106,99 €
Mehr erfahren.
- Herausgeber: Wiley-VCH
- Kategorie: Fachliteratur
- Sprache: Englisch
Introductory resource on nanoscience and molecular engineering stressing the interdisciplinary nature of the field
Principles of Nanoscience and Molecular Engineering introduces nanoscale principles in molecular engineering, providing hands-on experience and stressing the interdisciplinary nature of this field. The book integrates phenomenological knowledge of material and transport properties with atomistic and molecular theories, bridging the gap between unbound classical three-dimensional space and the constrained nanorealm.
The book challenges conventional wisdom derived from anecdotal experiences and fosters an understanding of nanoscale molecular collective phenomena that do not violate classical physical laws but rather expand upon them. The surprise exotic awe is replaced by improved insight into the workings of atoms and molecules under interfacial, dimensional, and size constraints.
Readers will find detailed insights on molecular phase behavior under confinement, the atom model and wave equation, quantum mechanics, the electronic structure of molecules and matter, molecular modes and energetic properties, self-assembly, and statical mechanics of pair interactions in gases.
Written by a highly qualified professor in chemical engineering with significant research contributions to the field, Principles of Nanoscience and Molecular Engineering includes information on:
- Shared perceptions of our world and their shortcomings, applied to the nanoscale, specifically to transport properties
- Structured condensed systems affected by interfaces and size constraints, examining the effect of non-interacting solid interfaces on liquid phases and free surfaces of solid crystal lattice arrangements
- The liquid condensed state, highlighting boundary conditions in thermally equilibrated systems
- Electronic transport in relation to the electronic structure of molecules, focusing on the movement of electrons through lower-dimensional systems
Principles of Nanoscience and Molecular Engineering serves as an excellent introductory resource on the subject for readers studying or working in related fields.
Sie lesen das E-Book in den Legimi-Apps auf:
Seitenzahl: 859
Veröffentlichungsjahr: 2025
Ähnliche
Table of Contents
Cover
Table of Contents
Title Page
Copyright
Dedication
Preface
Units, Fundamental Constants, and Symbols
About the Companion Website
Chapter 1: The Realm of Nanoscience and Molecular Engineering
1.1 Nanoscience and Molecular Engineering
1.2 Properties in Lower Dimensionalities
1.3 Mechanical System Responses
1.4 Driving Forces and Responses in Thermal Transport
1.5 Electronic Transport of Lower Dimensional Systems
1.6 Acoustic Transport and Dimensionality
1.7 Critical Molecular Response Times in Nanoconstrained Systems
1.8 Miniaturization, Scaling, and System Constraints
1.9 Organization and Outlook for Nanoscience and Nanotechnology
Study Problems to Chapter 1
Notes
Chapter 2: Interfacial and Size-Constraint Systems
2.1 Overview
2.2 VdW Molecular Interactions
2.3 Interfacial Effects on Liquids and VdW Solids
2.4 Interfacial Effects on Spin-Coated Polymer Films
2.5 Size and Interfacial Constraints in Metal Nanoclusters
2.6 Two-Dimensional Systems and Surface Energy
Study Problems to Chapter 2
Notes
Chapter 3: Size-Constrained Condensed Fluid Molecular Systems
3.1 Molecules and Phase Properties
3.2 Metastable Liquid Phenomena
3.3 Hydraulic Transport in Capillaries and Boundary Conditions
3.4 Nanoconduit Flow – BL Model and Nanocapillaries
3.5 Membrane Transport
Study Problems to Chapter 3
Notes
Chapter 4: First Steps Toward Quantum Mechanics
4.1 Thermal Emission: From Boltzmann to Quantum Distribution Law
4.2 First View into Quantum Mechanics
4.3 Atom Structure and a Simple Model
4.4 Wave and Particle Interferences and Probability
4.5 Quantum Wave Theory, Quantum Constraints and Uncertainty
Study Problems to Chapter 4
Notes
Chapter 5: Electron Transport and Electronic Structure of Molecules
5.1 Electron Transport in One-Dimensional Quantum Wire
5.2 Electron Tunneling
5.3 Single Electron Device Technology
5.4 Electrons, Energy States, and Distribution in Atoms
5.5 Electron Distribution and Bonding in Molecules
5.6 Mobile Electrons
Study Problems to Chapter 5
Notes
Chapter 6: Electronic Structure of Matter
6.1 Electronic States and Transport in Condensed Material Phases
6.2 Background on Doped Inorganic Semiconductors
6.3 Photovoltaic Cells
Study Problems to Chapter 6
Notes
Chapter 7: Molecular Modes and Energetic Properties
7.1 Molecular Modes
7.2 Bond Vibrations in Molecules
7.3 Rotational Molecular Mode in Diatomic Molecules
7.4 Polyatomic Molecules
7.5 Lattice Vibrations – Phonons
Study Problems to Chapter 7
Notes
Appendix to Chapter 1
A.1 Acoustic Wave Equation
A.2 Homogeneous Second-Order Differential Equation
A.3 Solution of the 1D Wave Equation in Cartesian Coordinates
Appendix to Chapter 5
A.4 Solution to the Schrödinger Wave Equation for Hydrogen
Index
End User License Agreement
List of Illustrations
Chapter 1
Figure 1.1 The nanoscale, microscale and macroscale. The significant difference between the...
Figure 1.2 Trial-and-error discovery: Sulfur vulcanization of natural rubber (patented by C...
Figure 1.3 (a) LNP delivery system for mRNA payload. (b) 1–4 delivery steps of genetic mRNA...
Figure 1.4 “Liquid” films are sheared, and the lateral response force F is measured. Viscou...
Figure 1.5 Orientation of houses, roofs, and openings in regards to the direction of rain i...
Figure 1.6 Capillary piston-die rheometer. Polymer phase regimes in capillary are highlight...
