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COMPOSITE MATERIALS
ENGINEERING
Modeling and Technology
COMPOSITE MATERIALS
ENGINEERING
Modeling and Technology

Edited by
Alexander V. Vakhrushev, DSc
A. K. Haghi, PhD
Apple Academic Press Inc. Apple Academic Press Inc.
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Title: Composite materials engineering : modeling and technology / edited by Alexander V. Vakhrushev, DSc, A.K. Haghi, PhD.
Names: Vakhrushev, Alexander V., editor. | Haghi, A. K., editor.
Description: Includes bibliographical references and index.
Identifiers: Canadiana (print) 2019016574X | Canadiana (ebook) 20190165774 | ISBN 9781771887960 (hardcover) |
   ISBN 9780429242762 (ebook)
Subjects: LCSH: Composite materials.
Classification: LCC TA418.9.C6 C623 2020 | DDC 620.1/18—dc23

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Title: Composite materials engineering : modeling and technology / edited by Alexander V. Vakhrushev, DSc,
   A. K. Haghi, PhD.
Other titles: Composite materials engineering (Apple Academic Press)
Description: 1st edition. | Oakville, ON ; Palm Bay, Florida : Apple Academic Press, Inc., 2019. | Includes bibliographical
   references and index. | Summary: “This book provides a compilation of innovative fabrication strategies and utilization
   methodologies that are frequently adopted in the advanced composite materials community. It addresses developing
   appropriate composites to efficiently utilize macro- and nanoscale features. It covers a selection of key aspects of composite
   materials, including history, reinforcements, matrix materials, mechanical properties, physical properties, theory, and
   applications. The volume reviews the research developments of a number of widely studied composite materials with
   different matrices key features. Contains new coverage of nanocomposites that reflects the latest theoretical and engineering
   and industrial applications of composite materials. Provides design methods with numerical information and technical
   formulations needed for researchers. Presents a critical review of progress in research and development on composite
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About the Editors

Alexander V. Vakhrushev, DSc

Professor, M.T. Kalashnikov Izhevsk State Technical University,
Izhevsk, Russia; Head, Department of Nanotechnology and
Microsystems of Kalashnikov Izhevsk State Technical University,
Russia

Alexander V. Vakhrushev, DSc, is a professor at the M.T. Kalashnikov

Izhevsk State Technical University in Izhevsk, Russia, where he teaches
theory, calculating, and design of nano- and microsystems. He is also
the Chief Researcher of the Department of Information-Measuring
Systems of the Institute of Mechanics of the Ural Branch of the Russian
Academy of Sciences and Head of the Department of Nanotechnology
and Microsystems of Kalashnikov Izhevsk State Technical University.
He is a Corresponding Member of the Russian Engineering Academy. He
has over 400 publications to his name, including monographs, articles,
reports, reviews, and patents. He has received several awards, including
an Academician A. F. Sidorov Prize from the Ural Division of the Russian
Academy of Sciences for significant contribution to the creation of the
theoretical fundamentals of physical processes taking place in multi-level
nanosystems and Honorable Scientist of the Udmurt Republic. He is
currently a member of the editorial board of several journals, including
Computational Continuum Mechanics, Chemical Physics and Mesoscopia,
and Nanobuild. His research interests include multiscale mathematical
modeling of physical-chemical processes into the nano-hetero systems at
nano-, micro-, and macro-levels; static and dynamic interaction of nanoel-
ements; and basic laws relating the structure and macro characteristics of
nano-hetero structures.
vi About the Editors

A. K. Haghi, PhD
Former Editor-in-Chief, International Journal of Chemoinformatics and
Chemical Engineering and Polymers Research Journal;
Member, Canadian Research and Development Center of Sciences
and Cultures (CRDCSC), Montreal, Quebec, Canada,
E-mail: [email protected]

A. K. Haghi, PhD, is the author and editor of 165 books, as well as 1000
published papers in various journals and conference proceedings. Dr.
Haghi has received several grants, consulted for a number of major corpo-
rations, and is a frequent speaker to national and international audiences.
Since 1983, he served as a professor at several universities. He is the
former Editor-in-Chief of the International Journal of Chemoinformatics
and Chemical Engineering and Polymers Research Journal and on the
editorial boards of many international journals. He is also a member of
the Canadian Research and Development Center of Sciences and Cultures
(CRDCSC), Montreal, Quebec, Canada. He holds a BSc in urban and
environmental engineering from the University of North Carolina (USA),
an MSc in mechanical engineering from North Carolina A&T State
University (USA), a DEA in applied mechanics, acoustics, and materials
from the Université de Technologie de Compiègne (France), and a PhD in
engineering sciences from Université de Franche-Comté (France).
Contents

Contributors.............................................................................................. ix
Abbreviations............................................................................................ xi
Preface.................................................................................................... xiii

1. Conformational Analysis of Ag-Au Nanoalloy Clusters:

A CDFT Approach....................................................................................... 1
Prabhat Ranjan, Ajay Kumar, and Tanmoy Chakraborty

2. Methods for Determination of Nanostructures

Mechanical Properties............................................................................... 17
A. A. Shushkov and A. V. Vakhrushev

3. Multilevel Computer Simulation: Basic Tool of Nanotechnology

Simulations for “Production 4.0” Revolution.......................................... 35
A. V. Vakhrushev

4. On Strengthening of Epoxy-Composites by Filling with

Microdispersions of SiC, TiN, and Cement............................................. 51
D. Starokadomsky

