Book Index
A
initio quantum chemistry,
Absorption of light, 151
Abstraction reactions:
models of mechanochemical, 226-229
of nonhydrogen atoms, 247
potential energy surfaces, 62-63, 226, 228
by radicals, 215
Acceleration, 25, 349
Accommodation coefficients, 182, 183, 358
Acenaphthyne, 214
Acoustic noise, 91
Acoustic power and control, 472-476
Acoustic radiation:
and energy dissipation, 162-168
equal-speed approximation, 163
moving disturbances, 166
oscillating force at a point, 163
oscillating pressure, 166
oscillating torque at a point, 165
in sleeve bearings, 290
in sliding of irregular objects, 283
uniform medium assumption, 162
Acoustic transmission lines, 363
Activation energy, see Potential barriers
Activation length, 202
Activation volume, 201
Actuation time, 197
Actuators, electrostatic, 335
Adamantene, 214
Adhesive interfaces, 270-271, 412,413-414
Agoric open systems, 371
Alignment bands:
and acoustic radiation, 167
and dislocations, 173
phonon scattering, 173-175, 292
thermoelastic drag, 181
Alkene reagents, 213-215, 229-232
Alkylidenecarbene, 242
Alkyne reagents 213-215, 241-243
Alkynyl radical, 216-217, 227, 232-233
Allenes, 214
Aluminum, 149, 153
AMBER force field, 43
Amines and lone pairs, 45
AM1 semiempirical method, 41
Anharmonicity, 179
Antibodies, 265, 374, 375, 448, 462, 466
Anti-Morse function, 62
Approximation, role of, 11, 23-24, 497
Assembler, see Mechanosynthesis;
Molecular manufacturing
Atmosphere, model of probability gas, 77
Atomic-point bearings, 303
Atoms, see also names of elements
generation of free, 9,195
MM2 properties, table of, 44
radii of, under load, 44, 60-61
B
Band flutter, 173, 175, 292
Band-stiffness scattering, 174, 292
Barrier heights, see Potential barriers
Barth, Phillip, 150, 429
Basis functions, in quantum chemistry, 40
Bearings, see also Sleeve bearings
atomic point, 303
bonded, 303
dry . lubricated, 27
as example of nanomachine, 2-5
interfacial structures, 294-295
interfacial stability, 296
roller, 308
Belt and roller systems, 309-310, 386-390
Benzyne, 214
Bevel gears, 308-309
Binding sites, see Receptors
Biochemistry, 10, 510-511
Boltzmann factor, 75
Bonaventura, Joseph, 482
Bond angle-bending, 45, 47, 51, 205
Bond cleavage:
by applied tension, 221-225
cage effect, 139
energy dissipation in, 222-224, 237
Lippincott potential for, 54, 56, 223
and molecular orbital methods, 61
Morse potential for, 51-56, 223
photochemical, 151
rates of thermal, 138
solid cage effect, 139
by stress and tunneling, 142
and support stiffness, 222
thermal,
thermomechanical, 140-143
Bonded bearings, 303
Bonds:
allowable stresses, 142
metal-ligand, 219-220, 234-237
properties, table of, 52
weakness of nitrogen-nitrogen, 298
Bond stretching, 44, 45, 51, 54
Bond torsion, 47, 48. See also Pi-bond torsion
Born-Oppenheimer approximation, 39-40
Boron-nitrogen compounds, 232, 270
Bounded continuum models, 12, 257
of logic rods, 346
and molecular mechanics, 67-69
and nanomechanical design, 318
Brittleness, and cracks, 254
C
Cage effect, 139,148
Cams, 172, 310, 374, 388-389
Capacitance, scaling of, 30
Capacitative time constant, scaling of, 32
Carbanions, 213
Carbenes, 195, 217, 218, 232, 242-243
Carbon, 195. See also Diamond; Diamondoid structures; Graphite
Carbonium ions, 213
Carry chains, 365
Casimir-Polder equation, 64
Catalysis and mechanosynthesis, 204
Chaos and statistical mechanics, 75
Charge distribution, molecular, 41, 48, 264
Charging, electrical, 150, 337-338
CHARMM, 43
Chemical synthesis, see Mechanosynthesis; Organic synthesis
Chemistry, see also Mechanosynthesis; Organic synthesis; Reactions
contrasts between machine and solution phase, 6, 88, 135-137, 152, 196-207
Classical continuum models and scaling laws, 23-35. See also Bounded continuum models
Classical electromagnetic systems, 28-32
