Index 1357
Debye function, 1168
Debye length, of electrodes, 597
Debye, Peter J. W., 271, 858
Debye temperature, 1168–1169
Debye theory, for bimolecular processes, 530
Debye unit, for dipole moment, 858
Debye–Hückel theory, 237, 270–274, 271, 299
for cell voltage, 360
Degeneracy
of energy level, 670
in free-electron theory, 1176, 1176f
in rotational spectra, 964
Degenerate orbitals, 845
Degenerate perturbation theory, 803–805,
1285–1287
Del.SeeGradient operator
Delocalized bonding, 885–890, 912
Hückel method, 887–890, 888–890f
LCAOMO treatment of, 886–887
valence-bond method and resonance,
885–886
Denatured, polymers, 1197
Dense gases, classical statistical mechanics
of, 1147–1150
Density, 14
one-componentvs. two-component system,
230–231, 231f
Density functional method, 789, 805–806, 819
for computational chemistry, 908
Dependent variable, 5
from mathematical function, 620
Dephase, spins, 1027
Derivative(s), 14
partial, 14–15, 623
second, 16
variables related to, 17–19
Derived units, 8
Destructive interference, of classical
waves, 629
Detailed configuration, orbital wave
functions, 772
Determinants, 1251–1253
Deterministic, classical mechanics as,
625, 1267
Diagonal elements, of matrix, 1250
Diagonal matrix, 1251
Diagonal rule, for neutral atoms, 810, 810f
exceptions to, 811, 811t
Diamagnetic shielding
impurity and solvent effects, 1021
in NMR, 1015–1017, 1016f
Diamagnetism, 1015
Diatomic molecules
electronic spectra of, 972–974, 974f
electronic states of, 823–866
Born–Oppenheimer approximation,
824–832
homonuclear, 838–850
summary for, 865–866
Fourier transform infrared spectroscopy
of, 969–971, 969f
heteronuclear, 823
homonuclear, 823
nonelectronic states of, 919–929, 921f
rotation of, 922–929, 922f, 926f
population of, 943–944
rotational spectra of, 961–964
vibration of, 922–929, 922f, 926f
population of, 944–945
vibration-rotation spectra of, 964–968,
966–967f
Dielectric constant, 270
Dieterici equation of state, 23, 23t
Difference equation, 1194
Differentiable, 14
Differential calculus
with several variables, 1235–1238
state variables and, 14–16
Differential equation, 14, 67, 396–397,
624
exact and inexact, 48, 1237–1238, 1245
of Gibbs energy, 153–154
of Helmholtz energy, 153
partial, 449, 631
of thermodynamic functions, 151
Differential heat solution, 279
Differential scanning calorimetry (DSC),
phase diagrams with, 287–288
Diffraction
of electrons, 656, 657f
from interference, 629–630, 630f
of a plane wave, 630, 630f
Diffuse double layer.SeeElectrical double
layer
Diffusion, 441–442, 482
diffusion flux for, 444
driving force for, 445–446
equation of continuity, 447–448, 447f
Fick’s second law of diffusion, 449–452,
450–451f
of liquids, 1189–1192, 1189f
molar activation energy for, 470self-diffusion in hard-sphere gas, 460–464,
461f
temperature dependence of, 470–472
Diffusion coefficient, 446
in liquids, 470, 538, 1189
of macromolecular or colloidal
substance, 469
in self-diffusion, 463
Diffusion flux, 444
in bimolecular processes, 528–529
Diffusion-controlled, bimolecular elementary
process, 528
Diffusion-limited, bimolecular elementary
process, 528
Dilute gas, 5, 386
activated complex theory for, 1106–1115
potential energy surfaces, 1107–1108,
1108f
trajectory calculations, 1108–1109
in canonical ensembles, 1130–1132, 1131f
classical, 1135–1137
classical thermodynamic functions,
1142–1144
chemical equilibrium in, 1101–1105
energy of, 398–399
model system for, 386–393
classical mechanics, 387
effusion and wall collisions, 416–417
hard-sphere gas, 422–433
mean values of mechanical variables,
392–393
microscopic states of, 390–391f,
390–392
molecular speed distribution, 405–410
Newton’s laws of motion, 387–389, 388f
potential energy, 389
with potential energy, 418–421
summary for, 436–437
velocity probability distribution, 394–404
molecular partition function for,
1057–1063, 1059f
calculation of, 1064–1075
canonical, 1127
diatomic gases, 1065–1072
monatomic gases, 1064–1065
nuclear contributions to, 1075
polyatomic gases, 1072–1075
product partition function corrections,
1070–1072
rotational partition functions, 1066–1069,
1067f, 1073