5. Some Innovative Results-Oriented Scientific Research

That Leads to the Development in the Field of Inorganic
Polymers Science........................................................................................ 63
M. Avaliani

6. Nanocomposites for Environmental Protection: Technological

Vision and the Next-Generation Environmental Engineering
Technique.................................................................................................... 75
Sukanchan Palit

7. Transport Coefficients in Multicomponent Systems: Mutual

Diffusion, Self-Diffusion, and Tracer Diffusion........................................ 97
Ana C. F. Ribeiro

8. Condensed Phosphates as Inorganic Polymers and Various

Domains of Their Applications............................................................... 111
M. Avaliani, V. Chagelishvili, N. Barnovi, N. Esakia, M. Gvelesiani,
and Sh. Makhatadze
viii Contents

9. Quantum Molecular Spintronics, Nanoscience, and Graphenes......... 121

Francisco Torrens and Gloria Castellano

10. Characterization Techniques for Polymers and Polymer

Nanocomposites........................................................................................ 131
Shrikaant Kulkarni

11. Mechanisms of Action of Multifunctional Media Submitted by

Nano- and Ultrafine Iodine Compounds on Pathogens of
Bacterial and Fungium Etiology............................................................. 181
V. B. Golubchikov, A. V. Zhivotkov, and A. V. Vakhrushev

12. Methods of Obtaining and Application of Graphene........................... 199

A. V. Gumovskii and A. V. Vakhrushev

Index.................................................................................................................. 213
Contributors

M. Avaliani
Iv. Javakhishvili Tbilisi State University, R. Agladze Institute of Inorganic Chemistry and
Electrochemistry, 0186 Mindeli Str., 11, Tbilisi, Georgia,
E-mails: [email protected], [email protected]
N. Barnovi
Iv. Javakhishvili Tbilisi State University, R. Agladze Institute of Inorganic Chemistry and
Electrochemistry, 0186 Mindeli Str., 11, Tbilisi, Georgia

Gloria Castellano
Departamento de Ciencias Experimentales y Matemáticas, Facultad de Veterinaria y Ciencias
Experimentales, Universidad Católica de Valencia San Vicente Mártir, Guillem de Castro‑94,
E‑46001 València, Spain
V. Chagelishvili
Iv. Javakhishvili Tbilisi State University, R. Agladze Institute of Inorganic Chemistry and
Electrochemistry, 0186 Mindeli Str., 11, Tbilisi, Georgia
Tanmoy Chakraborty
Department of Chemistry; Manipal University Jaipur, DehmiKalan, Jaipur – 303007, India,
E-mails: [email protected]; [email protected]
N. Esakia
Iv. Javakhishvili Tbilisi State University, Faculty of Exact and Natural Sciences,
Department of Chemistry, 0179 Chavchavadze ave. 3, Tbilisi, Georgia

V. B. Golubchikov
Scientific and Production Company “Nord,” Perm, Russia

A. V. Gumovskii
Department of Nanotechnology and Microsystems, Technic Kalashnikov Izhevsk State
Technical University, Izhevsk, Russia, E-mail: [email protected]

M. Gvelesiani
Iv. Javakhishvili Tbilisi State University, R. Agladze Institute of Inorganic Chemistry and
Electrochemistry, 0186 Mindeli Str., 11, Tbilisi, Georgia

Shrikaant Kulkarni
Department of Chemical Engineering, Vishwakarma Institute of Technology, Pune (M.S.), India,
E-mail: [email protected]

Ajay Kumar
Department of Mechatronics Engineering, Manipal University Jaipur, DehmiKalan,
Jaipur – 303007, India

Sh. Makhatadze
Iv. Javakhishvili Tbilisi State University, R. Agladze Institute of Inorganic Chemistry and
Electrochemistry, 0186 Mindeli Str., 11, Tbilisi, Georgia
x Contributors

Sukanchan Palit
43, Judges Bagan, Post-Office-Haridevpur, Kolkata – 700082, India,
Tel.: 0091-8958728093, E-mails: [email protected], [email protected]

Prabhat Ranjan
Department of Mechatronics Engineering, Manipal University Jaipur, DehmiKalan,
Jaipur – 303007, India

Ana C. F. Ribeiro
Centro de Química, Department of Chemistry, University of Coimbra, 3004-535 Coimbra,
Portugal, E-mail: [email protected]

A. A. Shushkov
Udmurt Federal Research Center of the Ural Branch of the Russian Academy of Sciences,
Institute of Mechanics, Department of Mechanics of Nanostructures, Izhevsk, Russia
D. Starokadomsky
Department of Composites, Chuiko Institute of Surface Chemistry, NAS of Ukraine, 03164, Kiev,
Ukraine, E-mail: [email protected]
Francisco Torrens
Institut Universitari de Ciència Molecular, Universitat de València, Edifici d’Instituts de Paterna,
P. O. Box 22085, E‑46071 València, Spain, E-mail: [email protected]

A. V. Vakhrushev
Department of Mechanics of Nanostructures, Institute of Mechanics,
Udmurt Federal Research Center, Ural Division, Russian Academy of Sciences,
Izhevsk, Russia | Department of Nanotechnology and Microsystems,
Technic Kalashnikov Izhevsk State Technical University, Izhevsk, Russia,
E-mail: [email protected]