Figure 1.7 (a) Simple jump model: Submolecular activation barrier without stress and with ...
Figure P1.4.1 1D Heat flux through a plane wall.
Figure P1.4.2 Maxwell-Boltzmann distribution of Ar, O
2,
and CH
4
gas at 1 bar and 300 K. The ro...
Figure 1.8 Thermal conductivity as a function of the critical size for a mean free pa...
Figure 1.9 Zero, one-, and two-dimensional systems: Nanoparticles (0D), nanofilaments (1D) ...
Figure 1.10 (a) Constant conductance (Ohm’s law) in bulk systems. (b) Quantum point contacts and...
Figure 1.11 Double slit experiment of (a) corpuscular particles, and (b) waves. The wave dif...
Figure 1.12 Train model to contrast bulk transport to quantized transport. (a) Single wagon ...
Figure 1.13 Quantized staircase-like conductance for 1D quantum wires at zero Kelvin. The co...
Figure 1.14 Huygens principle: A wave propagates through a medium where each point on the ad...
Figure 1.15 Surface acoustic wave (Rayleigh wave) applications in (a) microfluidics as fluid...
Figure 1.16 (a) AFM friction setup. Illustrated is the tip-apex/sample-surface VdW interaction. ...
Figure 1.17 Maxwell model for longitudinal deformation: Combines a viscous damper of viscosi...
Figure 1.18 Maxwell creep-recovery response.
Figure 1.19 (a) Shows the synchronized by time-delayed (phase-shifted) response between the harm...
Figure 1.20 Friction on glassy PtBA at a reference temperature of 315 K modeled based on Eq....
Figure 1.21 (a) Re < ~0.1: Stokes’ potential flow around a sphere in a gravitational field passi...
Figure 1.22 Terminal velocities for creeping flow (Stokes, Eq. (1.69)), and faster flow velo...
Figure P1.8.2 1D Mass flux through a polymer composite membrane.
Figure 1.23 Linear fits of reduced relative gas permeabilities of N
2
, H
2,
and C
2
H
6
through n...
Figure 1.24 Interface between a solid substrate and a polymer. Distinguished are the polym...
Figure 1.25 PTMSP chemical structure. Numbered are (1) the trimethyl-silyl rotation, (2) the...
Figure 1.26 Single-walled (5,5) CNT with longitudinal heat conduction, as depicted with heat...
Figure 1.27 (5,5) Thermal conduction coefficient as function of the length of a single-walle...
Figure P1.8.3a Graphene structural elements.
Figure P1.8.3b Power law coefficient as a function of the CNT length.
Figure 1.28 Technologies meet fundamental sciences on the nanoscale.
Figure SP1-1 Cantilever and forces
Figure SP1-2 I-V characteristic of multiwall CNT fit to literature data.
48
Chapter 2
Figure 2.1 (a) Symmetric or nonpolar molecules, such as CO
2
, exhibit (some distance away) no di...
Figure P2.2.2 Heuristic model of dispersion interaction involving a Bohr atom with a proton ce...
Figure 2.2 Electric permittivity for polar (water) and nonpolar (hexadecane) media. For non...
Figure 2.3 Effect of interfaces on liquid and solid material structures at room temperature...
Figure 2.4 An atom or molecule (dark red colored) positioned in a HCP system (
left
) in the ...
Figure 2.5
Top
: A positive spreading coefficient yields perfect wetting.
Bottom
: A negati...
Figure 2.6 VdW interaction potentials between (a) sphere-plane, (b) plane-plane (two infini...
Figure 2.7 Extreme directional alignment of a straight linear chain alkanes: (a) vertical a...
Figure 2.8 (
Left
) Tetracene C
18
H
12
. (
Right
) Pyrene C
16
H
10
.
Figure 2.9 D
2h
molecular structure, illustrated with ethylene (C
2
H
4
).
Figure 2.10 Tetracene crystal: (
Left
) Triclinic crystal structure with two molecules per uni...
Figure 2.11 Pyrene crystal: (
Left
) Monoclinic crystal structure with four molecules per unit...
Figure P2.3.3a Slipped parallel pyrene dimer arrangement.
Figure P2.3.3b Pyrene dimer interaction energy as function of the dimer separation.
Figure 2.12 Silicon (111) surface reconstruction: (
Left
) 1 × 1 surface structure (in red) at...
Figure 2.13 (a) Mechanical response (stiffness [MPa]) of a polymer as function of temperature. ...
Figure 2.14 (a) Sketch of entangled polymer chains: (Top) Low entanglement for and high ...
Figure 2.15 Polymer solution: (Left) dilute, (middle) semi-dilute, (right) concentrated – en...
Figure 2.16 Substrate-supported thick (»100 nm) polymer film: Free energy adjusted sidechain...
Figure 2.17 Sketch of a mechanical relaxation spectrum of a polymer, where represents t...
Figure 2.18 Polystyrene secondary relaxations: (a) -relaxation, local segmental motion (cra...
Figure 2.19 (a) In ultrathin films the bulk-regime is replaced by an interfacially constrained...
Figure 2.20 (a) Sketch of glass transition profile of polystyrene (12.1 kDa) on Si(100) ad...
Figure 2.21 (a) Illustration of the surface stress (tension) expressed by the Laplace pressu...
Figure 2.22 (a) 38 atom TO nanocluster (e.g., silver). Visualization of two additional Plato...
Figure 2.23 Surface energy and cohesive energy of Ag nanocrystals of IH, TDH, and TO structu...
Figure P2.5.1 lattice with <111> and <100> crystal faces, and NN distance .
Figure 2.24 List of four selected allotropes of carbon: (a) HOPG, (b) graphene, (c) C
60
mole...
