exist ,in gas phase, with dissociation energies (to atoms)
as 51.9, 37.6, 41 kcal/mol, resp., significantly lower then H 2 -104.2, unlike Na, Li, Mg, Ca,
Mg, Zn, Hg (a noble metal!). Gold is found in nature as pure material. Pure silver and
mercury result from their compounds by the action of light, heat...When the nuclei of
metals become larger, the attraction between the nuclei and the electrons increases.
Proceeding higher in the periodic table d-shells begin to be filled, s is already half occupied
(except Re, Os, Ir). The electrons in the d-shells have higher energy than s-shell electron.
They join in part s-electrons, forming the sea of electrons. Gold, silver and copper are
different, having minimal hybridization amount over Fermi level¹, what results in 1) Lower
melting points (softer metals). 2) Highest conductivities. This sea of electrons is the glue
causing most transition metals to be so dense, hard and of high MP's. In contrast – metals
without partially empty d-shell are softer, of lower MP's and of higher atomic diameters. In
case of reaction or conduction, in most transition metals, d-electrons hybridized with s-
electrons, make them sluggish,or directional rather than free, resulting in lower conduction
and slow reaction rates (passivation, kinetic delay). At one point, where the list of noble
metals light group begins (Ru, Rh, Pd, Ag), said attraction and enveloping glue combine in
raising the oxidation potential thus protecting any particular electron from reacting. In the
heavier group (Re, Os, Ir, Pt, Au, Hg), the relativistic contraction (p. 16) makes it still
harder, stabilizes further the contracted atoms. To look better into the electronic shell of
noble metals, we need to know something about electronic transitions. We'll limit our
discussion to a couple of outer shells – what determines the behavior. Let us start with
ionization – taking an electron from an a neutral atom and forming a positive ion from that
metal. The energy needed is from 7.6eV (silver) and over. For mercury for instance, it is
10.4, gold 9.2eV. This is well inside the UV (invisible) range. No change of colors result
(e.g. gold ion is yellow). Then we have band to band (e.g. s-p, p-d) transitions, mostly in
the UV range, but not only. Then inter band transitions, especially of interest in noble
metals, belonging, mostly, to d-block or transition metals, known for their ability to form,
in their compounds, visible colors (d-d transitions). Generally, but not always, this occurs
when d sub shell is almost full, (less when it is full), there is a tendency for d-electron to
“jump”, hybridize with s-electrons and be involved in reactions, complexes formation,
conduction, luster, depending on position towards Fermi level; involve in gas adsorption.
When electrons are “lost” to ligands they become “bonds” and may shift Ligand To
Metal Charge Transfer (LMCT) or vice versa (MLCT),vibrate, rotate by absorbing energies
in the infrared. Then red to UV, in between giving rise to visible colors. In LMCT case the
colors are deep, intense. This charge transfers differ from transitions, they're more like a
shifting, moving towards one direction or another, so positioning electrons closer to the
acceptor side. From organic chemistry, we know about electron couple de-localization and
stabilization, where it is described by a curved arrow, accompanying an existing bond
which is described by a straight line. For example the electrons taken from two potassium
atoms to chromate ion may be shifted towards the Cr+6 ion. This shifting absorbs a peak
wavelength of 0.37 microns, and looks pale yellow. If Pb++ replaces K+ the peak is 0.43
(resulting in deeper yellow) and if silver(0.45 microns)resulting in orange- red. You should
take in account the “width” surrounding the peak and getting over to the higher values.
E.g. The peak of 0.45 has complementary color of orange (p. 12) but 20% weaker
absorption at 0.47 has the complementary red etc. Conclusion: shifting electrons in the
presence of Ag+ ion is easier then Pb++, lead easier then K+. In other words, K+ is best
acceptor, of electron previously gained from it. When it takes less energy, a higher
wavelength absorbed, a color of higher wavelength (0.4-0.58 microns – see p.11) results.
 5
..
O:
.. ll
2 K+ - :O ̶ Cr = O:
·· l ··
- :O:
··
electron couple de-localization in chromate ion

The specified absorptions are exemplified in the following graph, also typical of many
charge transfer absorptions, namely, a single, quite symmetric peak in the visible region.

Chromates visible absorptions

B=K2CrO4, C=PbCrO4, D=Ag2CrO4
0.35
Relative intensity

0.3

0.25
‫ע מו ד ה‬ B
0.2 ‫ע מו ד ה‬ C
0.15
‫ע מו ד ה‬ D

0.1

0.05

0 Wavelength, micron
0.32 0.34 0.36 0.38 0.4 0.42 0.44 0.46 0.48 0.5

Additionally band gap considerations give rise to transitions, e.g. from valence band to
above Fermi level conduction band, a transition also often involved with visible colors, if in
the same energy range. However, this last transition does not necessarily involve a
transition metal. Here is a reminder: a table of visible colors and wavelengths
(approximate, since they merge with each other), energies associated with them:
14 1
wavelength λ, microns energy E, electron volts frequency,10 sec¯
ultraviolet 0.3 and less 4.1 and more 7.31
violet 0.42 (0.4-0.425) 2.93 7.14
blue 0.47 (0.425-0.5) 2.64 6.38
green 0.53 (0.5-0.57) 2.34 5.66
yellow 0.58 (0.57-0.59) 2.14 5.17
orange 0.6 (0.59-0.625) 1.93 5
red 0.7 (0.625-0.74) 1.77 4.28
infra-red 1 and more 1.24 and less 3

each color is associated with energy, according to:

(1) f (frequency) = c/λ, where c is light velocity in air, 3x10¹º cm/sec, and λ =
wavelength. Take for example, red:
 6
4 14 1
f= (3x10¹º cm/sec)/0.7x10¯ = 4.28x10 sec¯
14
this means a red photon oscillate 4.3x10 times per second! (more than that, our eye can
differentiate between frequencies of that magnitudes!)
Down below there is a graphical representation of red photons, showing wave and
quantized character and color sensualizing ability (imagine flow of many). Now, when
associated with an electron of mass me, charge e, absorbing a red photon will increase its
energy by 1.77ev (emitting – decrease) since

1) charge x potential = energy

2) E (energy) =hxf

34
where h = Planck's constant = 6.62x10¯ m²kg/sec, f= frequency (fluctuations per
second). Again, take red

34 14 20
E = 6.62x10¯ x 4.28x10 = 28.334x10¯ joule , joule being wattxsec

19
whereas electron charge equals 1.602x10¯ coulomb, coulomb being amperexsec

20 19
therefore, red photon energy = 28.334x10¯ / 1.602x10¯ = 1.77 ev. In short,

wavelength λ = 1.239/E, E=energy, ev. And so the whole above table was built.

Now, where are energies of this magnitude found inside metal atoms or ions? Of course,
in d-d subshell electron transitions or d-surroundings transitions. The red photons shown
above are part of the white light we know. Provided there is such a transition in the
material hit, when the red photons interact with the d-electrons (absorbed) causing them
to be in the excited state, then a cyan color will be perceived, which is what left, or
complementary color) of all the components making the white light. You have in fact in
this case a filtration of one of light ingredients.

3.Copper
Copper is related to noble metals for several reasons. 1stly, it oxidizes electrochemically,
namely, loses an electron, harder than hydrogen (0.337v vs. H). All metals having this
 7
character, especially from copper and higher are considered noble. Ennobling means (in
chemistry) is rendering a material not rusting or being etched by its environment (what
begins with said electron taking). Copper surface will remain unstained and shiny in the
absence of water, for a long time. Similarly to gold (see p. 31) losing 1 electron (0.54v) is
harder than 2. Copper's conductance electrons are, almost perfectly enveloped by Fermi
surface having form of almost perfect ball in the case of copper, silver and gold. This
means that valence electrons are fully used for conducting (electricity or heat) by full
overlapping of conductance band with valence band electrons, below Fermi surface. This
is why copper, silver and gold are the best conductors, having conductivities well over that
of other metals. All three belong to “electron rich metals” like Al and Mg which will not
spontaneously adsorb “electron rich” hydrogen. And this is another reason why those
three are called real noble metals (by physicists). Few words about adsorption,
hydrogen taken as test case:
The adsorption of gases involves interaction between the d-orbitals of noble metals and
molecular orbitals of gases, notably H2, CO, NO, NO2, O2, H2O, CO2, N2. Of special interest
are platinum, palladium and rhodium. The irregularity of Fermi surface, especially crossing
of it by d-bands (2 for platinum), gives rise to those interactions. Unlike gold, silver and
copper, which have almost perfect (spherical) Fermi envelope, also called the electron rich
elements and hence, can't adsorb “electron rich” H2, neither readily adsorb other gases.
On the other hand they will be readily liganded by CN-, a strong electron acceptor.
4. Hydrogen adsorption
The molecular orbitals of hydrogen (H2) include only filled bonding orbital σ and an
empty σ* anti bonding orbital.
To adsorb it, an interaction between the nonbonding orbital and “mobile” d-electrons
from unfilled metal d-band is needed. Nickel, which is lower only in one atomic number
than Cu, will have strong spontaneous interaction with hydrogen, adsorbing it as: H-H
because it has just two more vacant d- positions. Every line in the scheme / \
represents 2 electrons. In contrast Cu Fermi level (also Ag, Au) is not crossed by Ni - Ni
d-electrons. Adsorption will be accompanied by exothermic heating. For dissociating the
H2 adsorbed on Ni an energy should be injected, to transfer 1 electron from σ to σ* (as 1st
step). Here the adsorbing metal acts as a catalyst, namely, reducing energy requirements
for a given process. So, the energy gained at the adsorbing stage, facilitates dissociation.