A. V. Zhivotkov
Scientific and Production Company “Nord,” Perm, Russia, E-mail: [email protected]
Abbreviations

AAS atomic absorption spectrometry

AFM atomic force microscopy
B3LYP Becke’s three-parameter Lee-Yang-Parr
BFC biofuel elements
CA catalytic activity
CDFT conceptual density functional theory
CNT c-nanotube
CVD chemical vapor deposition
CVDG chemical vapor deposition graphene
DFT density functional theory
DMTA dynamic mechanical thermal analysis
DRI differential refractive index
DRS dielectric relaxation spectroscopy
DSC differential scanning calorimetry
DVM digital voltmeter
ECD electrocodeposition
EPGG epitaxial growth graphene
ESR electron spin resonance
FEM finite element method
FLG few-layer GR
FTIR Fourier transform infrared spectroscopy
GC gas chromatography
GIC intercalated graphite compound
GICG graphene intercalated graphite compounds
GMR giant magnetic random
GO graphene oxide
GOx glucose oxidase
GPC gel permeation chromatography
GRs graphenes
HETP height equivalent to a theoretical plate
HOMO highest occupied molecular orbital
HPLC high-performance liquid chromatography
IC ion chromatography
xii Abbreviations

ICP inductively coupled plasma

IEC ion-exchange chromatography
LALLS low-angle laser light scattering
LC liquid chromatography
LLC liquid/liquid chromatography
LSC liquid/solid chromatography
LUMO lowest unoccupied molecular orbital
MMEC metal matrix composite electrochemical coatings
MRAM magnetic random access memory
MS mass spectrometry
NCs nanocomposites
NMR nuclear magnetic resonance
NMs nanomaterials
NP nanoparticle
NS nanoscience
NT nanotechnology
OM optical microscopy
PMMA polymethylmethacrylate
PTE periodic table of the elements
QDs quantum dots
QML quantum machine learning
RS Raman spectroscopy
RT room temperature
SEC size exclusion chromatography
SEM scanning electron microscopy
SMMs single-molecule magnets
SWCNT single-wall c-nanotube
TA thermal analysis
TCPP tetrakis(4‑carboxyphenyl)porphyrin
TEM transmission electron microscopy
TGA thermogravimetric analysis
TLC thin-layer chromatography
TMA thermomechanical analysis
TMR tunneling magnetic random
VDW Van Der Waals
VIS viscometer
WAXRD wide-angle x-ray diffraction
XPS x-ray photoelectron spectroscopy
XRD x-ray diffraction
Preface

Composites materials are basically the combining of unique properties of

materials to have synergistic effects. A combination of materials is needed to
adapt to certain properties for any application area. Composite materials have
grown rapidly in their applications; they will no doubt continue to do so.
Composite materials are versatile materials with a variety of applications.
A greater use of composite materials in many areas of engineering has led
to a greater demand for engineers versed in the design of structures made
from such materials.
Composites are now established engineering materials, offering weight
savings and longevity to a rapidly expanding range of applications.
This book is unique in that and it not only offers a current analysis of
mechanics and properties, but also examines the latest advances in theory
and applications and design aspects involving composites. This book also
provides the foundation for traditional basic composite material mechanics,
making it a comprehensive reference on this topic.

Key features of this book:

Each chapter begins with an overview of the key points to be addressed:
• Contains new coverage of nanocomposites.
• Reflects the latest theoretical and engineering applications.
• Provides design methods with numerical information and technical
formulations needed for researchers.
• Systematic and comprehensive information on composite materials.
• Critical review of progress in research and development on
composite materials.
• Comment on future research direction and ideas for product
development.
• Presents advanced material on composite structures.
• Provides industrial applications of composite materials.
CHAPTER 1

Conformational Analysis of Ag-Au

Nanoalloy Clusters: A CDFT Approach
PRABHAT RANJAN,1 AJAY KUMAR,1 and TANMOY CHAKRABORTY2
Department of Mechatronics Engineering, Manipal University Jaipur,
1

DehmiKalan, Jaipur – 303007, India

2
Department of Chemistry, Manipal University Jaipur, DehmiKalan,
Jaipur – 303007, India, E-mails: [email protected];
[email protected]

ABSTRACT

The study of Ag-Au nanoalloy clusters is of considerable interest due to a

unique optical and electronic and large range of technological applications
in biosciences, material sciences, and catalysis. Density functional theory
(DFT) is the most efficient technique of quantum mechanics to explore the
electronic properties of matter. Conceptual density functional theory (CDFT)
has been proven to be an essential tool to correlate the experimental proper-
ties of clusters with CDFT-based descriptors. In this chapter, conformational
analysis of Ag-Au clusters has been studied by using DFT methodology.
We have computed CDFT-based descriptors viz. HOMO-LUMO energy
gap, electronegativity, hardness, softness, electrophilicity index, and dipole
moment of trimers by changing the angle between the atoms.