Classical dynamical models, 73,74
Classical statistical mechanics, 73, 75-80
Clocking of CPUs, 367-369
Clutches, 314
Col, 36. See also Transition states
Combinational logic, 359-362, 364
Compression, see Nonisothermal compression
Computation, see also Nanocomputers agoric open systems, 371
computer as a hierarchical system, 12
cost of molecular modeling, 40, 41, 42
and entropy, 83
logically reversible, 83
Computer-aided design, 434-441
chemical . nanomechanical, 319
of components, 271
of dislocations, 269
of irregular structures, 265
Kaehler bracket approach, 266
of mechanochemical syntheses, 249
of strained shells, 268
Concentration, 5
Conditional repetition, 210, 388, 396
Conductors, electrical, 333
Configuration interaction, 40
Configuration space, 77-80
and chemical reactions, 194
and the PES, 36,77
probability densities in, 76
Conformations, 86
Conjugated bonds in MM2, 49
Conservative assumptions, list of, 13
Constraints, list of, 3
Contact potentials, 337
Continuum models, 12
Cooling systems, 330-332, 370
Cope rearrangements, 146
Correspondence principle, 76
Coulomb energy, 38
Coupled sites, 283
CPUs, 361, 367-370. See also Computation; Nanocomputers
Critical angular velocity, 339
Cubane, 88, 195
Cubene, 214
Cumulenes, 214, 245
Current density limits, 334
Curved-shell structures, 268
Cycle times for reactions, 208
Cyclo[18]carbon, 195
Cycloadditions, mechanochemical, 233
Cyclobutene, 148
Cyclopentyne, 214
Cyclopropane, 195, 217
D
Damage, see also Thermomechanical damage
dominance of radiation damage, 157
energy sources, 120
mechanisms of,
photochemical damage,
Dampers, 314
Damping, 91
Darcy-Weisbach formula, 327
Debye model, 169,170
Deformation, scaling of, 25
Density, table of values, 256
Design, see also Computer-aided design and approximation, 23, 497
computer support for, 434-441
errors in, 89
Detailed balancing, principle of, 78
Detents, 314
Diamond, see also Diamondoid solids; Diamondoid structures
chemical vapor deposition, 241
Debye temperature, 170
hexagonal, 246, 262
modulus and surface effects, 262
surfaces, 150, 239
synthesis as model, 238
theoretical tensile strength, 142
Diamondoid structures, 13, 255
vs. biological structures, 10
mechanosynthesis of, 238-248
number of, 263
stiffness and predictability, 87
. protein, for receptors, 375
Dielectric constant, 64
Diels-Alder reactions:
for adhesive interfaces, 270
mechanochemical forcing, 233
and molecular orientation, 136
in molecular processing, 386
piezochemistry of, 214
Diffusion, 139, 149, 329
Digital logic, 8, 36. See also Computation; Nanocomputers
Dipolar bonds for adhesive interface, 270
Dipoles, 48, 201
Dirac, P. A. M., and quantum theory, 37
Dislocations, 166, 254, 268
Dispersion force, see van der Waals force
Dissociation constants for antibodies, 374
DNA, 446-447
as structural material, 510
synthesis of, 196
Dodecahedrane, 195
Double bonds, torsional stiffness of, 48
Drag, see Energy dissipation
Ductility of metals, 254
E
Effective concentration, 198, 199
Effective volume, 124
Efficiency, scaling of mechanical, 27
Elastic springs vs. entropic springs, 118
Electrical current, scaling of, 29
Electrical switches, 335
Electric fields, 203, 320, 334
Electrochemistry, 203
Electromagnets, scaling of, 31
Electromechanical devices, 333-341
Electromechanical power, scaling of, 30
Electromechanical power density, 30
Electromigration, 29, 334
Electron correlation, 39, 40, 61
Electronegativity in MM2, 49
Electronic transitions, 29, 39 Electron relaxation time in metals, 31
Electrostatic actuators, 335, 366
Electrostatic energy, scaling of, 30
Electrostatic fields, 29, 200
Electrostatic force, scaling of, 29
Electrostatic generators (DC), 336-341
Electrostatic interactions in MM2, 48
Electrostatic motors, 336-341, 370
Elimination reactions and pyrolysis, 146
Ene reactions, 147