H2 filled σ bonding molecular orbital H2 empty σ* nonbonding molecular orbital

H· ·H

Now, let's get back to copper:

Electronic configuration – Cu
3 4
sp d s
2 6 10 1
7 -1 -1
electric conductivity σ: 5.9x10 m Ω. Oxidation potential 0.34v
n, the number of (assumed free-) electrons per cubic centimeter of metal, for copper (1
free electron per atom) - 6x10²³ in 63.6g of density 8.92 gives n=8.4x10²²
The time between collisions of electrons in nuclei inside a metal of electric conductivity
 8
σ and n free electrons per cubic cm:
18 7 18 14
for copper it is τ= σx8.1x10¯ = 5.9x10 x8.1x10¯ = 2.5x10¯ sec
nx23x10¯²º 8.4x10²²x23 x10¯²º
7
as electrons have thermal velocity around 10 cm/sec, it gives free path of 25 angstroms,
approximately 9.7 copper atom diameters (D), which has to be calculated: e.g. copper,
like many metals has the Face Centered Cubic (FCC) configuration, meaning 4 atoms in a
cube whose face diagonal equals 2 atoms D(=diameters). Therefore, the cube side equals
1.41 D's, its volume 2.82 D³. That means, 74% of 4 cubes containing 4 copper atoms of
diameter D. In the case of BCC structure, e.g. Sodium, which is less compact, the volume
diagonal of unit cell equals 2D's, in this case the packing ratio would be 68%. Fermi
calculated velocity at 0°K: instead of thermal velocity, he assigned electrons with Fermi
velocity (at the Fermi surface, 0ºK), which is dependent only on the molar volume of the
element, and number of free electrons. In the case of copper (1 free electron):

VF = ( 2EF/m )½ , where m=electron mass, EF = copper's Fermi

8 7
energy, equaling 7ev. That gives VF for copper of 1.57x10 cm/s (instead of 10 ) and the
mean free path becomes 386 angstroms(!)
7
Sodium, electric conductivity σ = 2.1x10 with density 0.97 and atomic weight 23 gives

22 7 18 14
n=2.5x10 , τ = 2.1x10 x 8.1x10¯ =2.9x10¯ sec
2.5x10²²x23x10¯²º
7
free path 29.2Aº. ( 93.8 according to Fermi) Aluminum, σ = 3.53x10 with 3 “free”
electrons, density 2.7 and atomic weight 27 gives
14
n=18x10 ²³ x2.7 that is, 1.8x10 ²³ and τ =0. 69x10¯ sec, free path 6.9Aº
27
(49.1 according to Fermi velocity).
The following table gives results for 3 common metals together with the 3 “noblest”
metals, namely, copper, silver and gold.
What we learn from it, that the noblest metals are very transparent to electrons in
comparison to “common” metals, giving an electron ability to “cross” 9.5, gold (131.3
according to Fermi) atomic diameters, 9.7, copper (151) and 13.1, silver (183) until
colliding and changing direction. This is versus free paths 8(94), 2.4(49), 1.75(32) atomic
diameters for sodium, aluminum and zinc respectively. It is obvious that silver, copper and
gold (sometimes called the royal metals) are giving the sea of electrons the best flowing
conditions. Notice: gold and silver have about equal molar volumes, hence equal Fermi
energies. However, they are not able to form the Cooper conducting electrons pairs (at
low temperatures), which produce superconductivity, as will be described below. Nobility
≠ superconductivity.
 9
5. Fermi level, conductivity and superconductivity
The behavior of the ‘royal metals’, Cu, Ag and Au near the Fermi envelope deserves
additional explanations. The existing concept is: d-bands of the 3 metals are filled and
narrow and are contained completely within the Fermi level:

d-band
Fermi
LEVEL
L

STATES
No. OF

s-band

ENERGY

On the other hand, we consider d-electrons as an envelope which protects the s-electron
from reacting especially in gold and the rest heavy elements within the noble metals
group, for which the relativistic contraction causes s-lonely electron to be hidden for
reaction. However several papers show the existence of d-originated positions over Fermi
level, few in copper, silver and gold and higher numbers for other noble metals.
Furthermore, the number increases with temperature, as the population probability arises
by going from zero temperature to higher temperatures. So is there a crossing of Fermi
level for these metals by d-electrons or not? And why this is important at all? To settle the
dispute we need to assume that d-originated positions (Nd) over Fermi level are based on
sd or spd hybridizations. We summarize the information about copper, silver and gold²:
Nd Ns Np Nf N(0)=total
Copper 1.99 0.56 1.42 0.03 4.00
Silver 1.03 0.77 1.70 0.04 3.54
Gold 3.7
Palladium 30.6 0.30 0.50 0.19 31.6
(for comparison)
What we see, is low density of states as a whole and particularly of d-origin on Fermi
envelope of royal metals vs. other noble metals. The role of d-electrons crossing the
Fermi level in transition metals (of which noble metals are part) is causing them to be
harder, or raising their melting point, by forming directional bands, rather than free-to-
move-in-all-directions electrons. On the chemical side the transition metals are sluggish in
reactions, and become easily passivated during reaction. So, on one hand, it is clear why
Cu, Ag and Au have low MP’s and are consequently relatively soft, having full 10 d-
electrons with slight inclination for a d-electron to part from the full d-band. On the other
hand some curiosities arise, e.g.:
1) Platinum, similar to palladium, having many d electrons over Fermi level (the base level
of conduction band), 1 -6s electron. How come its electrical conductivity is 4.75 times
lower than that of gold, with 1-6s electron and minimal Nd?
2) Sodium with 1 free 3s-electron, has lower electrical conductivity than gold
The 2nd question is simpler, we assume for simplicity a similar thermal velocity for the s-
electron of Na and Au, and 1 conducting electron for each atom, despite the different
attraction from the nucleus, hence the difference is mainly by the population of s-
electrons. Au – 5.88x10²² per cc, Na – 2.53x10²² per cc, because gold density is 19.9
times that of sodium. What means that on weight basis sodium is a better conductor
 10
electrically.
The 1st question is harder to answer, but definitely the platinum s-electron is not free,
the d-electrons crossing Fermi level, hybridize with it, the bands which are produced are
directional. So we could assume that the minimal number of d-electrons crossing Fermi
level in gold also are hybridized with s-electrons so lowering its conductivity rather than
increasing it. A Japanese researcher says both issues contribute, presence of d-states over
Fermi level and the hybridization they cause with sp bands to render the conducting
electrons ‘not free’. In this respect, silver is the best conductor by having practically
almost no d-bands crossing the Fermi level³. On the other hand, this causes silver to be
more vulnerable chemically than gold. As a consequence, here is the ‘conductivity track’
for the 3 most conductive metals:
7 1 1
SILVER 6.28 x 10 Ω¯m¯

7 1 1
COPPER 5.90 x 10 Ω¯m¯

7 1 1
GOLD 4.52 x 10 Ω¯m¯

Conductivities, electron velocities, free paths for several metals:

Metal and structure Copper, FCC Sodium, BCC Aluminum, FCC Gold, FCC Silver, FCC Zinc, HCP
Atomic weight 63.50 23.00 27.00 197 107.9 65.4
Density, g/cc 8.92 0.97 2.70 19.3 10.5 7.14
Electric conductivity,Ω ¹ ̄ m̄̄¹ 5.90E+007 2.10E+007 3.53E+007 4.52E+007 6.28E+007 1.74E+007
Free electrons per atom 1 1 3 1 1 2
Free electrons per cc 8.46E+022 2.53E+022 1.80E+023 5.88E+022 5.84E+022 1.31E+023
Time between collisions, sec 2.46E-014 2.92E-014 6.91E-015 2.71E-014 3.79E-014 4.68E-015
Mean free path, classic, cm 2.46E-007 2.92E-007 6.91E-008 2.71E-007 3.79E-007 4.68E-008
Aº 24.7 29.2 6.91 27.1 37.9 4.68
Atom diameter, Aº 2.55 3.67 2.86 2.88 2.88 2.68
Atomic volume, cc per atom 1.19E-023 3.95E-023 1.67E-023 1.70E-023 1.71E-023 1.53E-023
Free path in atom diameter 9.68 7.95 2.42 9.42 13.14 1.75
Lattice constants a, b, c 3.61 4.24 4.04 4.07 4.082.66, 4.93*
Unit cell side, cm 3.62E-008 4.29E-008 4.05E-008 4.08E-008 4.09E-008
Unit cell volume, cm³ 4.75E-023 7.90E-023 6.67E-023 6.80E-023 6.85E-023
Fermi energy, ev 7 3.94 11.7 5.53 5.49 9.47
Fermi velocity,VF cm/sec 1.57E+008 1.18E+008 2.03E+008 1.40E+008 1.39E+008 1.83E+008
Mean free path, Fermi,, cm 3.86E-006 3.44E-006 1.40E-006 3.78E-006 5.27E-006 8.54E-007
In atom diameters 151.23 93.77 49.08 131.33 182.58 31.88
Γ(Cai-Shalaev) for comparison s ˉ¹ 1.40E+014 9.20E+014 1.08E+014 3.20E+013
Mean free path, VF/Γ , cm 1.12E-006 2.21E-007 1.30E-006 4.35E-006

We added in the table, newer estimates, based on damping factor, Γ which takes into
account that some of the electrons are not really free, but bound (e.g. d-electrons, see
cover drawing). For silver, with the low Γ , the free path is almost identical, however for
 11
gold, copper and aluminum the free path is decreased 3.5, 3, 6 times respectively (so
“correcting” somewhat back towards classic values). But the story does not end with that..
Today, electric conductivity of most metals is considered the result of electron-phonon
interactions. What are phonons? If we look at an electron moving very fast among
protons, we may imagine that the protons enter into vibrations as the electron attracts
them by passing nearby. This vibration has a typical frequency ω and is called a phonon.
If the electron velocity (at 0ºK) is v, then λ, the coupling factor between electrons and
phonons is directly related to N(F) v² and inversely related to Mω², where N(F) is the
number of states at the Fermi level and M the atomic weight. Here are approximate*
coupling factors ( dimensionless):