1.1 INTRODUCTION

It is a well-known fact that structure and property are very much closely
related to each other [1]. There is not any particular method to determine
the symmetry structure of a molecule. Though, density functional theory
2 Composite Materials Engineering: Modeling and Technology

(DFT)-based global descriptors like HOMO-LUMO energy gap, hardness,

softness, electronegativity, and electrophilicity index have been invoked
to relate structure and property of molecules [1–3]. Even if there is not any
distinctive relationship between structure and properties, the structure and
property of molecules are interrelated. Nowadays, science and technology
has been developed to a new level for understanding the biological and
molecular activities of the system [4–7]. Researchers are examining the
descriptors in terms of mathematical values that pronounce the structure
and physicochemical properties of the molecular system [8–11]. But, for
the prediction of the relationship between structure and property, it is very
important to investigate the electronic structure and operational forces
on the molecular system [10, 11]. Though some researchers have tried
to show the relationship between properties and reactivity of a molecule
with reference to its equilibrium structure, a molecule rarely stays in its
stationary equilibrium shape. The physical process of the dynamics of
internal alternation begins the isomerization process mechanism, and it
produces countless conformations [13, 14]. The conformational analysis
has an acute result on biological activities and response on the result of
various stereochemical reactions [1]. Therefore, an insight of the rela-
tive energies and the mechanism of the advancement of conformational
analysis will be able to predict information regarding the sensitivity, the
spatial arrangement of atoms and their effects on the physicochemical
properties and product dissemination in reaction [15]. Thus, the study of
conformations as to the source of a barrier to internal alternation within a
molecule is of high importance to theoretical, experimental, and biological
scientists.

1.2 COMPUTATIONAL DETAILS

Since the last couple of years, DFT has been a dominant and effective
computational technique for bimetallic and multi-metallic clusters. DFT
methods are open to many new innovative fields in material science,
physics, chemistry, surface science, nanotechnology, biology, and earth
sciences [16]. Among all the DFT approximations, the hybrid functional
Becke’s three-parameter Lee-Yang-Parr exchange-correlation functional
(B3LYP) has been proven very efficient and used successfully for
bimetallic clusters [17–20]. In this section, conformational analysis of
Conformational Analysis of Ag-Au Nanoalloy Clusters 3

bimetallic nanoalloy clusters has been performed with the help of hybrid
functional Becke’s three-parameter Lee-Yang-Parr exchange-correlation
functional (B3LYP). The basis set LanL2dz has high accuracy for metallic
clusters, which has been recently analyzed by researchers [17, 21, 22]. For
optimization purpose, Becke’s three-parameter Lee-Yang-Parr (B3LYP)
exchange-correlation with basis set LanL2dz has been adopted. All the
modeling and structural optimization of compounds have been performed
using the Gaussian 03 software package [23] within the DFT framework.
Invoking Koopmans’ approximation [24, 25], we have calculated
ionization energy (I) and electron affinity (A) of all the nanoalloys using
the following ansatz:

I = – ɛHOMO (1)
A = – ɛLUMO (2)

Thereafter, using I and A, the conceptual DFT-based descriptors viz.

electronegativity (χ), global hardness (η), molecular softness (S) and elec-
trophilicity index (ω) have been computed. The equations used for such
calculations are as follows:

I+A
χ = −µ = (3)
2
where μ represents the chemical potential of the system.

I−A
η= (4)
2

1
S= (5)
2η

µ2
ω= (6)
2η

1.3 RESULTS AND DISCUSSION

In this study, conformational analysis of three atoms of bimetallic clusters

AgAu, i.e., AgAu2, and Ag2Au have been performed. The orbital energies
4 Composite Materials Engineering: Modeling and Technology

in the form of highest occupied molecular orbital (HOMO)–lowest unoc-

cupied molecular orbital (LUMO) energy gap along with DFT-based
descriptors have been investigated as a function of dihedral angles.

1.3.1 AGAU2 NANOALLOY CLUSTERS

a. In Figure 1.1, Au atom is fixed at the center, and other species, i.e., Ag
and Au placed at corners are not fixed.

FIGURE 1.1 Cluster AgAu2 with Au atom fixed at the center.

The orbital energies in the form of HOMO-LUMO gap along with

computed DFT-based descriptors viz. electronegativity, hardness, soft-
ness, electrophilicity index, and dipole moment have been analyzed as
a function of dihedral angles and reported in Table 1.1. Figure 1.1 and
Table 1.1 establish that the preferred conformation of the instant cluster
has a linear structure with Au atom fixed at the center. The maximum
HOMO-LUMO energy gap is obtained at the dihedral angle of 180º, while
the least gap is obtained at a dihedral angle of 20º. The instant cluster
has constant HOMO-LUMO gap, and DFT-based descriptors for dihedral
angles varying between 20º–80º and 90º–170º; however, an exception has
been marked at an angle 60º.

b. In Figure 1.2, the triangular structure of AgAu2 cluster is formed with

fixed Au atom at the center, and other Au and Ag atoms are placed at
the corners of the triangle. The computed physicochemical properties
of all the generated conformations are shown in Table 1.2 with the
corresponding dihedral angles.
Conformational Analysis of Ag-Au Nanoalloy Clusters 5

TABLE 1.1 Computed DFT-Based Descriptors of AgAu2 Cluster with Au Atom Fixed at
the Center
Angles HOMO- Electro- Hardness Softness Electro- Dipole Symmetry
(in Degrees) LUMO Gap negativity (eV) (eV) philicity Moment
(eV) (eV) Index (eV) (Debye)
20 1.605 4.258 0.803 0.623 11.295 3.223 Cs
30 1.605 4.258 0.803 0.623 11.295 3.222 Cs
40 1.605 4.258 0.803 0.623 11.295 3.222 Cs
50 1.605 4.258 0.803 0.623 11.295 3.226 Cs
60 1.687 4.218 0.844 0.593 10.544 3.752 Cs
70 1.605 4.258 0.803 0.623 11.295 3.225 Cs
80 1.605 4.258 0.803 0.623 11.295 3.225 Cs
90 2.694 4.394 1.347 0.371 7.169 3.341 Cs
100 2.694 4.394 1.347 0.371 7.169 3.341 Cs
110 2.694 4.394 1.347 0.371 7.169 3.341 Cs
120 2.694 4.394 1.347 0.371 7.169 3.341 Cs
130 2.694 4.394 1.347 0.371 7.169 3.34 Cs
140 2.694 4.394 1.347 0.371 7.169 3.34 Cs
150 2.694 4.394 1.347 0.371 7.169 3.341 Cs
160 2.694 4.394 1.347 0.371 7.169 3.342 Cs
170 2.694 4.394 1.347 0.371 7.169 3.341 Cs
180 2.966 4.530 1.483 0.337 6.920 1.924 C∞V

FIGURE 1.2 Triangular structure of cluster AgAu2 with Au atom fixed at the center.