Energy, see also Potential energy; Potential energy surfaces; Power
mean value, 75
and nonbonded force, 59
and partition function, 75
release in adhesion, 271
units for molecular phenomena, 11
Energy barriers, see Potential barriers
Energy dissipation, 161
acoustic radiation, 162-168
band-flutter scattering, 175
band-stiffness scattering, 174
in bond cleavage, 222
dislocations as model, 166
in electrostatic motors, 339
free expansion losses, 188
in gears, 307
interfacial sliding, 273
and intersystem crossing, 224
in logic rods, 348
in mechanochemistry, 221
in molecular mills, 395
moving disturbances, 166
moving harmonic oscillators, 172
nonadiabatic quantum processes, 168
nonisothermal compression, 181-186
phonon-phonon scattering, 179
phonon scattering drag, 170
phonon viscosity, 180
radiating alignment bands, 167
in registers, 358
in roller bearings, 172
scaling with speed, 162
shear-reflection drag, 177
sleeve bearings,
in sliding of irregular objects, 282-283
in sorting rotors, 378
thermoelastic damping, 179
time-varying potential wells, 186-189
Entropic springs, 111-113, 118
Entropy:
defined in terms of probability, 82
of fusion, 263
and information, 82-83, 523
and partition function, 75
in quantum statistical mechanics, 75
Enzymes and mechanosynthesis, 200
Equilibrium, 80, 121
Error rates, see also Damage; Failure rates equilibrium model, 132
instantaneous-onset model, 133 in logic rods, 352
in mechanosynthesis, 197, 205
models for placement, 131
in molecular assembly, 130
worst-case decoupling model, 134
Errors:
in design, 89
in mechanochemical modeling, 192
in placement,
in radical addition, 229
sinusoidal well model, 132
switched coupling model, 132
Ethyne, 385, 391
Eutactic, definition, 6
Evolution and nanomechanical systems, 10
Exciton for "photochemistry," 203
Excluded-volume, 66
Exoergic s. endothermic, 196
Exothermic vs. endoergic, 196
exp-6 potential, 49,274
Experimentation, role of, 89, 137, 438, 480
F
Fail-stop systems, 393
Failure, single-point assumption, 15, 156
Failure rates, . See also
Damage; Error rates
False-negative errors, acceptability of, 16
False-positive errors, avoidance of, 16
Fan-in and fan-out, 362
Fatigue, 157, 317
Fault-tolerant systems, 390
Feedstocks, 373
Feynman, Richard, 27, 37, 83, 511-512
Field emission, 28
Field emission current, scaling of, 30
Field-ion microscope, 203
Field strength, limits to electrostatic, 28
Finite-state machines, 359-363
Flexibility of devices, 200
Fluid mechanics, 326
Fluids, 27, 328, 329. See also Liquids
Flywheels, 370
Follower and cam, 310
Force, see also Bond cleavage; Molecular mechanics
measurement of, 322
in mechanochemistry, 201
in molecular mills, 386
and nonbonded contact radii, 60
and nonbonded energy, 59
and nonbonded stiffness, 59
scaling of, 24
Foresight Institute, 513
Fourier transforms, 274-277
Fragmentation reactions, 146
Framework structure, 259
Free energy:
and gas in cylinder problem, 112
and information, 82 and mean-force potential, 85
and partition function, 75
Frequency, scaling of, 25, 32
Friction, 27, 80, 316
Fullerenes, 247
G
Gases, 326, 328, 329-330. See also Fluids
Gates, 343-355, 364
Gears:
barrier heights for rotation, 304
bevel, 308
energy dissipation, 307
helical, 308
planetary, 311
rack and pinion, 308
spur, 304-308
worm, 309
Generators, see Electrostatic generators
Graphite, 184, 256
Gravitation, effects of, 25,409
Grignard reagents, 219
Grüneisen number, 179
H
Hagen-Poiseuille law, 327
Hall, J. Storrs, 400
Hamaker constant, 63, 64
Harmonic drives, 323
Harmonic oscillators:
and classical mechanics, 71
and classical uncertainty, 91
damping by acoustic radiation, 164
damping of torsional, 165
energy of quantum mechanical, 93
Gaussian PDF, 91
graph of rms displacements, 95
mean energy, 93
mean square displacement, 93
phonon scattering, 172