Figure 2.25 (
Left
) (a) HOPG AB-structure with basic unit cell (dashed red lines) in the form...
Figure P2.6.1 Unit cell projection within the graphitic layer (shaded rhombus) identifying exa...
Figure 2.26 Surface free energy of graphene layers determined from experimental data at la...
Figure P2.6.2(a) HOPG single sheet (gray) versus isolated graphene sheet.
Figure P2.6.2(b) Semi-qualitative plot of contamination kinetic differences between HOPG in nitro...
Figure SP2.1 Change in the relative permittivity with temperature of liquid determined with t...
Figure SP2.2 OMCTS.
Figure SP2.3 Strain in nanocomposite with particle density below and above .
Chapter 3
Figure 3.1 L J potential between two methane molecules as a function of the molecular distance.
Figure 3.2 London dispersion parameter obtained from Eq. (3.8) with data provided i...
Figure P3.1.2 One-electron atom model. (
Left
) No external electric field is applied. (
Right
) A...
Figure 3.3 Visualization of the gas coefficients data ( and ) and the molecular electroni...
Figure 3.4 Reduced pressure-volume diagram of a pure substance based on VdW EOS, Eq. (3.13)...
Figure 3.5 Reduced compressibility charts for , 1.2, and 1.5, comparing the VdW EOS t...
Figure 3.6 Contrasted dispersion energy calculations based on London’s equation (Eq. (3.8))...
Figure 3.7 (
Left
): EOS (solid black line) of a VdW fluid at expressed in terms of ...
Figure 3.8 Cavitation in static fluids. (a) Huygens vial experiment: (
Left
): Liquid water u...
Figure 3.9 Free energy on bubble nucleation as a function of the vapor bubble volume f...
Figure 3.10 Nucleation barrier on bubble formation as a function of the applied tensile ...
Figure 3.11 Probability for cavitation as a function of the tensile stress for water at 25 °...
Figure P3.2.3 Fixed temperature consideration of (a) the original system liquid volume unde...
Figure 3.12 (a) Illustration of a tree emphasizing the two endpoints regarding water transfer, i...
Figure 3.13 (
Left
): Solid black line, a fit of the cavitation resistance (adapted from...
Figure 3.14 (a, b) Cutin monomers: Selected oxygenated long-chain (16- or 18-carbon) fatty a...
Figure 3.15 Poiseuille flow of a Newtonian liquid in a cylindrical capillary, revealing a pa...
Figure 3.16 Shown are the three main boundary conditions for Poiseuille flow in a cylindrica...
Figure 3.17 Investigation of the BL in stationary liquids at ultrasmooth silicon oxide inter...
Figure 3.18 Wettability of smooth and rough surfaces and consequential change in the slip bo...
Figure 3.19 Effective viscosity of water ( and ) in a straight cyli...
Figure 3.20 (
Left
): Flow enhancement of water ( and ) in CNT with sel...
Figure 3.21 (a) Schematic illustration (adapted from [35]) of a carbon nanotube embedded at ...
Figure 3.22 (Top) Sketches of water structures in the liquid phase and solid (ice) phase. Mo...
Figure P3.4.2 Normal vibrational modes of water molecules in the gas phase, fundamental freque...
Figure 3.23 Osmotic transport of solvent through a semipermeable membrane. (a) Non-equilibri...
Figure 3.24 Simplified schematics of a SWRO plant, not detailing the treatment steps. Treate...
Figure 3.25 Rough classification of membrane types and configurations.
Figure 3.26 Two mechanisms of pressure-driven transport of component through a membrane. (...
Figure P3.5.4 Osmotic equilibrium: SD model for .
Figure 3.27 Sketch of the ion concentration profile within the SD model of pressure-driven o...
Figure 3.28 Desalination results using an aromatic polyamide FT-30
®
membrane (adapted from [...
Figure 3.29 Effect of the CP, captured by the membrane wall feed concentration, , on ...
Figure 3.30 Desalination results involving an aromatic polyamide FT-30
®
membrane, with data ...
Figure 3.31 AAO porous sieve membranes. (
Left
): Pristine AAO shown in top-view and side-view...
Figure 3.32 Pressure-driven capillary injection method of PTMSP solution into AAO sieve memb...
Figure 3.33 The development of impregnation height over time of PtBA in AAO shows faster imp...
Figure SP3.1 Nucleation rate of vapor bubbles in water.
Figure SP3.2 Tree resistance model with and .
Figure SP3.3 Tensiometer with pressure schematics.
Figure SP3.4 Osmotic pressure setup.
Figure SP3.5 Symmetric capillary meniscus.
Chapter 4
Figure 4.1 First steps toward quantum mechanics and quantum field theory.
Figure 4.2 Spectral irradiance spectrum of tungsten-halogen lamp at 0.5 meter at various te...
Figure 4.3 Spectral irradiation of blackbody radiator. The table inset provides the wavelen...
Figure 4.4 Blackbody cavity radiator setup.
Figure 4.5 Visualization of stationary standing waves in a 1D cavity of length . The obser...
Figure 4.6 Derived relationship between the spectral energy density within the cavity and t...
Figure 4.7 The Rayleigh-Jeans classical description of the spectral irradiation of blackbod...
Figure 4.8 Visualization of the three principal distribution laws in nature: (a) Thermal pa...
Figure 4.9 Principle distribution laws nature in comparison: .
Figure 4.10 Possible configuration of three particles assuming a constant total energy of .
Figure 4.11 Possible configuration of three particles assuming a constant total energy of .
Figure 4.12 Hertz spark experiment: the EM wavelength is changed when UV radiation falls on ...
Figure 4.13 Photoelectric effect: The photons provide enough energy to remove metallic elect...
Figure 4.14 Davisson-Germer experiment.
23
Schematics of diffraction on a grid with lattice s...