Table 1.2 reveals that least HOMO-LUMO energy gap is obtained

at dihedral angle 80º and maximum HOMO-LUMO gap is obtained at
dihedral angles varying from 90º–170º. It indicates that an instant cluster
is less stable at dihedral angle 80º, and maximum stability is achieved
between 90º–170º.
6 Composite Materials Engineering: Modeling and Technology

c. In Figure 1.3, one Ag atom is fixed at the center, and two Au atoms
placed at the corners are not fixed.

TABLE 1.2 Computed DFT-Based Descriptors of Triangular Structure of Cluster AgAu2

with Au Atom Fixed at the Center
Angles (in HOMO- Electro- Hardness Softness Electro- Dipole Symmetry
Degrees) LUMO negativity (eV) (eV) philicity Moment
Gap (eV) (eV) Index (eV) (Debye)
20 1.605 4.258 0.803 0.623 11.295 3.223 Cs
30 1.605 4.258 0.803 0.623 11.295 3.222 Cs
40 1.605 4.258 0.803 0.623 11.295 3.224 Cs
50 1.605 4.258 0.803 0.623 11.295 3.226 Cs
60 1.687 4.218 0.844 0.593 10.544 3.752 Cs
70 1.605 4.258 0.803 0.623 11.295 3.225 Cs
80 1.415 2.503 0.707 0.707 4.429 0.782 Cs
90 2.694 4.394 1.347 0.371 7.169 3.341 Cs
100 2.694 4.394 1.347 0.371 7.169 3.341 Cs
110 2.694 4.394 1.347 0.371 7.169 3.342 Cs
120 2.694 4.394 1.347 0.371 7.169 3.341 Cs
130 2.694 4.394 1.347 0.371 7.169 3.341 Cs
140 2.694 4.394 1.347 0.371 7.169 3.342 Cs
150 2.694 4.394 1.347 0.371 7.169 3.344 Cs
160 2.694 4.394 1.347 0.371 7.169 3.342 Cs
170 2.694 4.394 1.347 0.371 7.169 3.342 Cs

Figure 1.3. Cluster AgAu2 with Ag atom fixed at the center.

Table 1.3 and Figure 1.3 demonstrate that maximum HOMO-LUMO

energy gap is obtained at the dihedral angle 30º, and it is constant till 170º;
however, there is an exception at 50º. The instant cluster has the least
energy gap at 20º.
Conformational Analysis of Ag-Au Nanoalloy Clusters 7

Table 1.3 Computed DFT-Based Descriptors of Cluster AgAu2 with Ag Atom Fixed at
the Center
Angles (in HOMO- Electro- Hardness Softness Electro- Dipole Symmetry
Degrees) LUMO negativity (eV) (eV) philicity Moment
Gap (eV) (eV) Index (eV) (Debye)
20 0.163 4.218 0.082 6.125 108.953 0.125 C2v
30 1.687 4.218 0.844 0.593 10.544 3.75 C2v
40 1.687 4.218 0.844 0.593 10.544 3.751 C2v
50 1.605 4.258 0.803 0.623 11.295 3.224 C2v
60 1.687 4.218 0.844 0.593 10.544 3.752 C2v
70 1.687 4.218 0.844 0.593 10.544 3.757 C2v
80 1.687 4.218 0.844 0.593 10.544 3.75 C2v
90 1.687 4.218 0.844 0.593 10.544 3.751 C2v
100 1.687 4.218 0.844 0.593 10.544 3.751 C2v
110 1.687 4.218 0.844 0.593 10.544 3.75 C2v
120 1.687 4.218 0.844 0.593 10.544 3.752 C2v
130 1.687 4.218 0.844 0.593 10.544 3.751 C2v
140 1.687 4.218 0.844 0.593 10.544 3.751 C2v
150 1.687 4.218 0.844 0.593 10.544 3.751 C2v
160 1.687 4.218 0.844 0.593 10.544 3.751 C2v
170 1.687 4.245 0.844 0.593 10.680 3.75 C2v
180 0.980 2.394 0.490 1.021 5.853 2.59 D∞h

d. In Figure 1.4, the triangular structure of AgAu2 is formed with an Ag

atom fixed at the center and Au atoms located at the corners of the
cluster are not fixed. The computed physicochemical properties of all
the conformations are presented in Table 1.4 with the corresponding
dihedral angles.