Pure element crystal form N(F) λ superconduct

Cu, 29 FCC 4.1 0.15 no
Ru, 44 Hex 15 0.30 (0.71?) yes
Rh, 45 FCC 18.2 0.37 yes
Pd, 46 FCC 29.9 0.62 (0.4) no
Ag, 47 FCC 3.6 0.13 no
Re, 75 Hex yes
Os, 76 Hex yes
Ir, 77 FCC yes
Pt, 78 FCC 28-9 0.66 no (only powder)
Au, 79 FCC 3.7 0.14 no
Hg, 80 RHOMB yes
We added a last column in the table above showing some noble metals will show

*based on several calculation methods

super-conductivity at very low temperatures, 'mediated' by same phonons which slow the
flow of electricity in 'normal' temperature. Super-conductivity in metals means the ability
to form pairs of electrons which will flow indefinitely if a small current is applied. A low
coupling factor with a low number of electronic states in the Fermi surface N(F) as seen in
the almost perfect spherical Fermi envelope of Cu, Ag and Au – inhibits superconductivity.
Platinum has high N(F) but a low coupling tendency, so only powdered platinum will show
SC. Palladium is exceptional, electron-para-magnon coupling (Stoner effect) not permitting
cooper pairs to be formed. The other elements show vast imperfections in the Fermi
surface which imply a high density of states there, what aids in superconductivity. The
reason for high electrical conductivity in silver, copper and gold (sodium as reference), is
neglecting velocity changes of their conducting electrons and higher than 1 conducting
electron probably due to ds-shells hybridization (on one hand; on the other hand this
hybridization causes a loss of conductivity) is mainly higher atomic population due to
higher density. The conductivity increases further towards the absolute zero temperature,
but unable to reach infinite value that is by forming electron pairs.
From conductance back to valence electrons: Bivalent copper Cu++ will have 9
electrons left in the d-subshell. When a copper II sulphate, in hydrated crystals or in
solution, are illuminated, red photons conforming to 0.7 (up to 0.9) microns will be
absorbed, by having two energy levels in the Cu++ ion d-shell (splitting of shell). One,
assigned to 3 orbitals with 6 paired electrons and 2nd, a higher one, 2 orbitals with 3
electrons of which one is unpaired (all in all 5 d-orbitals) The transition from the 1 st, low
level to the 2nd, absorbs the red and leaves the cyan (its complementary color). If 4 NH 3+
groups replace H2O
 12
around the Cu ++ ion, a bigger gap will form, thus giving only 2 orbitals with paired
electrons, consisting the lower energy level, and other 3 orbitals, one of them with
unpaired electron, consisting the higher energy level. Thus a higher energy photon will be
needed for transition – a yellow one, making the copper ammoniacal complex dark blue
(which we all know). Notice that spin direction during transition is conserved (exhibited by
an arrow). Bear in mind, that all d-d transitions are spin allowed, that is conserving the
spinning direction.

Cu++ ion d-shell

<
red photon absorption

hydrated Cu++ d-shell (splitted one way)

<
yellow photon absorption

ammoniacal Cu++ d-shell (splitted 2nd way)

We said d-d transitions or d-surroundings...how about monovalent copper (which does

not have them)? Generally it would have no color, but let's take copper I oxide. When
copper is heated to 950ºC with 20mm mercury pressure of oxygen in a closed quartz tube,
it transforms to Cu2O, red copper I oxide (cuprite). Instead of the “regular” mingling of
copper lone electron from s-shell with one of the 10 electrons filling the d-shell, thus
giving the “regular” valence of copper which is 2 (with “regular” blue or green color- when
liganded), in this case the copper is mono-valent and it is orange-red. Also, cuprite is
diamagnetic distracted by a magnet, what is expected from a filled shell material, with no
unpaired electron. So, we have a copper ion with filled d-shell, no d-d transition possible,
where the color comes from?
Let's have a look at cuprite visible absorption spectra, for nano-powder, including one
bulk cuprite absorption peak for reference (kind of schematic spectra):
 13

nano-COPPER I OXIDE ABSORPTION

4.5

4 Bulk copper I oxide

relative intensity

3.5
<------ blue shift
3

2.5

1.5

0.5

0
0.2 0.3 0.4 Absorpttion
0.5 wavelength,
0.6 , micron
0.7 0.8 0.9

We see the following characteristics: 1stly, a difference between nano and bulk
powders, namely, bulk absorbance is red shifted, versus nano which is blue-shifted,
meaning, absorbing more to the blue side, therefore it is oranger, or yellower then the
bulk cuprite - a difference in color caused by size. 2ndly, a wide range of violet, blue and
green absorption, ended by a wide peak in 0.49 micron, that is, blue (for nano) or 0.57
micron, that is, green-yellow, for bulk. Note: the absorption stretches back to ultraviolet,
“complementary color” of which does not exist.
To make that clearer, in the following graph, one can see that passage from 0.57 to
0.49microns in the absorbed wavelength leads to passage from about 0.8 microns (red) to
0.6 microns (orange) in the observed wavelength. Less red is more blue – that's “blue
shift”. A further explanation: electronic transitions start somewhere in absorbing the high
energy and low wavelength of UV (invisible) resulting in white, then climbing in
wavelength and decreasing in energy to violet and blue, where yellow and pale green are
the resulted colors. Further decreasing of energy for e.g. blue and green results in orange
and red. This ends with IR absorption, resulting in black.
 14
Complementary vs.absorbed wavelength

Complementary wavelength, micron

0.9

0.8

0.7

0.6

0.5

0.4

0.3

0.2

0.1

0
Absorbed wavelength, micron
0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85

If you are in the middle range between violet-high energy and red-low energy
absorptions, an increase in absorbed wave energy can take you left, that's a blue shift. A
decrease in absorbed wave energy will take you to the right – that's a red shift.
The last peak in the former graph is referred to d-electrons jumping into conducting
band - overcoming band gap - of 2.17ev for the semiconductive bulk cuprite and about
2.5ev for the nano-cuprite.
The story is like this: the process of copper oxidation does not stop with Cu2O. Some
Cu2O molecules add additional oxygen atom and become 2CuO. This situation is called
nonstoichiometry (of Cu2O), causing a defect structure (in a filled band), where the
changing local Cu valence can wander from atom to atom along the lattice. Now, valence
can decrease by a gain of an electron,
(4) Cu++ + e- = Cu+
or increase with a gain of a hole,
(5) Cu+ + h+ = Cu++
In Cu2O, we have a positive Hall coefficient, up to 500ºC. That means the majority
carrier is holes. Another simple means for deciding that is finding the thermoelectric
effect, positive voltage when heating means = holes. The hole is mass-assigned, in the
case of Cu2O, 0.25me ( so, a slow hole). The best way to look at it is viewing the holes as
negative electrons, so flowing with the electric field, if any, contrary to electrons. Below
300ºK, excitons that is a unit paired of a hole and an electron, exist too. Those particles
form a whole set of light absorptions, e.g. “yellow exciton” (which by absorbing a yellow
photon dissociates to a hole and electron) especially in the ultra violet down to blue, which
add to the absorptions in that range, ending with the said broad peak at 2.17ev, (0.57
microns) which is about green-yellow (conforming to electrons, jumping from valence
band to conductivity band) and then drifting in the red region. This strong
absorption leaves Cu2O with red color as can be verified by the above graph. The hole
formed in the filled bands of Cu , creates a new “defect energy level” or “impurity level”.
When 1 of 2 electrons from “defect level in full band” of O in Cu2O are excited to the
conducting band level a red photon around 1.5 ev is absorbed (contrary to red
reflectance). Why should they be excited? Remember that being near room temperatures,
we are high above 0ºK, what means everything is absorbing energy (heat, light). Light
excites - absorbed in part and gives color. Part of the excited states, return to unexcited
state so cause heating. An equilibrium is established. However, the sum of those
 15
absorptions and reflections, is a net reflection of red-orange. The energy level of the
conduction band - 2.173ev above valence band is called E G, energy gap. According to
theory Fermi level in p-materials is a little below, say about 0.6ev below conduction band
energy, so if electron, is to absorb energy up to the edge of Fermi level (EF) it will use the
difference, about 1.5ev, conforming to deep red-IR. This is the difference in color
mechanism between red cuprite and blue-green copper compounds.
Let us mention also that “single crystal” that is, a pure crystal of cuprite has also the
hole character (without defect introduction).
Now, how about Cu++ in CuSO4.5H2O and in CuCl2.2H2O or in their solutions, they are
blue and green, respectively, while CuSO4 and CuCl (Cu2Cl2) are colorless. Explanation? Of
course, when one of 10 d-shell electrones mingles with lone s electron to form the “+2”
valence, an orbit is emptied in the d-shell, enabling d-d transition – in the case of copper,
blue. Cu+ in CuCl, that's an easy one – all d-shell filled and absence of defects. Same for
Cu(NH3)+, Cu+ in CuCN. But how about CuSO4 (anhydrous)? The reason why it is
colorless, unlike cobalt or iron sulfates, which also are transition metals? Well, the answer
is, that anhydrous CuSO4 is highly covalent (for comparison anhydrous H 2SO4). Copper
sulphate is conforming in structure to... zinc sulphate, which is electro-valent, in
everything... except one – a pre-edge x-ray absorption attributed to... again, what a
miracle, 3d-hole delocalized into the sulphate anion, causing it to become more radical
like, instead of anion like. The end result is covalence, meaning no clear cut between
copper and sulphate ions, a molecular unit without the red absorption (or cyan color)
characteristic to hydrated copper++ ion.