Figure 4.15 The Franck-Hertz Experiment: (
Left
) Accelerating apparatus (tube filled with low...
Figure 4.16 First steps toward Quantum Mechanics and Quantum Field Theory, with a focus on t...
Figure 4.17 Rutherford’s ɑ-particle (He
2+
) scattering experiment involving a thin gold foil....
Figure 4.18 Hydrogen emission spectrum with emission series ending at (Lyman series),...
Figure 4.19 (
Left
) Bohr shell orbital model. (
Right
) Energy levels for the hydrogen atom.
Figure 4.20 A periodic wave is shown at the time and . The wave moves with the...
Figure 4.21 Visual comparison of the periodic sine wave and a spinning wheel. The argument o...
Figure 4.22 Light diffraction at a single slit. Wavelet interference at the slit determines ...
Figure 4.23 Light diffraction at double slit: Parameter relationships visualized.
Figure 4.24 Light diffraction at the double slit. Constructive interference at
Figure 4.25 Double slit with macroscopic particles, waves, and electrons. Electrons exhibit ...
Figure 4.26 Fitted multiplicity increase over the years based on a wide variety of reported ...
Figure 4.27 Free particle of energy in a quantum box (well) of infinite wall dimension at ...
Figure 4.28 Free particle in a box (well) of infinite wall dimension at and . The...
Figure 4.29 Laser gain spectrum for quantum films, quantum wires, and quantum dots. (Inspire...
Figure 4.30 Electron energies and wave functions in quantum structures.
Figure 4.31 Quantum entanglement of a binary spin system. Spin-up and spin-down states of th...
Figure 4.32 Achieved numbers of linked qubits in quantum computers over the years.
Figure SP4.1 Single-slit diffraction.
Chapter 5
Figure 5.1 1D quantum wire confined in and of quadratic cross-section . The electrons...
Figure 5.2 Bulk diffusive (top) versus ballistic (bottom) transport in wires. Defining diff...
Figure 5.3 Single-mode 1D quantum wire for at (a) zero external electric field and (b) fini...
Figure 5.4 Multimode quantum wire. (
Left
) The bias between the source (S) and the drain (D)...
Figure 5.5 Finite quantum potential well.
Figure 5.6 A finite quantum well reveals a ghost-like state of existence of the quantum par...
Figure 5.7 Finite quantum well: (
Left
) Schematic wave function solution. (
Right
) Particle p...
Figure 5.8 Tunnel effect: Incident particle (electron) from the left is reflected and trans...
Figure 5.9 Tunnel junction with electrode work functions, Fermi energies, applied bias volt...
Figure 5.10 Schematics of STM 1D tunneling configuration. The two harmonic electron wave fun...
Figure 5.11 Schematic of a MIM tunneling junction. The gray area represents electron-filled ...
Figure 5.12 (a) (
Left
) STM constant current image (9 Å × 9 Å) of highly oriented pyrolytic g...
Figure 5.13 Modes of tunneling spectroscopy.
Figure 5.14 Electron levels and electron bands. (
From right
) The isolated atom reveals discr...
Figure 5.15 Conduction and valence bands for insulators, semiconductors, and conductors.
Figure 5.16 Simplified sketches of single electron transistor (SET) containing (a) a metal i...
Figure 5.17 (a) Coulomb parabolic potential yield to discrete electron transport. (b) The cu...
Figure 5.18 (
Left
) Schematics of a FET, more specifically a n-type FET. (
Right
) Schematics o...
Figure 5.19 Working schematics of a SET. In the off state, there are no electrons in the sou...
Figure 5.20 SET: Coulomb staircase at .
Figure 5.21 Temperature effect on Coulomb staircase.
Figure 5.22 Top: SET energy diagrams of (
left
) large (classical) islands ≥ 10 nm, and, (
right
) sm...
Figure 5.23 Energy dependencies on QD SET diameter.
Figure 5.24 Radial wave function and probability density for and . We employed th...
Figure 5.25 Radial distribution function of hydrogen atom for and .
Figure 5.26 Electron distribution of -orbitals (). orbital nodal planes.
Figure 5.27 An example of one of the five electron distributions of -orbitals () featu...
Figure 5.28 Degeneracies for 3p orbit. Spin-orbit coupling yields splitting of the orbital s...
Figure 5.29 Zeeman effect in hydrogen for transitions. Fine structure i...
Figure 5.30 Angular and magnetic moment of a moving charge in a closed loop.
Figure 5.31 Degeneracies compared between hydrogen and multi-electron atoms.
Figure 5.32 The occupied electronic states of carbon atom (1s
2
2s
2
2p
2
) and oxygen atom (1s
2
2s...
Figure 5.33 (
Left
) Hydrogen ion composed of two positively charged protons (P1 and P2) an...
Figure 5.34 Symmetric and antisymmetric linear combination of two hydrogen wave functions (...
Figure 5.35 (
Left
) MO energy-level diagram reveals that the asymmetric (stable) configuratio...
Figure 5.36 (
Left
) Overlap of two 1s hydrogen (H) atom orbits (AO) to form the hydrogen H
2
m...
Figure 5.37 Diatomic potential energy sketch featuring electronic, vibrational, and rotation...
Figure 5.38 Cylindrically symmetrical bonding between and AOs forming -bonds and -bonds.
Figure 5.39 Mixed and -bonding (bonding and antibonding) in dioxygen molecule.
Figure 5.40 Nonbonding and orbitals contrasted to bonding and antibonding o...
Figure 5.41 Hybridized state of carbon yields four potential binding sites.
Figure 5.42 (
Left
) Hybridized state of carbon yields three potential binding sites. (
Rig
)...
Figure 5.43 Bonding situation of benzene with (
left
) localized and (
right
) delocalized ele...
Figure 5.44 Energy diagrams and structures of (
left
) benzene with six MOs and three ...