FIGURE 1.4 Triangular structure of cluster AgAu2 with Ag atom fixed at the center.
8 Composite Materials Engineering: Modeling and Technology

TABLE 1.4 Computed DFT-Based Descriptors of Triangular Structure of Cluster AgAu2

with Ag Atom Fixed at the Center
Angles (in HOMO- Electro- Hardness Softness Electro- Dipole Symmetry
Degrees) LUMO negativity (eV) (eV) philicity Moment
Gap (eV) (eV) Index (eV) (Debye)
20 0.163 4.218 0.082 6.125 108.953 0.125 C2v
30 1.687 4.218 0.844 0.593 10.544 3.751 C2v
40 1.687 4.218 0.844 0.593 10.544 3.75 C2v
50 1.605 4.258 0.803 0.623 11.295 3.224 C2v
60 1.687 4.218 0.844 0.593 10.544 3.752 C2v
70 1.687 4.218 0.844 0.593 10.544 3.757 C2v
80 1.687 4.218 0.844 0.593 10.544 3.747 C2v
90 1.687 4.218 0.844 0.593 10.544 3.748 C2v
100 1.687 4.218 0.844 0.593 10.544 3.751 C2v
110 1.687 4.218 0.844 0.593 10.544 3.751 C2v
120 1.687 4.218 0.844 0.593 10.544 3.751 C2v
130 1.687 4.218 0.844 0.593 10.544 3.751 C2v
140 1.687 4.218 0.844 0.593 10.544 3.749 C2v
150 1.687 4.218 0.844 0.593 10.544 3.75 C2v
160 1.687 4.218 0.844 0.593 10.544 3.749 C2v
170 1.687 4.218 0.844 0.593 10.544 3.751 C2v

Table 1.4 and Figure 1.4 demonstrate that maximum HOMO-LUMO

energy gap is obtained at the dihedral angle 30º, and it is constant till 170º;
however, an exception is marked at 50º. The instant cluster has a minimum
HOMO-LUMO energy gap at 20º.

1.3.2 AG2AU NANOALLOY CLUSTERS

In Figure 1.5, Au atom is fixed at the center and other species, i.e., Ag and
Au placed at corners are not fixed.

FIGURE 1.5 Cluster Ag2Au with Ag atom fixed at the center.

Conformational Analysis of Ag-Au Nanoalloy Clusters 9

The orbital energies in the form of HOMO-LUMO gap along with

computed DFT-based descriptors viz. electronegativity, hardness, soft-
ness, electrophilicity index and dipole moment have been analyzed as
a function of dihedral angles and reported in Table 1.5. Figure 1.5 and
Table 1.5 establish that the preferred conformation of the instant cluster
has maximum HOMO-LUMO energy gap at the dihedral angles varying
between 160º–180º, while the least gap is obtained at dihedral angles
varying between 20º–110º.

TABLE 1.5 Computed DFT-Based Descriptors of Cluster Ag2Au with Ag Atom Fixed at
the Center
Angles (in HOMO- Electro- Hardness Softness Electro- Dipole Symmetry
Degrees) LUMO negativity (eV) (eV) philicity Moment
Gap (eV) (eV) Index (eV) (Debye)
30 1.388 3.850 0.694 0.721 10.682 2.439 Cs
40 1.388 3.850 0.694 0.721 10.682 2.351 Cs
50 1.388 3.850 0.694 0.721 10.682 2.44 Cs
60 1.388 3.850 0.694 0.721 10.682 2.44 Cs
70 1.388 3.850 0.694 0.721 10.682 2.442 Cs
80 1.388 3.850 0.694 0.721 10.682 2.44 Cs
90 1.388 3.850 0.694 0.721 10.682 2.44 Cs
100 1.388 3.850 0.694 0.721 10.682 2.44 Cs
110 1.388 3.850 0.694 0.721 10.682 2.44 Cs
120 2.857 4.095 1.429 0.350 5.870 3.116 Cs
130 2.966 4.122 1.483 0.337 5.730 3.244 Cs
140 2.966 4.122 1.483 0.337 5.730 3.253 Cs
150 2.911 4.095 1.456 0.343 5.760 3.158 Cs
160 3.374 4.218 1.687 0.296 5.272 3.844 Cs
170 3.374 4.190 1.687 0.296 5.204 3.792 Cs
180 3.374 4.286 1.673 0.299 5.488 2.272 C∞V

In Figure 1.6, the triangular structure of Ag2Au cluster is formed with

fixed Au atom at the center, and other Au and Ag atoms are placed at the
corners of the triangle. The computed physicochemical properties of all the
generated conformations are shown in Table 1.6 with the corresponding
dihedral angles.
10 Composite Materials Engineering: Modeling and Technology

FIGURE 1.6 Triangular structure of cluster Ag2Au with Ag atom fixed at the center.

Table 1.6 reveals that least HOMO-LUMO energy gap is obtained at dihe-
dral angle 110º and maximum HOMO-LUMO gap is obtained at dihedral
angles varying from 130º–170º. It indicates that an instant cluster is less
stable at dihedral angle 110º, and maximum stability is achieved between
130º–170º.

TABLE 1.6 Computed DFT-Based Descriptors of Triangular Structure of Cluster Ag2Au

with Ag Atom Fixed at the Center
Angles (in HOMO- Electro- Hardness Softness Electro- Dipole Symmetry
Degrees) LUMO negativity (eV) (eV) philicity Moment
Gap (eV) (eV) Index (eV) (Debye)
20 1.388 3.850 0.694 0.721 10.682 2.441 Cs
30 1.442 3.850 0.721 0.693 10.279 2.441 Cs
40 1.415 3.864 0.707 0.707 10.551 2.442 Cs
50 1.388 3.850 0.694 0.721 10.682 2.441 Cs
60 1.388 3.850 0.694 0.721 10.682 2.44 Cs
70 1.388 3.850 0.694 0.721 10.682 2.44 Cs
80 1.388 3.850 0.694 0.721 10.682 2.44 Cs
90 1.415 3.864 0.707 0.707 10.551 2.44 Cs
100 1.388 3.850 0.694 0.721 10.682 2.44 Cs
110 1.361 3.837 0.680 0.735 10.819 2.341 Cs
120 2.803 4.095 1.401 0.357 5.984 3.077 Cs
130 2.966 4.122 1.483 0.337 5.730 3.254 Cs
140 2.966 4.122 1.483 0.337 5.730 3.249 Cs
150 2.966 4.122 1.483 0.337 5.730 3.277 Cs
160 2.966 4.122 1.483 0.337 5.730 3.271 Cs
170 2.966 4.122 1.483 0.337 5.730 3.248 Cs