quantum mechanical uncertainty, 92
and quantum mechanics, 71
thermally excited, 91
total vs. classical variance, 94
Heat, waste, 397. See also Energy dissipation
Heat capacity, scaling of, 33
Heat flow, 33
Helical gears, 308
Helium and seals, 328
Hexagonal diamond, 246, 262
Hydrocarbons, thermal stability of, 147
Hydrogen bonding, 270
Hydrogen and seals, 328
I
Independent electron approximation, 40
Inductance, scaling of, 31
Inductive time constant, scaling of, 31
Information, 82
Infrared spectroscopy, 71
Institute for Molecular Manufacturing, 513
Instrumentation, 87
Insulation (electrical), 334
Interfaces in bearings, 294
Interfacial sliding, see Sliding
Intersystem crossing:
and energy dissipation, 224
in pi-bond torsion, 231
radical coupling, 215
rates of, 197, 216
and reaction reliability, 210
Intramolecular reactions, 122. See also Rearrangement reactions
Ion(s), 198, 200, 328
Ionic bonding, 270
Ionic solids as materials, 255
Ionic species, reactions of, 212
Ionization, 150, 151
Ionization energies, 41
Irregular objects, sliding of, 277-284
Isotopes, 373
J
Jahn-Teller effect, 39
K
Kaehler brackets, 266, 436
Kinetic decoupling in error models, 132
Knudsen number, 326
Krummenacker, Markus, 467
L
Latching, 321, 356
Least common multiple, 286
Lennard-Jones potential, 58
LEPS potential, see
London-Eyring-Polanyi-Sato potential
Lifetimes,
Lifshitz theory, 64
Ligands for mechanochemistry, 235
Light, see Photochemistry
Linear systems, 77
Lippincott potential, 54, 62, 223
Liquids, 27, 326, 379. See also Fluids
Lithography, 9
Logic rods, 343-355
alignment knobs, 345
applied forces, 347
bounded continuum model, 346
drivers, 345
drive springs, 345
dynamics, 348-352
electronic analogies, 343
energy dissipation, 348-352
energy per switching cycle, 354
error rates, 352
gate knobs, 345
geometry, 346
housing structure, 345
input rods, 345 interlocks, 345
mass, 348
nonthermal vibrations, 351
output rods, 346
probe knobs, 345
reset springs, 346
sliding-interface drag, 350
stiffness, 348
stored energy, 352
thermoelastic losses, 351
vs. transistors, 354
vibrational excitation, 349
volume, 354
London-Eyring-Polanyi-Sato potential, 62,226
Lone pairs, 45
Lubricants, 26, 316, 329
M
Machine-phase systems, 6, 14, 122, 135
Magnetic field energy, scaling of, 31
Magnetic fields, 31,320
Magnetic force, scaling of, 31
Maitland and Smith potential, 58
Manufacturing processes, 397. See also Molecular manufacturing
Margins of safety and reliability, 16
Materials, survey of, 254-256
Mean-force potentials,
Mean free path in gas, 326
Measurement:
devices,
and equilibrium, 84
error models, 130
iteration and reliability, 322
Mechanical energy, thermalization of, 81
Mechanical engineering, 7,24
Mechanochemistry, 191-192. See also Mechanosynthesis
comparisons, 192
energy dissipation in, 221
forcible processes,
as power source, 397
theoretical modeling, 192
Mechanosynthesis, 1, 191,197-207. See also Mechanochemistry
and catalysis, 204
cluster-based strategies, 246
competing reactions, 204
of diamondoid structures, 238-248
electrochemistry, 203
electrostatic effects, 200
error rates in, 205. See also Error rates
flexible components, 200
handle structures, 197
highly active reagents, 206
ionic reactions, 200
ions in, 198
large effective concentrations, 198
limited reagents, 197
for molecular manufacturing, 207-211
natural parallelism, lack of, 197
nondiamondoid structures, 248
and photochemistry, 198, 203
radicals in, 198
reaction cycle times, 208
reagent preparation . application, 208
sensitivity to modeling errors, 88
in solution, 14
vs. solution-phase synthesis, 196-207
solvation, lack of true, 198
summary of comparison, 211
temperatures in, 198
Melting point, table of values, 256
Memory, 365
Merkle, Ralph C., 246, 268, 269, 286, 296,
Merkle buckling logic, 354
Metals:
electron relaxation time in, 31
as materials, 254,430
optical transmittance, 153
surface instability, 149
Microtechnology, 8
Miller, Mark Samuel, 369
Misreaction rates, 209, 229
MM2 model, 44-51
accuracy of, 42
atom types, 44
bond angle-bending, 45, 50
bond stretching, 44, 45
bond torsion, 47,48
collision data, comparison to, 58
conjugated bonds, 49
conservatism of designs, 50
electronegativity correction, 49
electrostatic interactions, 48
errors in modulus prediction, 262
at high bond stresses, 51
and interfacial sliding, 274
and MM3, 43, 50
nonbonded interactions, 44,48
poor fit of vibrational frequencies, 50
stretch-bend interactions, 49, 50
van der Waals force, 48
MM3, 43, 50
MNDO, 41
Modeling errors as perturbations, 87
Modulus of slim rods,
Molecular beam experiments, 72
Molecular biology, 10
Molecular dynamics, 72-74
Molecular machinery, 253. See also Nanomachines
Molecular manufacturing, 1. See also Mechanosynthesis
mill and manipulator approaches, 207
misreaction rates, 209
omitted-reaction rates, 209
reagent stability for, 210
and reliability constraints, 207
resemblance to digital logic, 8 vs. solution-phase chemistry, 5
Molecular mechanics, 42-61
combined with quantum methods, 61
experimental basis, 42
as a level of approximation, 12
limitations of, 43
Molecular mills, 386-398
belt and roller systems, 386
conditional repetition, 388,396
energy dissipation, 395
error detection, 394
error rates, 393
fail-stop systems, 393
fault tolerance, 390
interfacing mechanisms, 390
mass, 391
pallets, 390
radiation damage, 394
reactive encounters, 386
reagent application, 391
for reagent preparation, 391
size, 391
waste heat generation, 397
Molecular nanotechnology, 1. See also Mechanosynthesis; Molecular manufacturing
Molecular orbital methods, 12, 40-42
Molecular ordering, 383-386
Molecular reaction dynamics, 61
Molecular solids as materials, 255
Molecular structures, geometry of, 86
Molecules, sorting and ordering, 373-386
Monte Carlo analysis, 278
Morrison, Philip, 503
Morse potential, 51, 52
and bond cleavage, 61
and bond stability limits, 54
in the LEPS potential, 62
in tensile bond cleavage, 223
and thermomechanical bond cleavage, 141
Motion, mechanical . thermal, 80
Motors, see Electrostatic motors
Murray's law, 331
N
Nanocomputers, see also Computation; CPUs; Finite-state machines; Gates; Logic rods; Memory; Nanomachines; Registers
cooling of large arrays, 370
electronic analogies, 342
interfaces, 366
material properties, 343
signal transmission, 342
why mechanical, 14
Nanoelectronic devices, 14, 29
Nanomachines, 2-5. See also Molecular machinery; Nanocomputers
Nanomechanical engineering: compared to chemistry, 51 vs. macromechanical engineering, 315-318
and mechanical engineering, 24
and PES requirements, 51,87
problem of positional uncertainty, 90
stability vs. sensitivity, 87
stiffness and error tolerance, 87
Nanomechanical systems:
vs. biological, 253
nanoelectronics, contrasted to, 14
relatively simple PES, 80
thermal vs. mechanical motion, 80
uncertainty in, 83
Neutrinos and radiation damage, 156
Nonblocking merging junctions, 390
Nonbonded interactions:
and collision data, 58
continuum models of, 63-67
effective mean stiffness, 172
and interfacial sliding, 274
Lennard-Jones potential, 58
Maitland and Smith potential, 58
in MM2, 44, 48
Nonisothermal compression:
harmonic wells, 184
in measurement, 321
multidimensional systems, 185
in registers, 358
and thermoelastic losses, 179-180
square wells, 181
Nonlinear effects, 71
Nuts, 301
O
Objectives, limitations in this volume, 15
Omitted reactions, 209
Orbital symmetry, 234
Organic synthesis, 193-196
Organometallic reagents, 219
Ostwald, Wilhelm, 191
Overlap forces, 63
Overlap repulsion in MM2, 49
P
Partition functions:
classical harmonic oscillator, 125
classical theory, 76