6. Colors of gold, copper and silver metals

Until today...
you may have thought you know and understand why metallic silver is white, copper is
red and gold is yellow. Let me surprise you: you may do not know.
Let us start with gold. You may have found somewhere that gold atom “captures” the
yellow part of light, what raises its energy, then emits the yellow photon and returns to
initial energy. Other less mistakable explanations exist.
What wrong with this concept is few things.
(1)To look yellow (around 2.1 - 2.17 eV) gold must absorb not in the yellow but in the
violet part of daylight (of higher energy around 2.9 -3.1 eV), what in fact it does
(2)The reason to absorb energy looks reasonable since the whole universe is in a state
of absorbing energy by being at higher temperature than 0ºK and in illumination (at
least during day) so every object is absorbing energy but why to emit, give it back?
(3)If an object absorbs in yellow, it looks violet “gives more energy than it takes?” so
how about the energy conservation here?
(4)We may assume that the reflected (or transmitted) energy is lower than absorbed,
what happens to the rest energy? Raises further the energy of the object? (so again
what reason to return to initial state? And what the mechanism?
(5) And... if it did not return to initial state, will it stop absorbing and looking yellow?
(6) Duration. The photons are very quick. So how the atoms absorb them (a matter of
ability+probability)
(7)Suppose that the energy absorbed, raised electron from d, which is full, to a vacant
state. The return back to full band is close to impossible (on probability ground)!
(8) And, if it absorbs, e.g. blue photon what will be returned is, at most, blue photon,
not yellow.
Let's clear things starting from the simplest metals, namely alkali metals having full
 16
bands and “free” s-electron. What characterizes the electron transition is the easy
transition from valence band to conductivity band, including passage of Fermi level, mostly
by photons in the range of IR and very few transitions up to 2eV. The spectral reflection
curve is sloping moderately in the visible range, hence they will look white.
Then let's continue to transition metals. D-bands, which are not full, cross the Fermi
level in addition to s-bands, again making the passage (from both bands) to over Fermi
level, easy and continuous. That is, reflectivity curve has no abrupt changes, no troughs,
just a moderate slope (in the visible range), giving no advantage to a specific absorption.
The naked eye will observe white, sometimes gray.
Gold, silver and copper are unique in electronic structure, hence characteristics (e.g.
highest conductivities). Full d-band, single s-band electron and d-s gaps which happen to
be close to visible photons energies. MOST IMPORTANTLY THOSE METALS HAVE ABRUPT
CHANGES IN THE REFLECTIVITY CURVE. Look at the curves of copper silver and gold
reflections below – behaving in accord with their densities of states (that is, population of
energy levels), observe a stepdown change in reflectance, parallel to an accumulation and
a peak in DOS at the same energy. Silver – in UV range. Therefore, silver is the ultimate
reflector (and conductor) in the visible range. The step changes in the visible range is
exactly what makes copper and gold colored. What is the origin of this step changes?
The step changes, parallel with the onset of the increase in density of d-states. Mathe-
matically speaking the density of states curve relates to the derivative of reflectance curve
for the metals Cu, Ag and Au. Meaning – high probability for this d-population (DOS
peaks) to climb the gap, provided the appropriate quanta of energy are supplied. For silver
it is of course in the IR – hence invisible (and easier). The following table shows calculated
D-band and energy gaps derived. Computed with one (of few) method, it shows a trend:
element Fermi level, eV D-band top*, eV gap eV
copper 7 4.3 2.7 visible
silver 5.49 4.99 0.5 IR
gold 5.53 3.43 2.1 visible *calculated

copper silver gold zinc light reflectances

120

100

80
Zinc
Copper
60
Silver
Gold
40

20

0
Energy, eV
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5

The unexpected low level of d-band top of gold, is certainly referred to the relativistic
contraction of gold atom.
 17
Copper silver and gold electronic structure
Inter band transitions
1 2 3 4 5 6 (in the visible range)
s p d s p d s p d s p d s
copper 2 2 6 2 6 10 1 (stable) to:
2 2 6 2 6 9 2 (less stable)
silver 2 2 6 2 6 10 2 6 10 1 (stable) none
gold 2 2 6 2 6 10 2 6 10 14 2 6 10 1 (stable) to:
2 2 6 2 6 10 2 6 10 14 2 6 8 3 (less stable)
2 2 6 2 6 10 2 6 10 14 2 6 9 2 (less stable)
What we see, for copper and gold there are possible transitions between the more
stable and the less stable configurations, what needs an injection of energy.
Copper has inter band transition absorbance at around 2.1eV (=yellow, which gold does
not absorb) in addition to range of absorbances at 2.25- 3eV (=green, blue, violet.
Including a weak step from top 3d-band to Fermi conductance band 2.7eV) and 3-4eV in
UV edge. The sum of all absorbances acts as green. Hence copper is red-orange at around
650nm (1.9eV) which is the green complementary. Let it be stressed out that without
using the Fermi level, although adjacent, very close to s-band in metals, the picture will
not be complete. Addition of zinc to copper (brass) raises the reflectance around yellow
thus imitating gold (see graph above). Continued on p. 18

visible Infra red

UV
We conceive noble metal surface as a labyrinth containing
energy openings (and barriers among openings which do not
exist for white metals in the visible range): Narrow wavelength
openings for UV rays of high energy over 4.1eV
Intermediate wavelength openings for visible rays 1.24 – 4.1eV
Wide energy openings for IR rays <1.24eV. Light components
may be absorbed (pass if the layer is extremely thin) in the
appropriate opening, provided the entrance probability exists,
if their energy is higher than the opening width, reflected if
smaller (unlike semiconductors, transparent below energy
threshold).
 18
Gold 2.3eV (=green) and 2.5- 3eV (= blue, violet) and 3-4eV in UV edge. Sum= violet.
Hence it is yellow ͠ 590nm (2.1eV). Adjacent absorbances by jumping below and above
Fermi level (e.g 5d top– Fermi, 2.38**eV – green). A lonely electron can jump from d to
the s band with close energy, besides merging of 2d and 1s electrons. (The phrase “gold
electronic enigma, 1, 2 or 3?” comes from this).
** notice the difference from calculated value

The drawing shows a daylight beam, passing through a

prism which refracts it into color components, then meets
a gold surface (with same results for the original and
separated beam). The gold lets enter/absorbs violet,
blue, cyan and a fraction of green, adjacent colors
complying with close electronic transitions: 1d-electron to
s subshel, 2 d-electrons to s-p subshells, electrons from
d to above Fermi level (conduction band). Yellow, red
and smaller part of green, are not absorbed. However
the human eye senses mainly yellow and remaining
green.
 19
Silver – absorbances up to IR range of 0.5eV (low frequency, low energy) contribute
activate the electronic states inside the conduction band, forming series of currents and
dissipations, ending in differential heating. Inter band absorbance around 3.8eV, that is
UV range, invisible to human eye hence silver is white and shiny.
Now, look at each of the inter band transitions as a guitar chord. An optical chord
(instead of acoustic chord). It is associated with a specific frequency and specific energy
quanta (related to said frequency) in the visible, or non visible radiation, e.g UV, IR,
Roentgen...(instead of sound frequency) and - instead of injecting energy by fingers, what
activates the “chords” is electromagnetic waves\photons. Both can never be seen because
they own light velocity. The chords provide “passages”, “barriers” in accord with incident
rays interaction with them. Interlayers (defects) provide damping (see 1 st drawing).
A certain frequency/energy of photon or wave will have the probability of causing the
chord to vibrate - electrons able of having comparable or lower frequency of oscillation -
to oscillate (between energy levels if d empty enough) and absorb energy. This includes
electrons close enough to surface. Until wave attenuated or damped. If thin enough
metal, the green, blue and to a lesser degree others, will propagate through bypassing
electrons on probability grounds. And this time the human eye will sense mostly the green
(same for copper). However light is absorbed, unlike sound which is emitted. The “stable”
state is returned when the oscillation was finished (damped).
How many incident photons "succeed” (oscillating electrons) is probability dependant.
During damping, a heat will be produced...and the metal temperature will rise differentia-
-lly. The multiplicity of photons and atoms + damping to initial state, enables the
continuity of coloring process. A simulation of photons is shown, showing the quantized
and wave characteristics. The cause of oscillation is the electromagnetic character of
photons (not shown). To conclude, an equilibrium is formed between emptying and filling
electronic levels, degree and kind of illumination and shine.