Figure P5.6.1 (a): Hückel Hamiltonian for benzene.
Figure P5.6.1 (b): Benzene-filled ground states.
Figure P5.6.1 (c) Benzene-filled ground states.
Figure 5.45 Heterocyclic five-membered aromatic rings: Furan, pyrrole, and thiophene.
Figure 5.46 (
Left
) Nitrile (cyano-) group. (
Right
) Cyano-substituted pyrazoloquinoline (PAQ)...
Figure 5.47 A second-order NLO FTC-type chromophore. Nonlinearity .
28
Figure 5.48 Schematic band diagram with emphasis on the conjugation length and bandgap in co...
Figure 5.49 Structure of repeat units in PPV, PPP, and PF, respectively.
Figure 5.50 Principle steps for LED. Energy/potentials, i.e., the work functions of the anod...
Figure 5.51 Simpler architectures of polymer LEDs: (
Left
) single layer, (
middle
) n-type/p-ty...
Figure 5.52 Schematics of charge generation in organic PV with a conjugated polymer.
Chapter 6
Figure 6.1 Fermi function for different temperatures. Inset: Density of states at .
Figure 6.2 Density of states for 3D, 2D, 1D, and 0D electronic systems. The qualitative plo...
Figure 6.3 Conduction and valence bands for insulators, semiconductors, and conductors.
Figure 6.4 (
Left
) From discrete orbital states of isolated atoms (e.g., carbon with filled ...
Figure 6.5 Effect of quantum dot size on photoluminescence. With decreasing size, the lumin...
Figure 6.6 Effect of doping on the Fermi edge.
Figure P6.2.3 Activation energy vs. acceptor concentration for boron-doped silicon.
Figure 6.7 (
Top
) p-type and n-type material combination forming a p-n junction. The depleti...
Figure P6.2.5 Fermi energy in respect to semiconductor bandgaps.
Figure 6.8 p-n junction with details on depletion zone and voltages.
Figure 6.9 p-n diode operated in forward voltage, . (a) Full extend of the depletion zone...
Figure 6.10 Electronic band diagram of (a) an open circuit p-n diode, and (b) a p-n diode wi...
Figure 6.11 Carrier concentrations in p-n diode under forward bias injection of minority car...
Figure 6.12 P-type photovoltaic cell: p-n diode exposed to photons that generate (1) electro...
Figure 6.13 Electronic band structure within the photovoltaic cell. (1) An incident photon w...
Figure 6.14 I-V characteristics based on Eq. (6.43) with , , ...
Figure 6.15 Equivalence circuit of a photovoltaic diode: Simple circuit composed of diode on...
Figure 6.16 dispersion sketch for (a) direct and (b) indirect bandgap material.
Figure SP6.1 Intrinsic carrier densities.
Chapter 7
Figure 7.1 Regimes of EM radiation.
Figure 7.2 Visualization of the degree of motion of a diatomic molecule.
Figure 7.3 Visualization of the degree of motion of a diatomic molecule.
Figure 7.4 Harmonic Oscillator Model. is the oscillation amplitude, and is the correspo...
Figure 7.5 One-dimensional quantum harmonic oscillator exhibiting the allowed vibrational e...
Figure 7.6 Comparison between the quantum mechanical probabilities (at allowed energi...
Figure 7.7 Schematic representation of the actual diatomic internuclear potential, often ap...
Figure P7.2.2 Birge-Sponer Plot for H
2
.
Figure 7.8 Rigid rotor composed of two masses, and connected by a rigid rod of length...
Figure 7.9 Degeneracies of visualized if a polar molecule is placed into a fixed e...
Figure 7.10 Energy levels and absorption spectrum of a linear rigid rotator. rep...
Figure P7.3.3a Rigid and nonrigid rotor.
Figure P7.3.3b The absorption spectrum of HCl shows in the inset that the spectral lines are co...
Figure P7.3.3c Effect of centrifugal distortion on the bond length of H
35
Cl at room temperature.
Figure 7.11 Molecular energy comparisons: From large energy separation of electronic states ...
Figure 7.12 (
Top
) The normal modes of water molecules. (
Bottom
) Absorption spectrum of pure ...
Figure 7.13 (
Top
) The normal modes of carbon dioxide. The bending mode is doubly degenerate....
Figure 7.14 Schematics of changes in the molecular dipole moment during vibrational bond str...
Figure 7.15 1D-coupled spring system, with springs of force constant . Each element re...
Figure 7.16 Phonon dispersion relation of a 1D chain of identical particles. The linear rela...
Figure 7.17 Longitudinal (L) and transverse (T) phonon transport in 1D crystal. (
Top
) Sketch...
Figure 7.18 Most common crystal structure types: Simple cubic , body-centered cubic ...
Figure 7.19 Linear chain of equidistantly placed atoms or molecules of alternating masses ...
Figure 7.20 Dispersion plot for a linear chain of binary alternating masses featuring below ...
Figure 7.21 Sketch of the phonon dispersion relation of NaCl-like crystal structure along th...
Figure 7.22 Molecular heat capacity based on Einstein’s model (black solid line). Highlighte...
Figure 7.23 Schematic: Bulk conductivity of silicon as a function of temperature.
Figure 7.24 Schematics: (a) Heat pulse width for SWNT shows super-diffusion behavior with ...
List of Tables
Chapter 1
Table 1.1 Fundamental approach toward materials/system engineering.
Table 1.2 Thermal properties, densities, and speed of sound of selected materials.
Table 1.3 Properties of selected gases at 300 K and 1 bar.
Table 1.4 Properties of selected metals.
Table 1.5 Intrinsic jump parameters of solids based on material structure.
Table 1.6 Topics related to transport phenomena under nanoconstraints.