and entropy, 75
and free energy, 75
and mean energy, 75
and pressure, 75
in quantum statistical mechanics, 75
quantum transition state theory, 126
ratios of quantum and classical, 127
transition state theory, 122
Partitioning of wells, 321
PDF, see Probability density function
Peroxide, 139
PES, see Potential energy surfaces
Phonons:
and ballistic heat transport, 33 energy density of, 169
optical modes, 170
phonon viscosity, 180
transmission coefficient, 175
Phonon scattering:
and energy dissipation, 169-179
harmonic oscillators, 172
phonon-phonon scattering, 179
in sliding of irregular objects, 282
Photochemistry, 151
avoidance via shielding, 15,153
as damage mechanism, 150-154
design for stability, 152
and mechanosynthesis, 203
Pi-bond torsion, 230-232, 387
Piezochemistry, 201
Pipe, fluid flow in, 327
Piston and cylinder, 111-113
Placement, error rate models, 131
Planetary gear systems, 311
PM3, 41
Poisson's ratio, 163,166
Polar groups, 150
Polarizability, 41
Polymeric solids as materials, 255
Polymer pyrolysis, 145
Polyynes, 214
Position, measurement of, 322
Positional uncertainty, 90,92, 118
Potential barriers:
for abstraction of hydrogen, 226
and applied force, 220
for cleavage of stressed bond, 141
and compressive load, 226
gear rotation, 304
in interfacial sliding, 274, 277
Monte Carlo analysis, 278
quantum corrections, 126
and reaction rates, 86
and reaction reliability, 209
reduction by compensation, 312
tunneling transmittance, 129
vector model, 278
Potential energy, 76, 93
Potential energy surfaces:
accuracy requirements,
basis for nanomechanical design, 36
chemical accuracy, 85
and conformations, 86
errors and later correction, 89
errors as perturbing forces, 87
and mechanosynthesis, 88
of nanomechanical systems, 80
perturbed by thermal bath, 80
physical accuracy, 85
sensitivity of designs to errors, 87
of a solution-phase system, 79
time dependent, 130
Potential wells, 36, 186, 321
Power:
electrostatic motors, 336-341 mechanochemical sources, 397-398
scaling of mechanical, 26,30
supply for CPUs, 370
Pressure, 75, 201, 202, 320
Probability density, 76
Probability density function, 38, 91
Probability gas, 77-78, 122
Probability of states, 75
Propellane, 195
Proteins, 86, 196, 380. See also Antibodies
Pumps, 329
Purification cascades, 380-383
Pyrolysis, 145-148
Q
Quality factor, scaling of, 32
Quantum chemistry, 192
Quantum electrodynamics, 37
Quantum electronics, 14, 29
Quantum interference, 85
Quantum theory and the PES, 37-42
Quantum uncertainty, 83
Quasiclassical approximation, 72
R
Rack-and-pinion gears, 308
Radiation, 33, 154. See also Acoustic radiation; Radiation damage
Radiation damage, 154-156
classical target theory, 154
dominance of, 157
in molecular mills, 394
shielding from, as difficult, 156
simple lifetime model, 155
track-structure lifetime model, 155
Radicals:
abstraction reactions, 215
addition reactions, 215, 229, 386
coupling, 62, 215
displacement, 232, 388
mechanochemical displacement, 232
in mechanosynthesis, 198
as reagents,
sigma, 216
stabilization by delocalization, 215
Random-access memory, 365
Random-walk model, 277
Ratchets, 315, 474-476
Reaction coordinate, 121
Reaction(s), see also Mechanosynthesis; Potential barriers; Rearrangement reactions; Transition state theories
bond breaking s. rearranging, 135
as cause of damage, 134, 144-149
elementary . nonelementary, 144
intramolecular, 137
and molecular mechanics, 61
potential energy functions, 61-63
rate of, and effective concentration, 198
rate of, and electrostatic effects, 200
rate of, and PES accuracy, 85 sensitivity to small energies, 41
Reaction cycle, 230
Reactive encounter mechanisms, 387
Reactive intermediates, 149
Reactive species, 212-220
Reagent(s):
application of, 208, 391
highly reactive, 206
multiply-bonded noncarbon atoms, 247
