P461 - Solids1 Solids - types MOLECULAR. Set of single atoms or molecules bound to adjacent due to weak electric force between neutral objects (van der Waals). Strength depends on electric dipole moment No free electrons --> poor conductors easily deformed, low freezing temperature freezing boiling bonding energy He 1 K 4 K H 14 K 20 K Ar 84 K 87 K.08 eV/molecule H 2 O 273 K 373 K 0.5 eV/mol CH 4 90 K 111 K 0.1 eV/mol correlates with bonding energy

P461 - Solids2 Ionic Solids Positive and negative ions. Strong bond and high melting point. no free electrons --> poor conductor similar potential as molecule. ~5 eV molecules and ~6 eV solid (NaCl) each Cl- has 6 adjacent Na+, 12 “next” Cl-, etc energy levels similar to molecules except no rotations….electronic in UV and vibrational in IR. Often transparent in visible R Potential vs sep distance R

P461 - Solids3 COVALENT. Share valence electrons (C, H, etc) strong bonds (5-10 eV), rigid solids, high melting point no free electrons --> insulators usually absorb in both visible and UV METALLIC. s-p shell covalent bonds. But d shell electrons “leftover” (smaller value of n -> lower energy but larger ) can also be metallic even if no d shell if there is an unfilled band 1-3 eV bonds, so weaker, more ductile, medium melting temp “free” electrons not associated with a specific nuclei. Wavelength large enough so wavefunctions overlap and obey Fermi-Dirac statistics ----> conductors ----> EM field of photon interacts with free electrons and so absorb photons at all

P461 - Solids4 Bands in Diatomic Molecules-Reminder assume all valence electrons are shared if both atoms are the same then |  2 same if switch atom(1) and atom(2) --- electron densities around each atom are the same (even sort of holds if different atoms like CO) H(1s) H(1s) close together H(“1s”)H(“1s”) electron wavefunctions overlap -“shared” two energy levels (S=0,1) (spatial symmetric and antisymmetric)which have E R=infinity (atoms) 1s*1s Vib and rot bands

P461 - Solids5 Bands in Solids lowest energy levels very similar to free atoms --> large kinetic energy ---> large p, small little overlap with electrons in other atoms and so narrow energy band higher energy levels: larger wavefunctions of electrons from different atoms overlap need to use Fermi-Dirac statistics many different closely spaced levels: Band 3s,3p 2s,2p 1s 4s,4p,3d E

P461 - Solids6 Multielectron energy levels 3/2 symmetric spin. Each 1/2 has different mixed symmetry --> 3 different spacial wavefunctions and (usually) 3 different energy levels the need for totally antisymmetric wave functions causes the energies to split when the separation distance R < wavelength if far apart -> N degenerate(equal) states overlap -> still N states but different energy E R 6 electrons

P461 - Solids7 N different combinations of spatial wavefunctions gives N energy levels N based on how many electrons overlap ---> large for the outer shell small  E between different levels ---> an almost continuous energy band nature of the energy bands determines properties of solid -- filled bands -- empty bands -- partially filled bands -- energy “width” of band -- energy gaps between bands -- density of states in bands

P461 - Solids8 Bands in Solids 2 as their atomic radii are larger (and wavelength larger) there is more overlap for outer electrons larger N (# shared) ---> wider bands (we’ll see later when discuss Fermi gas) valence electrons will also share though band width is narrower “valence” vs “conducting” depends on whether band if filled or not valence conduction E

P461 - Solids9 Li and Be Bands Atoms: Li Z=3 1s 2 2s 1 unfilled “conductor” Be Z=4 1s 2 2s 2 filled “insulator” But solids have energy bands which can overlap there is then just a single 2p2s band Be fills the band more than Li but the “top” (the Fermi Energy) is still in the middle of the band. So unfilled band and both are metals 2p 2s 1s Atom solid E

P461 - Solids10 Magnesium Bands Atoms: Z=12 1s 2 2s 2 2p 6 3s 2 filled “insulator” like Be the 3p level becomes a band with 6N energies. The 3s becomes a band with 2N energies They overlap becoming 1 band with 8N energy levels and no gaps BUT, if R becomes smaller, the bands split (bonds) giving an energy gap for C, Si, Ge 3p 3s E Atomic separation R 6N 2N 8N