Last, but not least, can the electromagnetic wave 'avoid' the 'trap' described and bypass
the electromagnetic medium. Can the wave “ignore” the medium? Of course not, the
interaction (gold – yellow, copper – brown-red twinkling) is immediate (of light velocity),
and repeatable. On the other hand, white metals have no 'obstacles' on their gently
sloping reflectivity curves, in the visible range (at least) hence they give equality of colors.
Now, when we see yellow, in “normal” light, it means the other components of
spectrum, red, violet, blue orange, green, altogether can be summed as violet, were
absorbed, leaving the yellow.
On the other hand, illumination with violet light can color an object violet. Because
of absorbing probability lower then 100%, some violet is reflected.
Look at the following gold refletances, at visible:(approximate, depending on surface
conditions)
wavelength, micron 0.420 0.450 0.500 0.550 0.600 0.650 0.700
approximate color violet blue cyan green yellow or-red red
reflectance, % 29.3 33.1 47.0 74.0 84.4 88.9 92.3 (electrolytic gold)
26.5 30 49.5 65.5 73.8 79 83.6 (non electrolytic)
 20
What we learn here, that violet, blue and blue-green are strongly absorbed by gold.
Green, intermediate, yellow red and orange are strongly reflected. However, the human
eye response to yellow is the highest. Note the difference between reflectance and 100%
which is responsible for permanent optical absorption.
Next, observe the human eye reaction to colors:
Color Human eye color sensing (luminosity function):
0.450 micron 0.05
0.500 0.3
0.550 1
0.58 0.9
0.6 0.5
0.65 0.15
Orange, red are reduced significantly vs. yellow, even though they are well reflected by
gold. Bear in mind also that yellow is visible also in the orange and green light
components.
This is why the human eye defines gold as yellow, sometimes with orange and green
hints. See drawing below. 'By the way' gold vapor is green, since it loses the green
absorbance. Probable reason: Gold Au2 mollecules are formed so the s electron is
occupied, not permitting sd orbitals merging.
Copper is another simple case. With the significant yellow absorbance, the dominance
of yellow which signifies gold is non-existent in copper, “leaving the field” for red, orange.
7. What are the 5 shiniest metals? Gold, copper and silver shininess (glance)
By glance or shimmer we mean an extraordinary shine in the visible light region. The
phenomenon is multiplying the shining reaching our eyes many times. How it is explained?
There are 5 metals which shimmer. These 5 metals are:
Aluminum
Zinc
Copper
Silver
Gold
What distinguishes those metals is a refractive index n significantly lower than 1 (in this
visible region or part of it). Using more complicated terms, the real and imaginary
dielectric constants (permittivities) hold a relation that enables a standing light wave
(resonance of plasmons - electrons) to be produced instantaneously along the surface of
the metal when it is hit by a light wave. This coherent appearance of practically infinite
number of light waves to the observer eyes is the essence of brilliance. See drawing.
Other metals have this ability in the infra red light region, that is invisible to human eyes.
Gold and to a certain extent silver, maintain this brilliance for long owing to an existing
transparent skin of few nanometers over the bulk metal (which is reflecting). Copper,
aluminum and zinc on the other hand become covered with surface films inhibiting the
glance.
Gold is thereby used to characterize adsorbed species of many kinds (e.g. DNA) by
measuring the effect on the glance and color they create.
 21

A standing wave formed on gold surface

8. Mercury
Electronic configuration - Hg
5 6
sp d f s
2 6 10.. 2
6 -1 -1
electric conductivity: 1.04x10 m Ω. Oxidation potential 0.79v
notice: Hg conductivity is 1/57 that of copper.
Mercury is certainly a noble metal. It is harder to oxidize then copper, comparable to
silver. Its surface will remain unstained, shiny for a long time in the presence of water and
air. When it gives (hardly) its s electrons it will become monovalent Hg+, or bivalent
Hg++ ion. Its compounds will readily transform back to pure mercury by reduction,
heating... the same way as gold. Mercury is a liquid, implying even less connectivity and
more nobleness. What is the relativistic effect which makes mercury a liquid? Here is a
reminder: an electron can have a higher mass by having near light velocity:
examples:
42% of light velocity 10% mass enlargement
55% “ “ “ 20% “ “
86% “ “ “ 98% “ “ (almost double) !

The s-electronic orbitals of mercury, beginning with 1s, 2s .... 6s, arranged (symbolically
speaking) as spherical envelopes on top of each other, contract about 17.5%, or above
9% from what “expected” (see following graph), so one can calculate the electronic mass,
inversely proportional to radius. The last pair, 6s², is “dug” into the mercury 5d shell and
consequentially stabilized, “unwilling” to be bonded..
 22
Preceding mercury(80), Rhenium(75) – 11% contraction, or 4% above “expected”
Osmium(76) – 11.5%, 4.5%
Iridium(77) – 12.3%, 5%
Platinum(78) – 12.7%, 5.2%
Gold(79) – 16.5%, 8.7%
The reason for this tendency (to increase inner s-electron velocity and contract
correspondingly) seems the preference by mother nature of keeping 2 paired electrons in
outer s-shell while leaving p, d shells electrons to “organize”. One exception is gold,
another, platinum, although formally having 1 outer electron in s-shell, behaves as bi- or
tetra-valent what implies it behaves part of the time as having 2 electrons in outer shell.
With gold, a somewhat different story, d-electrons spend time in Fermi envelope – this
passage absorbs in the blue, so giving the yellow hue of gold. Not surprisingly, the
oxidation potentials (meaning the difficulty of electrons to be taken – the heavier the
positive nucleus) of the noble metals go up with the atomic numbers, until dropping
slightly in mercury, as follows:

Rhenium(75) +0.259v,
Osmium(76) +0.838v,
Iridium(77) +1.156v,
Platinum(78) +1.18v,
Gold(79) +1.498v,
Mercury(80) +0.7973v.
Of the other metallic elements shown in the graph, only Bismuth and Polonium have
positive oxidation potentials of +0.308v, +0.65v respectively. Tl (Thallium) and Pb (lead)
also shown, have favorable valences of 1 and 2 respectively (instead of 3 and 4 expected)
by the same digging or stabilizing of 6s² pair of electrons from 6s shell.

Relativistic contraction for atomic numbers 70 - 90

20
Relativistic contraction , %

Mercury
18 Gold
16
Tl
14 Platinum
Iridium
Osmium
Rhenium
12 Bi Po
W Pb
10 Hf Ta
8 Yb Lu
6
Expected contraction
4

0
69 70 71 72 73 74 75 76 77 78 79 Atomic
80 81 number
82 83 84 85 86 87 88 89 90 91 92

By the way, this is why gold whose inner s-electrons have 0.6 of light velocity, has a
yellow hue, since its 5d electrons are so close to 6s! (sp-d passage conforming to around
blue absorption) d-electrons involved jump to s shell, leaving d vacancies.
Remember: noble gases are monoatomic, not having the ability to form overlapping of
electrons. On the other end there are the common metals having full overlapping. Hg is an
intermediate case, as implied also by its so low conductivity.
23
 Hg is not a d-block element (6s full and stabilized - no d-electron transition). So, where
the color of mercury II oxide comes from? What about tetragonal mercury iodide which
has special red hue, transforming at 127ºC to yellow rhombic HgI 2. And vermilion paint of
hexagonal mercury sulfide (cinnabar)?
The case of mercury II oxide seems, surprise! amazingly similar to copper I oxide, that
is, a series of absorptions stemming from the semi conductive nature. Even the colors are
similar. The fine HgO powder formed by chemical precipitation is yellow-orange, while the
coarse HgO produced by heating mercury in air is red-orange. What a similarity to cuprite.
Look at the following graph:

Mercury II oxide visible spectra

2.5
Density of states

1.5

0.5

0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
wavelength, micron

When we watch the graph, we observe absorptions in violet and blue. Whose
complementary color is orange, exactly as the color of fine HgO. When these absorptions
are red shifted, the same way as in cuprite the absorption peaks move to the right and we
get the red color of coarse HgO. Note: peaks at the ultra-violet range, has no visible
complementary color (material looks white, while absorption in infra red results in black).
Now watch another absorption spectra, that's of nano-mercury sulphide:
Absorbance, relative intensity

nano-HgS visible absorption spectra

9
8
7
6
5
4
3
2
1
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1
Wavelength, micron

We see an about symmetrical peak around 0.55 micron, that is green, somewhat lower
then 0.62 micron of orange expected from a band gap of 2eV alone. The complementary
24
color is vermillion, as the name of HgS (also cinnabar) implies. But it lacks the absorption
block to the left (associated with holes formation). In molecular orbitals language, what
occurs here is ligand to metal charge transfer (LMCT). Electrons from S= ( π), previously
gained from Hg, are shifted towards Hg++(6s), The semi conductive nature associated
with band gap passage, has absorptions in 0.64microns, 0.4microns (same range). May
we guess that HgI2 red color is also stemming from similar reasons? The answer is
positive. A reminder: mercury ions, either I or II has no vacant d-orbitals, same as
copper I ion. For comparison, CdS, having same configuration, is a semiconductor with
yellow color, somewhat lower than the orange expected from a band gap of 2.6eV
conforming to blue absorption. Of special interest is the following virtue of Hg atom:
When mercury atom is excited (by, e.g. argon plasma) its external electrons, 2 6s² electrons can
enter into 6s¹6p¹ meta-stable state in 2 main modes (6³P1 , 6¹P1), both polarized, differing in spin
numbers. After a short time (ns) they return to basic state, emitting radiation (UV, which can be
translated to observable illumination by phosphorescent material). What is special about this
process is 1. It has a high degree of over 60% exploitation of plasma energy 2. It occurs in low
temperature, 42°C, due probably to low MP of mercury (?), very close to room temperature in
relation to incandescent lamps. Hence the energy loss as heat is minimal, resulting in 4 times
reduction of energy use.
The following graph shows reflectivities of noble metals. Reflected is the complementary
of absorbed. What we see is about even distribution of wavelengths in the visible range
for most of the metals – what means they will look white (with metallic luster due to the
sea of electrons). Exceptions: Silver has a strong absorption in the UV range, a sharp
absorption peak (reflection trough) of silver at 0.32 microns (3.87 ev), which we cann't
see. Gold, absorption 'block' in the violet-green range (0.3 up to 0.5 micron) whose
complementary color is yellow-gold and copper in the violet-yellow range (0.3 up to 0.55
micron) whose complementary color is orange-copper (see graph on page 12 and theory
on p. 13). Remember that yellow is adjacent to green, so if included in the absorption as
in copper (respectively to gold) the complementary color moves also one step to orange.