preparation of, 208, 391
stability of, 210
Reagent devices, 149, 200
Rearrangement reactions:
of carbenes, 218
of ionic species, 213
photochemical, 151
and pyrolysis, 146
radicals, 217
of unsaturated hydrocarbons, 215
Receptors:
antibodies as models, 374
diamondoid structures, 265, 375
rotor with modulated, 374
for selective transport, 373-380
specificity, 376
tight-receptor mechanism, 377
Reconstruction of surfaces, 149, 239-240
Redundancy, 159. See also Reliability
Refractive index, 64
Registers, 355-359
Relativistic effects, 37
Relaxation of vibration, 81
Reliability, 16,36,159, 207. See also Damage; Error rates; Failure rates
Resistance, scaling of, 29
Resistive power density, scaling of, 30
Resonance effects, 129
Reynolds number, 327
Ribosomes, as machine tools, 10
Rods:
approximate total longitudinal uncertainty, 101
classical longitudinal uncertainty, 96
as entropic springs, 113
longitudinal positional uncertainty of, 94-101,113-117
quantum mechanical longitudinal uncertainty, 97
signal transmission, 342
sliding in sleeves, 302
thermally excited bending, 104-110
transverse vibrational effects, 113-117
Roller bearings, 172, 308
Rollers and belts, 309
Safety, 16. See also Reliability
Scaling, 35
of capacitance, 30
classical laws, 27, 28, 33
of classical mechanical systems, 24-28 constant electric field assumption, 28
constant shape and stress, 24
of deformation, 25
of electric current, 29
of electromagnets, 31
of electromechanical power, 30
of electrostatic energy, 30
of electrostatic force, 29
of energy dissipation with speed, 162
of field emission current, 30
of force, 24
of frequency, 25,32
of heat capacity, 33
of inductance, 31
of inductive time constant, 31
of magnetic fields, 31
of mass, 25
of mechanical efficiency, 27
of mechanical power density, 26
of positional variance with temp., 118
of quality factor, 32
of resistance, 29
of resistive power density, 30
of shear stress, viscous, 26
of skin depth, 31
of speed, 26
of stiffness, 25
of strength, 24
of temperature elevation, 33
of thermal conductance, 33
of thermal speed, 28
of thermal systems, 32-33
of thermal time constant, 33
of wear, 27
of reaction yield, 204
Schrödinger, Erwin, 38
Schrödinger equation, 12, 38-39
Schwinger, Julian, 37
Screws, 301
Second law of thermodynamics, 83
Semiconductors, reconstruction of, 150
Semiempirical methods, 41
Shape, 262-266, 320, 322
Shear, 327
Shear-reflection drag, 177, 291
Shear stress, scaling of viscous, 26
Shielding, 153,156
Signal transmission, 342, 343, 363
Singlet states and bond formation, 62
Size and surface effects, 258
Skin depth effects, 31
Sleeve bearings, 284-301
acoustic radiation in, 290
construction-simplifying asymmetry, 300
load-compensating asymmetry, 300
loaded, 288
rotational symmetries, 285
shear-reflection drag in, 291
small bearing designs, 298
spatial frequencies, 285
stiffness, 289 strained-shell design, 297
unloaded, 286
Sliding, 277-284, 312
Software, see also Computer-aided design for large systems, 371
automated design-rule checking, 160
Solution-phase systems, PES of, 79
Solvation, eutactic analogue, 200
Solvents, 138, 144
Soreff, Jeffrey, 168, 174, 175, 177, 178, 324, 340,436
Sorting rotors,
Spectral density, 275
Speed, scaling of, 26
Sphere, fluid drag, 327
Spin and energy dissipation, 224
Spin-orbit coupling, 37, 216
Stability, 137, 296. See also Reliability
States in configuration space, 78
Static friction, 283
Statistical mechanics, 73-85
applicability of classical, 77
assumption of equilibrium, 74
classical partition function, 76
classical and quantum uncertainty, 83
classical theory, 75
departures from equilibrium, 80
vs. detailed dynamics, 74
equilibrium assumptions, 80
and estimated failure rates, 74
mean energy, 75
nonequilibrium conditions, 80
partition function, 75
and probabilistic descriptions, 74