Table 1.7 Viscosity values in the melt phase of polystyrene (MW 135k).
Chapter 2
Table 2.1 Properties of selected molecules and its condensed media electric permittivity.
Table 2.2 Phase properties of selected materials at 25 °C.
Table 2.3 Selected properties of OMCTS, n-hexadecane, and silica at .
Table 2.4 Interfacial properties of OMCTS, n-hexadecane, and silicon oxide.
Table 2.5 Surface stress, surface energy, and compressibility of bulk metals at .
Table 2.6 Selected surface energies of solids and water contact angles at 20–25 °C.
Chapter 3
Table 3.1 L J parameters between selected molecules.
Table 3.2a VdW molecular and gas properties of alkanes and cycloalkanes.
Table 3.2b VdW molecular and gas properties of polar substances.
Table 3.2c VdW molecular and gas properties of selected materials.
Table 3.3 Critical temperatures and pressures of selected materials.
Table 3.4 VdW rescaling parameters for selected material classes.
Table 3.5 Cavitation properties of water based on CNT.
Table 3.6 List of symbols.
Table 3.7 Uniform feed solute concentration: relevant solvent and solute permeation parame...
Table 3.8 Solvent and solute permeance in terms of CP.
Table 3.9 Relevant solvent and solute permeation parameters.
Table 3.10 List of symbols – SD theory.
Table 1 Selected water properties and observation parameters.
Table 2 Critical volume.
Chapter 4
Table 4.1 Emissivity of selected material.
Table 4.2 Available energy states.
Table 4.3 The three principle distribution laws of nature.
Table 4.4 Microsystems.
Table 4.5 Summary: Wave-particle duality.
Chapter 5
Table 5.1 Work function , Fermi Energy , and density of states for common metals.
Chapter 6
Table 6.1 Fermi energy, density of states, and electron number densities for selected metals.
Table 6.2 Dispersion and density of states for electronic systems (0D to 3D).
Table 6.3 Bandgap energy for selected insulators and semiconductors at 300 K.
Table 6.4 Parameters relevant for for semiconductors.
Table 6.5 Exciton effective mass and size of selected inorganic semiconductors.
Table 6.6 Carrier-specific effective density of state values at 300 K.
Chapter 7
Table 7.1 Bond vibrational wave numbers of selected diatomic molecules.
Table 7.2 Energetic properties of vibrational bonds and rotations.
Table 7.3 Moments of inertia for selected rotor-types of molecules.
Table 7.4 Degrees of freedom of polyatomic molecules.
Table 7.5 Rotational constants of some polyatomic molecules.
Table 7.6 Speed of sound and Debye frequency for selected materials.
Appendix
Table A.5 First Legendre polynomials and related polar functions.
Guide
Cover
Table of Contents
Title Page
Copyright
Dedication
Preface
Units, Fundamental Constants, and Symbols
About the Companion Website
Begin Reading
Appendix to Chapter 1
Index
End User License Agreement
Pages
i
ii
iii
xi
xii
xiii
xiv
xv
xvi
xvii
xviii
xix
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
118
119
120
121
122
123
124
125
126
127
128
129
130
131
132
133
134
135
136
137
138
139
140
141
142
143
144
145
146
147
148
149
150
151
152
153
154
155
156
157
158
159
160
161
162
163
164
165
166
167
168
169
170
171
172
173
174
175
176
177
178
179
180
181
182
183
184
185
186
187
188
189
190
191
192
193
194
195
196
197
198
199
200
201
202
203
204
205
206
207
208
209
210
211
212
213
214
215
216
217
218
219
220
221
222
223
224
225
226
227
228
229
230
231
232
233
234
235
236
237
238
239
240
241
242
243
244
245
246
247
248
249
250
251
252
253
254
255
256
257
258
259
260
261
262
263
264
265
266
267
268
269
270
271
272
273
274
275
276
277
278
279
280
281
282
283
284
285
286
287
288
289
290
291
292
293
294
295
296
297
298
299
300
301
302
303
304
305
306
307
308
309
310
311
312
313
314
315
316
317
318
319
320
321
322
323
324
325
326
327
328
329
330
331
332
333
334
335
336
337
338
339
340
341
342
343
344
345
346
347
348
349
350
351
352
353
354
355
356
357
358
359
360
361
362
363
364
365
366
367
368
369
370
371
372
373
374
375
376
377
378
379
380
381
382
383
384
385
386
387
388
389
390
391
392
393
394
395
396
397
398
399
400
401
402
403
404
405
406
407
408
409
410
411
412
413
414
415
416
417
418
419
420
421
422
423
424
425
426
427
428
429
430
431
432
433
434
435
436
437
438
439
440
441
442
443
444
445
446
447
448
449
450
451
452
453
454
455
456
457
458
459
460
461
462
463
464
465
466
467
468
469
470
471
472
473
474
475
476
477
478
479
480
481
482
483
484
485
486
487
488
489
490
491
492
493
Principles of Nanoscience and Molecular Engineering
René M. Overney
University of Washington
WA, US
Author
Professor René M. Overney
University of Washington
Benson Hall, Box 351750
Seattle
WA, US, 98195
Cover Design: Wiley
Cover Images: Courtesy of Vincent P. Overney
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
Bibliographic information published by the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at http://dnb.d-nb.de.
Paperback ISBN 9783527354474
ePDF ISBN 9783527849628
ePub ISBN 9783527849611
Supplementary instructor material available at www.wiley-vch.de/ISBN9783527354474
© 2026 Wiley-VCH GmbH, Boschstraße 12, 69469 Weinheim, Germany
All rights reserved (including those of translation into other languages, text and data mining and training of artificial technologies or similar technologies). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
The manufacturer’s authorized representative according to the EU General Product Safety Regulation is Wiley-VCH GmbH, Boschstr. 12, 69469 Weinheim, Germany, e-mail: [email protected].