Noble metals reflectivities

120

100
reflectivity, %

Copper
80 Silver
Gold
Platinum
60
Iridium
Rhodium
40 Palladium

20

0
0.1 0.2 0.3 0.4 0.5
wavelength,
0.6
micron
0.7 0.8 0.9 1 1.1 1.2 1.3 1.4 1.5 1.6

Note that reflectivity, is never 100% what means we always have absorbance and
heating. It will be mentioned that without the relativistic effect gold would absorb at UV
3.5ev. Silver, as mentioned has but the UV absorption (3.9ev), in addition to evenly
distributed absorptions in the visible range. Copper has in the visible spectrum but the
25
transition from d-band to Fermi level of conduction band, similar to gold but at somewhat
higher wavelength, hence the observed wavelength is the orange of copper. “By the way”,
the yellow of gold is converted to red-brown chocolate when amorphous or nano gold is
produced, because amorphous gold has kept the green side of the violet-green absorption
block observed for bulk gold, whose complementary color is red. See p. 12. This is
contrary to the shifts met in cuprous and mercurous oxides (where going from bulk to
nano yields a lower wavelength).
A reminder: said shifts, from hole forming situations... in copper I oxide, (p. 11)
mercury II oxide (p. 15), where a 'block' of absorption wavelengths exists between 0.3
micron and up to 0.57 microns translates into red, orange and yellow reflections.

9. Ruthenium
Electronic configuration - Ru
4 5
sp df s
2 6 7.. 1
7 -1 -1
electric conductivity: 1.4x10 m Ω at 273ºK
oxidation potential 0.49
Despite having 1 electron in s shell, monovalent ruthenium is rare.
10. Adsorption of oxygen on Ru Ru has a complex Fermi surface, what 'helps' in
adsorption
the same way as platinum and palladium. Ruthenium can occlude many volumes of
oxygen (also hydrogen). Ruthenium is unique in explodability, in oxidizing environments,
probably by virtue of this occlusion, which easily ends with oxide formation, due to the low
oxidation potential. The oxygen molecule is somewhat complex but stable:

(empty) (σ * antibonding)
(π * antibonding)

O O
(π bonding)
(σ bonding)
Each oxygen is keeping 4 electrons and the rest 8 electrons are distributed between 1 σ
bonding orbital , 2 π bonding orbital and 1 π * antibonding orbital. Another possibility
(instead of 3 π orbitals) is 2 π orbitals with 3 electrons each.
Now, how Ru will adsorb O2 : π orbital electron(s) will “hybridize” with empty positions
of Ru d-band. Also some “back donation” from filled positions of same d-band into
antibonding π * orbit. This is accompanied by widening the gap between the 2 O atoms
forming the O2 molecule. The form is: O-O
\/ O-O O-O
Ru / \ /
If the catalytic character is wanted, then we observe more forms, e.g.: Ru Ru , Ru
The last form is σ -form donation from O to Ru-d band. A further step in dissociating
O2 will be a passage of electron from bonding to nonbonding orbitals.. a story we already
know (in H2). This shows the value of Ru in catalysis, especially as addition to Pt (in fuel
26
cell's CO oxidation). It is supposed that the strength of O-Ru bond, is what prohibiting its
sole use. On adding Ru to Pt catalyst, a maximum in catalytic activity is found, at an
average concentration.
This and absorption spectra data show vicinity of energy levels for Ru ds electrons and
presence of many oxidation states at the same system, unless steps are taken to isolate
(at least momentarily) any species. The single s electron is hidden in some way however it
is easy to oxidize Ru electrochemically (close to copper).
Ruthenium compounds are tending towards brown (=red + orange + green) coloring,
what is indicative of various valences since brown quanta does not exist. For example:
RuCl3, Brown, has visible range absorptions peaks at 2.55eV (0.49microns blue) and about
3eV (0.39microns violet) in addition to non visible range absorptions in common with Ru+
+++ (as RuCl6=) always co-existing with it. Valence = 3, implies 2 d-electrones join the
single s-electron, leaving 5 d-electrons behind. Orientating with same spin in 5 orbits
(as in the case of iron) produces the paramagnetic α – RuCl3. The following chart shows
absorptions for most abundant ruthenium valences, namely +3, +4, +6, +7, +8.
The highest valences, +7, +8, have violet absorptions which translate into white-yellow
color. Probably – LMCT absorption. The lower valences have additional absorption near
0.5 microns, which take the color to orange, brown and green. Absorptions belonging to
+3 and +4 coexist, so, we see them always together. Maybe, it is the absorption of d-
electron joining s-electron (so changing valence from 3+ to 4+). Could be also from full
molecular orbital based on Cl- to empty molecular orbital based on Ru. On the spectrum
of RuCl3 a peak belonging to Ru+8 is observed, showing the difficulty of getting it pure.
Ru+6 as K2RuO4, orange in solution, black on drying, has somewhat lower absorption
peaks, 0.47 and 0.38 microns, respectively. RuO 4, yellow (absorption peak at 0.39
microns) ruthenium tetroxide of 25.5ºC m.p. a covalent liquid, readily distilled from Ru
systems in the presence of an oxidizer, e.g. KClO 4. Valence = 8, implying all 7 d-electrons
join the s-electron. It has also a strong absorption near 0.31 microns (uv).
Absorbances of Ru compounds
0.9

0.8
Absorbance

0.7

0.6 RuCl3
RuCl6 --
0.5 K2RuO4
RuO4-
0.4
RuO4
0.3

0.2

0.1

0
0.200 0.250 0.300 0.350 Wavelength,
0.400 0.450microns
0.500 0.550 0.600

KRuO4 , also white-yellow in solution and of tetragonal structure, has same absorption in
0.39 micron (border of visible range – violet). Valence = 7, implying 6 d-electrons join the
s-electron. Both have also a strong absorption near 0.31 microns (uv). The visible yellow
may be the result of ligand to metal charge transfer as we saw in the case of CrO 4 =. On
drying, the high valences of Ru compounds, get a black-blue coating of RuO 2 received by
27
reduction (oxygen emitted) through photosensitivity. Some ruthenium complexes, e.g.
reddish brown RuCl2(PPh)3 has the photosensitivity enabling exchanging solar energy into
current by way of changing valence together with crystal structure and coiled orientation,
back and forth, when absorbing and releasing energy.
11. Rhodium
Electronic configuration - Rh
4 5
sp df s
2 6 8.. 1
7 -1 -1
electric conductivity: 2.31x10 m Ω at 273ºK . Oxidation potential 0.8
Rhodium with the single s-electron, which is also somewhat hidden itself, but joined
with 2 d-electrons has preferably the 3+ valence (2+, 4+, 6+ not significant). Short living
monovalent rhodium can be 'artificially' synthesized, as well as other valences. It has the
same tendency, like other transition metals of forming complexes. To affect dissolution of
Rh, sort of complexing with SO4= anion is needed, the hardest conditions and the slowest
process, among noble metals. The main function of the special configuration of Rh is
adsorbing NO2, so assisting in converting this irritating gas into nitrogen. Rhodium
compounds are tending towards the wine-red color, but they can have also the yellow
color, what depends on joining ligands. For understanding the effect ligands have on
color, go to copper ion on p.12.
The chart below shows some variations in color of Rh+3 caused by change of
ligands. Addition of H2O and loss of Cl- causes the stronger absorption, 0.49 microns –
(gives orange instead of red) and then 0.46 microns - gives yellow instead of orange. This
means the energy gap for the specific transition increased. See p. 10 for comparison.
It should be mentioned that H2O ligand is more influential than Cl- ligand in this respect.
Rh+3 absorbances
0.15

0.13

0.11
Absorbance

0.09

0.07

0.05

0.03 R hC l6---(R ED)

R h(H2O)Cl5-- (ORANGE)
0.01 R h(H2O)2C l4-(YELLOW )

-0.01
0.3 0.35 0.4
wavelength,
0.45 0.5
micron0.55 0.6 0.65

12. NO, NO2 adsorption on Rh

Rhodium d-crossing of Fermi surface, plays an important part in NO, NO 2 adsorption.
Added to platinum CO and O2 adsorption ability completes the recycling of NOx -es
(in the fuel burning) to N2. To explain this better, let's look at the electronic system of NO:
 28

. O
N
:N ̶ O: adsorption configuration: Rh

The simplified diagram shows σ bond, derived from 2px atomic orbits of N and O, two π
bonds derived from py and pz orbits. N-based spherical σ orbits (doubly occupied) and
double-helical π* orbits (singly occupied). The amplitudes of the N -derived orbitals are
bigger than the O's. Therefore, interaction with an adsorber atom is through the N-side.
The σ part is donating, while the π* part is accepting, so both of them involve,
mainly the π* part in this case (called back donation from the metal d-band). Rh
special Fermi envelope enables 3 ds external electrons to interact with σ electrons, while
some of the 6 remaining d-electrons overlap with the singly occupied π* orbit. At the time
of adsorption, the N-O bond is weakened (lengthened) by the filling of the antibonding π*,
causing more rejection between N and O. Despite that lengthening, N-O bond length is
still about 1.2A, against 1.8A distance between N and adsorber atom. Also contributing to
adsorption, the σ donation to the metal. Rh is a stronger adsorber of NO than Pd, heats
50% more during adsorption.
The reason is, possibly, the more difficult “seclusion” of 4 d-electrons in the case of Pd,
(filled d-shell) so the σ contribution in the case of Pd is much lower.