probability of quantum state, 75
quantum theory of, 75
of single molecules, 74
uncertainty and equilibrium, 84
Steric crowding and piezochemistry, 203
Stewart platform, 476-477
Stiffness:
and bond cleavage, 222
of bond stretching, 44
and effective concentration, 199
and error rate in radical addition, 230
under large loads, 51
and mechanosynthetic errors, 205
in molecular mills, 386
and nonbonded force, 59
scaling of, 25
and sensitivity to modeling errors, 87
of sleeve bearings, 289
of surface atoms, 225
torsional, 47
of transition metal bonds, 237
Stokes's law, 327
Storage systems, 365
Strain, see also Bond stretching
in diamondoids . steel, 317
in MM2, 42
and reaction rates, relief by dislocations,
in shell surfaces, 267-268
Strength, 24, 221, 256
Stretch-bend interactions, 49, 50
Surface(s):
atomic stiffness of, 225
forces between, 63
interaction forces in vacuum, 66
softness relative to macroscale, 316
stability of, 149
Surface effects, 13, 257, 258-262
Symmetrical structures,
Synthesis, 3. See also Organic synthesis; Mechanosynthesis
T
Taylor, Dean, 476
Temperature, operating, 15
Temperature elevation, scaling of, 33
Temperature of single molecule, 74
Tensile loads and bond PESs, 51
Thermal bath, 72, 80
Thermal bond cleavage, 138-140
Thermal conductance, scaling of, 33
Thermal equilibrium, 72
Thermal expansion, 179, 181
Thermal gradients, 80
Thermalization of mechanical energy, 81
Thermal motion, 28,77-80, 92
Thermal speed, scaling of, 28
Thermal systems, scaling of, 32-34
Thermal time constant, scaling of, 33
Thermodynamics, see also Energy; Entropy
of molecular manufacturing, 426
second law, 83,505
and statistical mechanics, 73-77
third law, 82
Thermoelastic damping, 179, 181, 283, 292
Thermomechanical damage, 134-150
Time, scaling of mechanical motion, 26
Time-dependent PES, models of, 130
Tomonaga Shini'chirō, 37
Toroidal worm drives, 323
Torsional stiffness, magnitude of, 47
Transformation time, 197
Transistors, 12, 354
Transition metals and complexes, 219
bond stiffnesses in complexes, 237
ligands for mechanochemistry, 235
mechanochemical processes, 234
in molecular processing, 386
multiply bonded complexes, 234
pi-bond torsion in complexes, 232
and power generation, 397
Transitions, forced, 81
Transition rate, 224
Transition states, 121, 122, 205
Transition state theories, 121-128
classical, 121-126
equilibrium assumption, 121 and error rate models, 131
partition function, 122
probability gas, 122
quantum rate constant, 128
quantum theories, 126
and time-dependent potentials, 131
transition rate, 122
transmission factors, 126
variational theories, 125
Wigner tunneling correction, 127
Transverse-continuum approximation, 289
Tribble, Eric Dean, 253
Triplet states, 62
Tube, fluid flow in, 327
Tunneling:
and bond cleavage, 142
charge neutralization reactions, 213
corrections to transition state theory, 126
and electrical contact, 334
and electrical insulation, 334
of electrons . atoms, 29
resonance effects, 129
transition rates, 128
Tunneling junctions, 335,366
Turbomolecular pumps, 329
U
Ultraviolet light, 151, 153
Uncertainty, quantum and classical, 83.
See also Positional uncertainty
Unsaturated hydrocarbons as reagents, 213
V
Vacuum pumps, 329
van der Waals force:
and adhesive interfaces, 270
continuum models of, 63-66
interactions between objects, 64
in MM2, 48
Vibration, 71, 351
Vibrational excitation of logic rods, 349
Viscosity, 27, 326
W
Waste heat, 397. See also Energy dissipation
Wave function, 38,129
Wear, 27, 157, 316
Wentzel-Kramers-Brillouin, 128
Wigner correction factor, 127
WKB approximation, 128
Work of compression, 84
Work functions, 337
Worm drives, toroidal, 323
Worm gears, 309
X-Z
Xenon, as a solvent, 482
Yield, scaling with size, 204
Young's modulus, table of values, 256
Zero-point energy, 52, 126
).