In Figure 1.7, one Au atom is fixed at the center, and two Ag atoms
placed at the corners are not fixed.
Conformational Analysis of Ag-Au Nanoalloy Clusters 11

FIGURE 1.7 Cluster Ag2Au with Au atom fixed at the center.

Table 1.7 and Figure 1.7 demonstrate that maximum HOMO-LUMO

energy gap is obtained at the dihedral angle 20º, and the minimum energy
gap is obtained at dihedral angles 40º and 70º. The instant cluster has
constant HOMO-LUMO energy gap, i.e., 2.367 eV between dihedral
angles 90º–170º; however, an exception is marked at angle 150º.

TABLE 1.7 Computed DFT-Based Descriptors of Cluster Ag2Au with Au Atom Fixed at
the Center
Angles (in HOMO- Electro- Hardness Softness Electro- Dipole Symmetry
Degrees) LUMO negativity (eV) (eV) philicity Moment
Gap (eV) (eV) Index (eV) (Debye)
20 3.211 3.320 1.605 0.311 3.432 0.674 Cs
30 2.204 3.850 1.102 0.454 6.726 1.525 Cs
40 1.388 3.850 0.694 0.721 10.682 2.392 Cs
50 1.442 3.850 0.721 0.693 10.279 2.428 Cs
60 1.442 3.850 0.721 0.693 10.279 2.417 Cs
70 1.388 3.850 0.694 0.721 10.682 2.441 Cs
80 1.415 3.837 0.707 0.707 10.403 2.395 Cs
90 2.367 3.877 1.184 0.422 6.351 1.146 Cs
100 2.367 3.877 1.184 0.422 6.351 1.147 Cs
110 2.367 3.877 1.184 0.422 6.351 1.146 Cs
120 2.367 3.877 1.184 0.422 6.351 1.145 Cs
130 2.367 3.877 1.184 0.422 6.351 1.146 Cs
140 2.367 3.877 1.184 0.422 6.351 1.145 Cs
150 2.422 3.877 1.211 0.413 6.208 1.098 Cs
160 2.367 3.877 1.184 0.422 6.351 1.144 Cs
170 2.367 3.877 1.184 0.422 6.351 1.145 Cs
180 2.531 3.905 1.265 0.395 6.025 1.598 D∞h

In Figure 1.8, the triangular structure of Ag2Au is formed with an Ag

atom fixed at the center and Au atoms located at the corners of the cluster
12 Composite Materials Engineering: Modeling and Technology

are not fixed. The computed physicochemical properties of all the confor-
mations are presented in Table 1.8 with the corresponding dihedral angles.

FIGURE 1.8 Triangular structure of cluster Ag2Au with Au atom fixed at the center.

TABLE 1.8 Computed DFT-Based Descriptors of Triangular Structure of Cluster Ag2Au

with Au Atom Fixed at the Center
Angles (in HOMO- Electro- Hardness Softness Electro- Dipole Symmetry
Degrees) LUMO negativity (eV) (eV) philicity Moment
Gap (eV) (eV) Index (eV) (Debye)
20 1.388 3.905 0.694 0.721 10.987 1.637 C2v
30 1.388 3.905 0.694 0.721 10.987 1.637 C2v
40 1.388 3.905 0.694 0.721 10.987 1.638 C2v
50 1.388 3.905 0.694 0.721 10.987 1.637 C2v
60 1.388 3.905 0.694 0.721 10.987 1.636 C2v
70 1.388 3.905 0.694 0.721 10.987 1.636 C2v
80 2.359 3.909 1.180 0.424 6.476 0.627 C2v
90 2.359 3.909 1.180 0.424 6.476 0.626 C2v
100 2.359 3.909 1.180 0.424 6.476 0.627 C2v
110 2.359 3.909 1.180 0.424 6.476 0.628 C2v
120 2.359 3.909 1.180 0.424 6.476 0.627 C2v
130 2.359 3.909 1.180 0.424 6.476 0.627 C2v
140 2.359 3.909 1.180 0.424 6.476 0.626 C2v
150 2.359 3.909 1.180 0.424 6.476 0.627 C2v
160 2.359 3.909 1.180 0.424 6.476 0.628 C2v
170 2.359 3.909 1.180 0.424 6.476 0.628 C2v

Table 1.8 and Figure 1.8 demonstrate that maximum HOMO-LUMO

energy gap is obtained at dihedral angle 80º, and it is constant till 170º.
The instant cluster has a minimum HOMO-LUMO energy gap at dihedral
angles varying between 20º–70º.
Conformational Analysis of Ag-Au Nanoalloy Clusters 13

1.4 CONCLUSION

In this chapter, we have studied the conformational effect of AgAu nano-

alloy clusters on the basis of DFT platform. We have computed CDFT-
based descriptors viz., molecular hardness, softness, electronegativity,
electrophilicity index, dipole moment and symmetry along with HOMO-
LUMO energy gap of trimer AgAu clusters. The result reveals that the
linear structure of AgAu nanoalloy clusters is more stable than other
conformations. The reason for the stability of small linear structures may
be understood from the molecular orbital concepts. However, an exception
has been observed in the case of Au2Ag (where Ag atom is fixed). In this
report, we have observed large HOMO-LUMO gap for linear structure,
except AgAu2 (where Ag atom is fixed at the center). In the case of AgAu2
cluster, where the Ag atom is fixed at the center, maximum HOMO-LUMO
gap is observed at dihedral angle 30˚. The computed HOMO-LUMO
energy gap of these clusters runs hand in hand, along with their computed
hardness values.