13. Palladium
Electronic configuration - Pd
4 5
sp df s
2 6 10.. 0
7 -1 -1
electric conductivity: 0.948x10 m Ω at 273ºK
oxidation potential 0.99
Palladium is an exceptional element, in many respects. 1Stly, it has the 2 and 4
valences, despite the d10 (not the noble gas configuration – but the pseudo noble gas)
configuration, what implies that 2 or 4 electrons from d shell pass to outer shell (in order
to make it react). 2nd – it - and platinum - have exceptionally lower conductivity among
noble metals, less than half of average. 3rd – despite the high oxidation potential it is
attacked more readily then most noble metals - gold and platinum sisters. So it is difficult
to separate it chemically from e.g. silver copper or nickel, if found together. Palladium in
atmosphere will get a film of carbon monoxide, as platinum. But platinum stays bright,
palladium does not.
14. CO adsorption on Pd, Pt
CO molecule is similar to NO molecule. Hence the way it is adsorbed is similar. The C-
side is what interacts. σ part is donating, empty here π* part is accepting.
(see drawing).
29
O
O O
- + C C C
: C Ξ O: adsorption configurations: Pd Pd (bridge) Pt Pt (on top)

The interaction between CO and transition metals

(1st stage in CO adsorption)
1. Localization (orientation) of metal full d-orbitals and donation to C - л* orbitals
2. C full σ – orbital donates to metal empty d-orbitals

Palladium will adsorb H2 almost 0.6 to one atom ratio, what conforms to PdH1.2,
palladium hydride, so strong is the link. NO, NO2, CHx (carbohydrates) are readily
adsorbed, in short – almost every gas, the same as platinum. Only platinum and other
noble metals do not form hydrides, but adsorb superficially.
The low conductivity of Pd deserves explanation – is it the lack, nominally, of “free” (s-)
electrons? The real explanation is more complex: one explanation – where instead of the
scattering mechanism, its conductivity is based on hopping, with a small energy hopping
gap of 0.1 – 0.2 ev. Another, unlike its neighbors Ag and Ru, its d-electrons which consist
85% of the higher density of states at the Fermi level (like Pt), have high λ, coupling
constant between electrons and phonons (lowering the conductivity see p. 9)
thereby becoming very slow. On the other hand, 15% (what the calculation shows instead
of nominal zero) s-electrons consist 80% of N(F)<v²> ...
15. Silver
Electronic configuration - Ag
4 5
sp df s
2 6 10.. 1
 7 -1 -1
electric conductivity: 6.28x10 m Ω at 273ºK
oxidation potential 0.8 close to mercury
30
Chemically, silver behaves similarly to mercury while nominally, mercury has 2 s-electrons
and silver one.. Basic reactions of silver has their parallels in mercury – mainly +2 valence.
Chloride precipitation, dissolution with ammoniac (I tried it myself), formaldehyde or sugar
reduction, red mercury chromate.. Therefore, separation between the two is best made
possible by physical means – e.g. vacuum distillation of low boiling mercury, or “playing”
with the different solubilities in hot water of mercury and silver chlorides.

Similarities among light and heavy noble metals:

light Ag(47) Pd(46) Rh(45) Ru(44)

d 10 of 10 10 of 10 8 of 10 7 of 10
s 1 0 1 1
heavy Hg(80) Pt(78) Au(79) Re(75) Os(76) Ir(77)
d 10 of 10 9 of 10 10 of 10 5 of 10 6 of 10 7 of 10
s 2 1 1 2 2 2
similarity points chemical chemical prefered multi valences
reactions reactions valence=+3 ready formation of
oxidation paramagnetic oxides
potentiai weak conductors

Silver will not adsorb hydrogen, but will adsorb oxygen – by donation of 5s (conduction-)
electrons to O2 σ* and π* antibonding orbitals. Same as gold (6s). It is said that the
energy of 5s electron (silver) and 6s electron (gold) is higher than σ* and π* of oxygen.
However, the blackening of silver was proved to be silver sulphide, by the “affinity' of
silver to sulphur even though its concentration in the atmosphere is so small...

16. Platinum
electronic configuration - Pt
5 6
sp df s
2 6 9 .. 1

7 -1 -1
electric conductivity: 0.95x10 m Ω at 273ºK
oxidation potential 1.2v
The identity of electrical (also heat-) conductivities with Pd implies similar Fermi
envelope with similar density of states there, from which the behavior is derived. In
fact Pt and Pd are twin sisters, where only the stronger attraction of electrons to the more
massive nucleus of Pt (relativistic contraction, see p.13) makes it nobler. Therefore,
spontaneous adsorption of all gases including exothermic heating, thereby catalyzing
reactions as dissociating H2, O2, H2O2 into radicals H·, O·, ·OH, what begins the chain of
desired reaction. Especially, the oxidation of unburned CO, CHx, NO from fuel burning. A
problem – the preferential adsorption of CO all over other ingredients at low temperature
is strangling the catalyst, so a high temperature is needed to remediate this. Certainly Pt is
a far better catalyst but when you 'augment” platinum with adding palladium, you, in fact,
can have the action of platinum from the ensemble. On the other hand, only platinum has
such a low hydrogen overvoltage among all metals, while in contrast, palladium only can
actually dissolve hydrogen. There are several opinions how – in the form of protons (H+)?
Atoms (H·)? Hydride ions (H-)? What made noble metals the preferable catalysts (besides
31
activity)? 1Stly, the stability or durability. 2Nd, the readiness with which they form spongy
mass – a high surface area powder. Taking platinum as an example, a stream of hydrogen
and oxygen over platinum will ignite, from the heat emerging by their spontaneous
adsorption and dissociation to H·, O·, followed by reacting to water. Presence of halide
ions, also readily adsorbed, can change the product to hydrogen peroxide.
When water is present, adsorbed hydroxyl ions (OH-)ads are formed and react with
(corrode) many metals even Cu and Ag, but not the nobler ones. A unique character of
platinum is the lack – almost – of over potential of proton (H+) transforming to H 2 in the
presence of water. This makes a clear difference with palladium, otherwise its twin sister
and makes platinum the ultimate catalyst. With Pt catalyst the energies needed for
producing H· radical atom +its diffusion +dissolution in metal +desorption and more - are
provided by adsorption and reaction heats.
17. Gold
Electronic configuration - Au
5 6
sp df s
2 6 10.. 1
7 -1 -1
electric conductivity: 4.52x10 m Ω at 273ºK
oxidation potential 1.4

18. Gold electronic enigma, 1, 2 or 3

Gold atom has nominally 1 6s-electron. However relativistic contraction works well
also for singly populated s-shell. See also p.13. If you polarize gold electrode potential
upwards in an electrolyte* (anodic metal dissolution) meaning pumping electrons out of it
forcibly (by connecting it to the positive pole of a rectifier) so raising the potential, to
around 1.5v versus hydogen couple it will tend to oxidize, give away three electrons, that
is additional 2 d- electrons (out of 10) to the 1 s-electron. If you further polarize it to
around 1.65v, the value for monovalent gold, the gold gives away only one electron. A
possible explanation: monovalent gold is formed firstly, as seems rational, then 3 gold
cations spontaneously react on the gold electrode like this: 3Au+ = Au+++ +2Auº (as
long as the potential is below 1.65v) meaning, 3 monovalent gold cations
comproportionate - returning to being 2 metallic gold atoms + one trivalent gold cation. In
trying to visualize that process, we may imagine two gold (+1) cations get electrons from
a third one, so becoming again gold atoms. This would imply that the third atom would
also pass a divalent stage. Indeed, some researchers use infrared absorption spectroscopy
– where Au+ and postulated Au++ have absorbances (around 0.28 microns) to verify
that. The incomplete d-shell of Au++ gives a weak absorbance at 0.48microns resulting in
yellow, similar to Au+++. They suggest a greater stability for a dimer, (Au++) 2 stemming
from the pairing of lonely electron in Au++. Trivalent gold can transform completely to
monovalent gold using special techniques, e.g. 60Co γ pulse-radiolysis in organic solvent.
Of course it can be observed by losing color (called bleaching) due to lack of absorbance
in the visible range (complete d-band). By reacting monovalent gold it was found that it is
easier to react than trivalent gold by a free energy differential which translates into that
voltage difference (0.15v). The spontaneity of reaction also implies a favorable free
energy change.
* The electrolyte must not be water, producing oxygen at such voltages.

32

Gold nano-triangles prisms⁴ view supporting

the existence of gold ions trimers (width: 40-210 nm; thickness: 7.5 nm)

A reminder: similar behavior is seen in rhodium where 2 d-electrons (out of 8) join the 1
s-electron to form the trivalent rhodium, so, in simple situations, no monovalent Rh exists.
Moreover then, all the three 'outer' gold atoms' electrons have close energies, so the
'bivalency' (or existence of outer pair) will hold only temporarily maybe. We can further
complicate things by asking whether a third electron, in the gold atom too, shows
absorbance, in addition to the one passing between d and s-shells (or Fermi envelope) or
both absorb in close wavelengths, since we know that those absorbances depend also on
size – gold change of color with size, in other way then expected (p. 16). To complicate
things further, let's look about ionization potentials. The 1 st, 9.2ev is slightly below
mercury's 10.4 due to somewhat lower relativistic contraction. However the 2 nd, 20.5 is
higher with gold having the pseudo noble gas configuration, full d-shell implying high
stability than mercury (18.9) with the dug s-electron, also having high stability. Anyhow,
there is similarity between the stabilities of d-filled to s-dug electrons. This
values, are characteristic for atom surrounded by vacuum/gas phase. Weakly bound gold
telluride, AuTe2, of ΔG0= -4.13 kcal/mol can form in such circumstances if abundant
tellurium is met, acting as 'gold capturer'. However, to explain the structure, one needs
2Te pairs, enveloping a pair of gold ions, one monovalent, the other trivalent (or both
divalent as seen in electrolyte solution above). This may support the existence of gold
dimer, also explain the difficulty in leaching of gold from it despite the weak bond.
Gold will adsorb dissociatively hydrogen peroxide, as platinum, ferrous iron and others,
to a lesser extent though, since it has less of transition metal character (as mentioned)
but still with a very low activation energy, against the total energy evolved – 52kcal/mol.