While the publisher and the authors have used their best efforts in preparing this work, including a review of the content of the work, neither the publisher nor the authors make any representations or warranties with respect to the accuracy or completeness of the contents of this work and specifically disclaim all warranties, including without limitation any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives, written sales materials or promotional statements for this work. The fact that an organization, website, or product is referred to in this work as a citation and/or potential source of further information does not mean that the publisher and authors endorse the information or services the organization, website, or product may provide or recommendations it may make. This work is sold with the understanding that the publisher is not engaged in rendering professional services. The advice and strategies contained herein may not be suitable for your situation. You should consult with a specialist where appropriate. Further, readers should be aware that websites listed in this work may have changed or disappeared between when this work was written and when it is read. Neither the publisher nor authors shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages.
To
Soraya
Preface
Nanoscience and Molecular Engineering are two multidisciplinary science and engineering fields that have significantly impacted our society over the past five decades. Cast into many disciplines, from physics, chemistry, and biology to bioengineering, chemical engineering, electrical engineering, mechanical engineering, and materials sciences, they have often been taught in a fragmented and non-curriculum-integrated fashion at universities around the globe. They have challenged educators and students alike in many ways, such as in content that seemed not to fit into existing curricula, hard-to-understand discipline-tailored language, and a general lack of understanding of the workings of the classical world. Oddly, “exotic” became the hallmark adjective about the turn of the millennium when describing molecular phenomena and material behavior on the nanoscale, emphasizing a deficit in paying attention to assumptions made and system boundary conditions.
Over the past decade, numerous institutions worldwide have made countless educational developments and progress to address these issues. At the University of Chicago, the Institute for Molecular Engineering was founded in 2011 (later becoming the Pritzker School of Molecular Engineering), with the goal of integrating science and engineering to address global challenges from the molecular level up. This was the first school in the country exclusively devoted to molecular engineering, and it offered undergraduate and graduate degrees on this topic. Of particular relevance to this textbook, in 2008 the University of Washington launched an undergraduate program in Nanoscience and Molecular Engineering, supported by funding from the U.S. National Science Foundation. This initiative sparked a collaborative, interdisciplinary effort across the relevant fields, ultimately culminating in the development of this course textbook–an introductory text intended to bridge disciplinary boundaries.
My aim in writing this book has been to integrate phenomenological knowledge of material and transport properties with atomistic and molecular theories, bridging the gap between unbound classical three-dimensional space and the constrained nanorealm. As the book is intended to serve undergraduate students across various disciplines, it lays the foundation for each topic beyond introductory chemistry and physics. However, it also challenges conventional wisdom derived from anecdotal experiences and fosters an understanding of nanoscale molecular collective phenomena that do not violate classical physical laws, but rather expand upon them. The surprise exotic awe is replaced by improved insight into the workings of atoms and molecules under interfacial, dimensional, and size constraints.
As the subject area is too extensive to be encapsulated within a single textbook, this work serves as a genuine introductory resource that offers entry into various disciplines that benefit from nanoscience and molecular engineering. Although designed for beginners, the text presents its material rigorously and steers clear of the buzzwords and empty phrases often seen in this field. Depending on their individual backgrounds, students may find certain sections of the text straightforward, while other parts may prove to be more challenging and require careful reading.
Depending on the year and the composition of the students in the class, which typically enrolls between 60 and 100 students, I chose to emphasize one topic over the other. This consideration led to the concept of writing this book in a modular format, allowing for a reading approach that does not require following the chapters sequentially. The chapters are intentionally designed to be decoupled and self-contained, providing significant flexibility for the instructor. Additionally, they can be utilized in different classes throughout the curriculum, as either introductory or supplementary reading. Consequently, the text is suitable for graduate courses as well as workforce development programs in the industry.
With the first chapter, I intended to cover the entire nanoscience and molecular engineering field. I discuss commonly shared perceptions of our world and their shortcomings in applying them to the nanoscale, specifically to transport properties. The exploration is limited to predominantly unstructured fluid phases composed of molecules of simple molecular structure.
In the second chapter, the focus shifts to structured condensed systems affected by interfaces and size constraints. I examine the effect of noninteracting solid interfaces on liquid phases and then move on to free surfaces of solid crystal lattice arrangements. Within the material phases, the emphasis is on weak molecular dispersion interactions and complex macromolecules with phase behaviors that mimic both liquid- and solid-like behavior. Critical size behavior and atomistic structures will be discussed with metal nanoclusters.
The third chapter delves into the liquid condensed state, highlighting boundary conditions and size constraints in thermally equilibrated systems. After exploring the Van der Waals equation, the discussion will shift to metastable states in liquids, mainly focusing on bubble nucleation and liquid stresses. This leads into a section on membrane technology, addressing species transport and separation through narrow conduits.
It is crucial to become acquainted with quantum mechanics to gain a comprehensive understanding of molecular behavior and solid-state phenomena. Historically, this field has often been overlooked in many engineering curricula; however, it has recently experienced a resurgence due to the rise of emerging technologies such as photonics, photovoltaics, and quantum computing, which are fundamentally rooted in quantum mechanical principles. This serves as a segue into the fourth chapter, which introduces the fundamental concepts of quantum mechanics.
The fifth chapter examines electronic transport in relation to the electronic structure of molecules, focusing on the movement of electrons through lower-dimensional systems, the development of quantum mechanical devices, and the molecular engineering of complex organic systems, including chromophores and conjugated polymers.
In the sixth chapter, the emphasis shifts to electronic states in solid condensed phases, from bulk materials to nanoscale structures, focusing on semiconductors, diodes, and photovoltaic cells.
The concluding seventh chapter will turn its attention to molecular degrees of freedom, exploring their role in energy dynamics and their impact on the thermodynamic properties of material systems under nanoconfinement.
