Appendix II: Notes on Silver and Its Clusters

A collection of scattered notes on the properties of silver as relevant to this project.
(experimental unless otherwise noted)

Studies of silver clusters:

See list in first page of Duncan Z. Phys. D. 1989, 13, 161

Silver has a common oxidation state of +1, Copper of +1 or +2, and gold +1 or +3.

Ag atom

IP: 7.574eV [ref in Morse, 1986]
EA: 1.303eV [ref in Morse, 1986]
Ionization potential:7.576 V
2S->2D excitation is at 3.74eV [] {note that this transition in Cu is at 1.38eV and at 1.13eV for gold (HackettRayner1993 ref elsewhere)
Atomic number: 47
Electron configuration: Kr: 4d¹⁰ 5s¹
There is a relativistic mass-velocity stabilization of the outer 5s orbital of the silver atom[Feng 1989] however this is not a strong as it is in gold.
atomic weight 107.868

Ag2

w.e Calc's: 178cm-1 [Walch 1986], 181.0 cm-1 [Koutecky1993] and others [see Koutecky1993]
w.e 192.4cm-1 r.e 2.480Ang(educated guess)
r.e 2.531Ang ()
D.0 = 1.65eV [Demtoreder][1.69eV Feng 1989][Morse, 1986]
much more info on molecule in Morse, 1986.
more info in Bonacic-Koutecky, 1993 [which see]
Much theoretical work summarized in ().
unreactive to CO, C2H4, NH3, H2, O2, N2O []

Ag2+

D.0 = 1.66eV [ref in Morse, 1986]
w.e 135.8cm-1, wexe 0.50cm-1 [both]
see Koutecky1993 for more info

Ag3 Total Binding Energy = 2.60eV [Feng 1989]

(stretch) 161.1cm-1, (bend) 96.3cm-1 []
see calc by [Walch 1986] which argees with this

Ag4 Total Binding Energy = 7.33eV [Feng 1989,approx]

Ag4 has an unusual stability [theory, Feng 1989]
Geometry of Ag4: rhombus [Feng 1989]

Ag2+ D.0= 12666cm-1 (1.57eV) [Demtroeder]

Ag3+ Total Binding Energy = 4.21eV [approx - Feng 1989]

obtuse triangle, Jahn-Teller distorted

Ag3

obtuse triangle, Jahn-Teller distorted

Ag4+ Total Binding Energy = 8.41eV [theory - Feng 1989] Rhombus

Ag4 Rhombus

side is 2.87Ang, angle 55.5deg {Balasubramanian Feng1989}
expected to be unusually stable by {Balasubramanian Feng1989}

For geometries of small (n<10) clusters see Koutecky1993

Bulk

cohesive energy estimate 2.95eV

heat of sublimination 2.99eV

lattice constant 4.09Ang [Murell 1993] {this is fcc unit cell dimension}

Free electron density

r.s = 1.60Ang = 3.02a0

e F = 5.49eV [Aschroft]

corresponds to electron density of 5.86e22/cm^3

both from Aschroft/Mermin, p5

Polycrystaline Work function: 4.26eV [ref in Morse, 1986]

Debye frequency: 156.4cm-1 [Kittel]{differs from Aschroft slightly}

Debye temperature 215K [Aschroft/Mermin]

The highest thermal and electric conductivity of any pure material

mp 961.93°C, bp 2212°C

plasmon: 3.78eV

Covalent radius:1.34Deg. A

Crystal structure: FCC

Density:10.5 g/cm(3) at 300K

Heat of fusion:11.3 kJ/mol at melting point

Heat of vaporization:250.58 kJ/mol at boiling point

Melting point:1234K

Comments:

Note that for trimers and tetramers (not for dimers) the ions are more stable than the neutrals.