Why conductors bonds in such way that leaves the valence band not full

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Discussion Overview

The discussion revolves around the differences in conductivity properties between metals, semiconductors, and insulators, focusing on the electronic structure and bonding characteristics that influence these properties. Participants explore theoretical concepts related to band theory, the nature of bonding, and the implications for electrical conductivity.

Discussion Character

  • Exploratory
  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant suggests that current flow in solids requires empty energy states for electrons to occupy, linking this to the conductivity of metals.
  • Another participant agrees that metals conduct electricity well due to the availability of higher energy states and discusses the nature of bonding in metals versus insulators.
  • Some participants propose that the difference between semiconductors and insulators lies in the size of the band gap, with uncertainty about what determines this magnitude.
  • It is mentioned that the filling of energy states in metals is influenced by the number of available electrons and their electronegativity, which differs from non-metals.
  • One participant introduces the concept of oxidation states and how they relate to the conduction of electrons in metals, describing the transition of bound electrons to a delocalized state.
  • There is a suggestion that the band gap can be determined experimentally using UV/Vis spectroscopy, although the exact threshold for distinguishing between insulators and semiconductors remains debated.

Areas of Agreement / Disagreement

Participants generally agree on the basic principles of conductivity and the role of band gaps, but multiple competing views and uncertainties remain regarding the specifics of bonding and the factors influencing the band gap.

Contextual Notes

There are limitations in the discussion regarding the assumptions made about bonding types and the definitions of terms like "band gap." The discussion also reflects unresolved questions about the exact mechanisms that determine the electronic properties of different materials.

abotiz
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Hi,

Iam trying to understand the differences between metals, semiconductors and insulators. Regarding the conductivity properties. Iam new to this area so please correct me if I am wrong.

I may be simplifying things now;

1) If I put a voltage over a solid, I only measure a current if there are empty energy states for the electrons to occupy with their available energy (thermal or whatever).

2) The reason why metals conduct electricity so good is because there are empty (higher) energy states. And the reason for that, is because when these atoms bind into a solid, they bond in such way that the electron configuration leaves some available states in the sub shells, e.g. s- or p-sub shells are not full.

3) Semiconductors and insulators bond in such way that all states are full. However, the differences between semi and insulators is the band gap, and Iam not really sure what determines this, the magnitude of the bandgap. Maybe something with cosinus function, K values and Schrödinger equation?

If I am right in this (2), why (or what makes them not to) does metal not bond in covalent bonds in such way that all states are full, like in insulators.

Thank you very much for your time!
 
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You're making a valiant effort to fuse a number of separate phenomena (electronic structure Fermi energy/level, their bonding together with electrical conductivity) within a unified coherent model. While this is a correct approach that maybe solvable with advanced computational techniques that are beyond me, I believe the introductory models split these up into separate phenomena (see textbook by ashscroft and mermin, and kittel)

1) electronic structure / band theory

2) electrical conductivity

There are many ways to get from 1 -> 2. (e.g. Drude model using 1 for collision time, semi-classical, Boltzmann diffusion, and phonon scattering)

I'll try and directly address some of your questions

if a band is empty, there are no electrons to carry current when voltage is applied.

if a band is full the electron is stuck cause it has no where to move to (see mott type insulators for a surprising application of this which will confuse you more).

yes the difference between insulators and semiconductors is the size of the band gap. I believe the threshold is around ~2eV, but don't quote me. Yes, it is arbitrary. Ab init calculations of the band gap is one of the unsolved problems in solid state, at least according to Wikipedia last I checked.

your (2) is correct

Your final question. The filling depends on the number of electrons available. Atomic transition metals have roughly half filled 3d states, so their condensed counterpart have the possibility to be half filled.

Atomic Si, Ge, can completely fill their spd shells, so their condensed counter part can be completely filled.
 
abotiz said:
If I am right in this (2), why (or what makes them not to) does metal not bond in covalent bonds in such way that all states are full, like in insulators.

Metals differ from non-metals in their electronegativity being low (the boundary being somewhere near 2.5).
That means that in non-metals, bonds are covalent, i.e. there is very little ionic character. On the other hand, in metals ionic structures are of large importance, e.g. something like ##\rm Na^+ Na^-\leftrightarrow Na^- Na^+## in addition to covalent contributions. As Coulombic interactions are not directed, a metal can have bonding interactions with much more neighbours than a non-metal.
 
abotiz said:
2) The reason why metals conduct electricity so good is because there are empty (higher) energy states. And the reason for that, is because when these atoms bind into a solid[...]

3) Semiconductors and insulators bond in such way that all states are full. However, the differences between semi and insulators is the band gap, and Iam not really sure what determines this, the magnitude of the bandgap.

The reason metals conduct electricity so well is because of the accessibility of their higher energy states. The band gap is defined as the energy required to liberate a bound valence electron into a delocalized, unbound "fluid." On average, metals are easier to oxidize than non-metals. In other words, they are more willing to allow for one of their electrons to become unbound. As electrons are promoted into the conduction band, they access this sort of pseudo-oxidation state. The sea is made up of charge carriers, so the oxidation state is still considered 0. However, these conduction electrons are no longer bound.

To answer your other question, band gap can be determined with UV/Vis spectroscopy. This would be a good page if you want to read more: http://science.unitn.it/~semicon/members/pavesi/CaseStudy_uv81.pdf

rigetFrog said:
yes the difference between insulators and semiconductors is the size of the band gap. I believe the threshold is around ~2eV, but don't quote me. Yes, it is arbitrary.

I've heard that a good line to draw it at is 3eV. Although, it is arbitrary, like you said :wink:. I guess it depends on the material's behavior during its usage. I would assume that temperature dependence plays into it.
 
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