About the Companion Website
Principles of Nanoscience and Molecular Engineering is accompanied by a companion website:
www.wiley-vch.de/ISBN9783527354474
The website includes:
Solutions to Study Problems for the chapters
Chapter 1The Realm of Nanoscience and Molecular Engineering
1.1 Nanoscience and Molecular Engineering
Nanoscience is most ordinarily defined by its scale, the nanometer that is equivalent to 10−9 m, or a thousandth of a micrometer. As illustrated in Figure 1.1, the nanometer is multiple times larger than the smallest distance between atoms in crystalline materials, matches roughly the smallest molecular distances in self-assemblies, and is approximately ten thousand times smaller than the thickness of a human hair. Practical material systems, devices, and technologies based on nanoscience are coined Nanotechnology.
Figure 1.1 The nanoscale, microscale and macroscale. The significant difference between the nanoscale and its two larger cousins is that it exhibits deviating physical properties for condensed materials.
Certainly, size plays a crucial role in various practical applications related to the nanoscale. But there is more to be said about this technology and its underlying science. Nanoscience and nanotechnology thrive on constraints that alter the boundary conditions of the macro world we are so accustomed to and present us with a world of wonders and surprises. The two employ and highlight, in particular, material interfaces and dimensionally constrained systems that alter molecular and atomistic arrangements and enhance fluctuations that affect the system equilibrium. We realize that most of our current technologies heavily rely on phenomenological bulk properties, often ignoring the fine subtleties that could be gained by involving interfaces in our designs to enhance or alter material properties.
In our world, material properties are important for several reasons, including:
ensuring the mechanical integrity of devices;
enabling and facilitating processes to run, such as chemical reactions;
providing adequate conduction properties for particles and energy (heat) transport;
customizing interaction interfaces between electromagnetic (EM) radiation and material transport systems toward energy production and communication, among others.
The processes developed to modify the bulk properties of materials have encompassed both mechanical and chemical methods, besides the blending of different materials. Steel, one of humanity’s oldest engineered materials, is produced through techniques such as mechanical folding, compressing, and stretching, while simultaneously incorporating carbon into the iron’s crystal lattice and removing oxygen through heating and stress. While the chemistry involved in metalworking was largely undertaken unintentionally in ancient times, these trial-and-error methods have been refined over the centuries, leading to a deeper and more fundamental understanding of the processes that occur at the atomistic and molecular levels. Thus, while Charles Goodyear invented the vulcanization process of rubber in the middle of the 19th century, a later generation of scientists recognized the true nature of the process, as chemical cross-linking between the polymer molecules, as sketched in Figure 1.2.
Figure 1.2 Trial-and-error discovery: Sulfur vulcanization of natural rubber (patented by Charles Goodyear in 1844). During vulcanization, chemical cross-links are formed between individual polymer chains. The degree of cross-linking density determines if the rubber is soft or hard.
With a fundamental understanding of material engineering, molecules with chemical linkers could be specifically synthesized to bring forward novel materials with properties tailored toward unique processes. This molecule-specific rational approach toward engineering is coined these days as Molecular Engineering. Thus, while molecular engineering deals with the rational design of functional molecules, nanoscience focuses on the fundamental understanding of the properties of material if confined to the nanoscale. Even if the two fields are not necessarily inclusive, their sweet spot lies in their shared realm, where we have control over the molecular building blocks, as well as a fundamental understanding of their collective properties under regulated conditions that go beyond far-field controls employed to bulk systems, such as externally applied electric fields, and concentration and temperature gradients.
To illustrate the shared realm between nanoscience and molecular engineering, let us revisit the cross-linking example and assume that the organic polymer molecules are electric conductive and the linkers function as switches that can be activated or deactivated by an external electric field. Notably, there are distinct differences between a bulk system and a nanowire composed of these materials: (1) The nanowires contain significantly fewer switches compared to the bulk system, and (2) the polymer chain molecules in the bulk system exhibit a more isotropic distribution than those in the nanowire. Point (1) emphasizes how a low number of switches in nanowires can significantly affect overall conductivity. In contrast, point (2) focuses on the directional spinning process that aligns polymer chain molecules along the length of the wire, showcasing the transition of electric current flow from three dimensions to one dimension. As a result, we can anticipate a fundamental change in how electric current flows and how we can manipulate it, particularly when confined to the nanoscale. Given that the on-state and off-state of electric current represent a binary signal, it follows that significantly fewer electrons are needed in a nanowire compared to a bulk wire. By utilizing local fields that influence the switches differently along the wire, the nanowire could evolve into a complex network with extensive logical functionalities akin to those found in a computer. Therefore, our molecularly linked nanowire system has the potential to function as a versatile electric conductor with a wide array of applications, often described as a “smart” and “unique” nanosystem.
It is important to note that in this example, the intricate rational design of the molecular building blocks plays a crucial role in determining the functionality of the nanowires. Factors such as the polymer length, the placement of linkers at end groups or side groups, and the linker reversible strength of binding are of equal importance as the physical confinement in dimensions and local fields. The entire system design and its functionality employ both nanoscience and molecular engineering. Through nanoscience, we can tap into the physical world of lower dimensionalities and the quantum world, both substantially different from our macroscopic world. Meanwhile, molecular engineering allows us to move beyond the limitations inherent in traditional material engineering, which is often constrained by the properties of inorganic materials or by trial-and-error methods. Consequently, by combining these two fields, we can unlock future possibilities filled with remarkable innovations in novel materials and device technologies.
1.1.1 Trial-and-Error Approach and Deductive Rational Engineering
Common to both nanotechnology and molecular engineering is the development of novel materials and systems that are based on deductive rational approach principles, in contrast to trial-and-error approach