Activation energy, kcal/mol

Forrous oxide, FeO 9.4
Platinum, Pt 13.0
Gold, Au 14.7
 The reaction is:

33
Au + H2O2 = Au+ + OH- + ·OH
This means that ·OH radical, hungry for electrons is readily produced – a useful base for
dissolving gold, or lifting it from “base metals” surfaces, in co-operation either with
hydrochloric acid or cyanide ions. With cyanide ions for example:
Au + 2CN- + ·OH = Au(CN)2 - +OH-
This is the famous “booming” reaction which polishes gold surface perfectly, giving it an
extra shine. The idea behind this polishing is that activity of defects on gold surface is
higher, so the defects 'help' in dissolving themselves. A similar mechanism with HCl,
forming chlorine to the extent of dissolving gold in various points so enabling penetrating
it and dissolving the metal below. Result: lifting of gold plating.
19. Nano-gold and nano-noble metals, crystal sizes and colors
Back in the old ages, an artist watched the hues appearing sometimes on edges of gold,
silver and copper articles. He noticed gold assumes a red and green hues, silver a yellow
hue, copper a blue-black. Genuinely he linked it to a thin layer of metal surrounding the
bulk of the metal. He then diminuted those metals to nano sizes, either mechanically or
chemically, embedded them in glass and got beautiful windows, durable for many years.
When the sun illuminated them strongly from the outside beautiful red (gold) and yellow
(silver) windows were revealed to the eyes of the men inside, outside of gold was green.
Nowadays we know other methods of “activation” as laser, electron beams and more
which cause the electrons in nano-metal particles to resonate, thereby absorbing some
frequencies and leaving others (however, the detection is simple with visible light
illumination refering to those metals).
When the size of gold particles is decreased, especially if arranged in arrays of identical
form and gaps, or thin layers, the color is changed from the known golden hue to red-
chocolate. At the same time, conductivity is no more metallic, since the particle size is
lower then the free path for electrons. (if metal particles come closer, e.g. 0.2 of particle
radius a passage event also changes the color from “isolated” or more spaced situation- in
the case of gold WL increase about 80-100nm. Differences in diameters of particles
decreases the WL). The passage from blue to red is termed red shift.

Nano-gold colors red shift bulk gold

The part of the visible light resonates with the free electrons in the confined thickness
available, being absorbed, while the complementary - left part - is reflected, or
transferred. The interband gap absorption is added. It was mentioned before that its shift
in metal is contrary to the shift in semi conductors (who blue shift in going from bulk to
nano). As most metals are white, meaning they absorb in the UV range, the shift can
hardly bring them to the yellow color, meaning the absorption is red shifted to violet. This
is the case with e.g. silver and Al(?). Copper, orange, will move to blue. However, the
34
hues may not be precisely consistent.
Bulk absorption
Metal visible range peak color nano absorption peak color
micron micron micron
gold to 0.5 0.38 yel 0.52 ± red

silver 0.305(UV) wh 0.42± yel

copper to 0.55 0.288(UV) or 0.59± blue-black

One reason for this behavior is that the resonance of electrons in metal nano particles
has a lower frequency, higher wavelength than the plasma resonance frequency of
electrons in the bulk metal. The bulk plasma frequency is less damped by having free
space, larger than the Mean Free Path for resonating (oscillating). Gold for example (see
p.9) has a MFP of 38nm (0.038 microns), plasma WL 138nm
Copper 39nm plasma WL 115nm
Silver 53nm 129nm
and what characterizes a damped frequency is...
1)Considering the possibility that energy is absorbed (lost by heating), the remainder of
energy has lower energy – meaning higher wavelength and lower frequency than the
plasma frequency
2)In page 9 we met the damping factor, Γ which stems from the interaction between free
electrons and bound (d-) electrons, causing a decrease of Mean Free Path. This means
that the oscillation, or resonance frequency is damped from the plasma frequency.
3)Another damping factor, γ, originates from smallness of particles and increased external
surface accordingly, having the same consequence, that is decreasing the MFP, because
the external surface of the particle also is a collision source. Mathematically speaking,
we can compare this to an oscillating spring under friction, what causes it to slow,
thereby increasing the period time and the WL, lowering the frequency.
According to---e.g., (one researcher) if the host material is air (Є host=1)and the particle
spherical, gold

ω= ωp = 0.58ωp
√(Єhost +2)
Other researchers give √(½ ± ½c) instead of 0.58, c being dependent on particle
geometry.
This would account nicely to the fact that water (Є=80), glass (Є=4) further reduce the
frequency (increasing the wavelength, widening the red shift), relatively to air (Є=1).
Gold lonely nano-sphere with bulk 138nm will have 138/0.58=238nm in air (still UV). In
glass 138x2.45=338nm and in water 138x9.05=1250nm (IR).
Unfortunately there is some trouble with using only the factor 0.58 since, WL p , the
nanoparticle absorption wavelength would be 1/0.58 or 1.73 greater than the plasma WL.
Instead, calculated nano particle dipole resonance (plasma) wavelengths (the lowest WL)
for gold, silver and copper are 0.138, 0.138, 0.115micron, respectively (all in the UV range
and 0.2 to 0.3 of nanometal particles known absorption WL) So we need to add to the
computed WL 100 – 200nm by considering multiplicity of particles, meaning prooceeding
from array of lonely nanosphere, to array of pairs, trios, quartets etc. until multiplicity of
nanospheres is achieved (with the intersphere distance below the limit of proximity), to
enter the visible range. Another point is the inter band gap which is still present, apart
35
from the damping effect. The combination of inter band absorption + the plasmon
resonance is what produces the resulted effect.
A numerical example:
A nano gold sphere should have a diameter of 25nm or less. A second gold nanosphere
with equal diameter, both on a substrate of є=2.25 (kind of wax, or PTFE) will resonate at
500nm if they are one diameter apart and 580nm if attached. If the second nanosphere
diameter will be reduced to 15nm the resonance frequencies will become 498 and 520
respectively. Checking the complementary wavelengths we see blue (0.45micron or
450nm) in the first case and red (0.65micron) in the second (both in the “attached”
situation). The 498-500nm absorption (orange – red) can be considered the absorption of
a lonely, or far away nanospheres. Certainly, 3 or more attached particles, will have a
higher WL absorption, more red shifted towards 700nm.
What is absolutely clear, gold in the nano configuration lacks the blue component (of the
violet summation) in absorption responsible for yellow hue, what supports the view of
nano-gold assuming a semiconductor gap. The “known” brown-chockolate color of
amorphous gold is a result of crystallization from the colloid stage to multiplicity of nano
sizes, whereas in the case of oxalic acid reduction (+ heat) the crystal size is over a
micron, the metallity is retained.
Silver is the less damped element in the list, so its plasma behaviour more researched.
Its bulk frequency yet close enough to visible. While most base metals do not have similar
absorptions. Anyhow, resonance frequencies can be manipulated to almost every value,
using all the factors mentioned, that is size, geometry, host material and not to forget the
capping material¹ (fact used in pregnancy test with gold particles turning blue from red)...
¹material used in producing nanoparticles
20. Rhenium, osmium, iridium
7 -1 -1
5d 6s conductivity, 10 m Ω oxidation potential, v valencies
Re(75) 5 of 10 2 0.52 +0.259v -1 - +7
Os(76) 6 of 10 2 1.25 +0.838v 0 - +8
Ir(77) 7 of 10 2 2.12 +1.156v -3 - +6

The three metals left, are of less concern as precious metals. Os (as well as Ru) find use
in medicine. Os was once used in electric bulbs before tungsten, due to high MP, Before
leaving it for toxicity. All three play a similar role to Ru as additives (or replacement) to
platinum for catalysis purposes. While rhenium has about half platinum conductivity,
osmium has a higher conductivity than Pt, iridium – more than twice. All three form stable
oxides (as well as Ru), of many valencies, but especially:

RuO4 from Ru, volatile

Re2O7 from Re, volatile
OsO4 from Os, volatile
IrO2 from Ir
what is helping in purifying them by distilling or isolation of the stable oxide. However,
the tetroxide of osmium is very toxic – kills living tissues, with heavy, irritating smell. The
low oxidation potential of rhenium results with sensitivity to water in the presence of
oxygen, same way as copper. As transition metals, their compounds are mostly colored in
accordance with possibility of d-d transitions, mentioned before. An exception, KreO 4,
obtained easily from yellowish Re heptoxide, is colorless. It would be expected, to show
absorbance from shift of electrons (see p. 4 for comparison) but the absorbance is rather
36
energetic, in the UV range.
Arik Lin, Ph.D. Lino_1406@yahoo.com
www.facebook.com/pages/Gold-electronic-enigma/162208933810735

Reference
1. Review of Energy Dispersion in Solids – MIT
Web.mit.edu/course/6/6,732/www/new part1.pdf p.25
2. Electron-phonon coupling and spin fluctuations in 3d and 4d transition metals:
implications for superconductivity and its pressure dependence. S.K. Bose
J. Phys.: Condens. Matter 21 (2009) 025602 p.1-13
3. Prominent 5d-orbital contribution to the conduction electrons in gold…etc. Akira
Sekiyama et al. New journal of physics, vol. 12, April 2010
4. Observation of a Quadruple Plasmon Mode for a colloidal solution of gold nanoprisms.
Millstone, J. E. et al, J. Am. Chem. Soc., 2005, 127 (15), 5312-13

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