KEYWORDS

•• Ag-Au •• dipole moment

•• conformational analysis •• HOMO-LUMO gap
•• density functional theory

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pretty girls and music. Well a showman’s business is to give the
public what they want.”
“I think that this city is full of people wanting inconceivable
things.... Look at it.”
“It’s all right at night when you cant see it. There’s no artistic
sense, no beautiful buildins, no old-time air, that’s what’s the matter
with it.”
They stood a while without speaking. The orchestra began
playing the waltz from The Lilac Domino. Suddenly Ellen turned to
Goldweiser and said in a curt tone. “Can you understand a woman
who wants to be a harlot, a common tart, sometimes?”
“My dear young lady what a strange thing for a sweet lovely girl to
suddenly come out and say.”
“I suppose you’re shocked.” She didnt hear his answer. She felt
she was going to cry. She pressed her sharp nails into the palms of
her hands, she held her breath until she had counted twenty. Then
she said in a choking little girl’s voice, “Harry let’s go and dance a
little.”
The sky above the cardboard buildings is a vault of beaten lead. It
would be less raw if it would snow. Ellen finds a taxi on the corner of
Seventh Avenue and lets herself sink back in the seat rubbing the
numb gloved fingers of one hand against the palm of the other.
“West Fiftyseventh, please.” Out of a sick mask of fatigue she
watches fruitstores, signs, buildings being built, trucks, girls,
messengerboys policemen through the jolting window. If I have my
child, Stan’s child, it will grow up to jolt up Seventh Avenue under a
sky of beaten lead that never snows watching fruitstores, signs,
buildings being built, trucks, girls, messengerboys, policemen.... She
presses her knees together sits up straight on the edge of the seat
with her hands clasped over her slender belly. O God the rotten joke
they’ve played on me, taking Stan away, burning him up, leaving me
nothing but this growing in me that’s going to kill me. She’s
whimpering into her numb hands. O God why wont it snow?
 As she stands on the gray pavement fumbling in her purse for a
bill, a dusteddy swirling scraps of paper along the gutter fills her
mouth with grit. The elevatorman’s face is round ebony with ivory
inlay. “Mrs. Staunton Wells?” “Yas ma’am eighth floor.”
The elevator hums as it soars. She stands looking at herself in the
narrow mirror. Suddenly something recklessly gay goes through her.
She rubs the dust off her face with a screwedup handkerchief, smiles
at the elevatorman’s smile that’s wide as the full keyboard of a piano,
and briskly rustles to the door of the apartment that a frilled maid
opens. Inside it smells of tea and furs and flowers, women’s voices
chirp to the clinking of cups like birds in an aviary. Glances flicker
about her head as she goes into the room.

There was wine spilled on the tablecloth and bits of tomatosauce

from the spaghetti. The restaurant was a steamy place with views of
the Bay of Naples painted in soupy blues and greens on the walls.
Ellen sat back in her chair from the round tableful of young men,
watching the smoke from her cigarette crinkle spirally round the fat
Chiantibottle in front of her. In her plate a slab of tricolor icecream
melted forlornly. “But good God hasnt a man some rights? No, this
industrial civilization forces us to seek a complete readjustment of
government and social life ...”
“Doesnt he use long words?” Ellen whispered to Herf who sat
beside her.
“He’s right all the same,” he growled back at her.... “The result has
been to put more power in the hands of a few men than there has
been in the history of the world since the horrible slave civilizations
of Egypt and Mesopotamia....”
“Hear hear.”
“No but I’m serious.... The only way of bucking the interests is for
working people, the proletariat, producers and consumers, anything
you want to call them, to form unions and finally get so well
organized that they can take over the whole government.”
“I think you’re entirely wrong, Martin, it’s the interests as you call
em, these horrible capitalists, that have built up this country as we
have it today.”
“Well look at it for God’s sake.... That’s what I’m saying. I wouldnt
kennel a dog in it.”
“I dont think so. I admire this country.... It’s the only fatherland I’ve
got.... And I think that all these downtrodden masses really want to
be downtrodden, they’re not fit for anything else.... If they werent
they’d be flourishing businessmen ... Those that are any good are
getting to be.”
“But I don’t think a flourishing businessman is the highest ideal of
human endeavor.”
“A whole lot higher than a rotten fiddleheaded anarchist agitator....
Those that arent crooks are crazy.”
“Look here Mead, you’ve just insulted something that you dont
understand, that you know nothing about.... I cant allow you to do
that.... You should try to understand things before you go round
insulting them.”
“An insult to the intelligence that’s what it is all this socialistic
drivel.”
Ellen tapped Herf on the sleeve. “Jimmy I’ve got to go home. Do
you want to walk a little way with me?”
“Martin, will you settle for us? We’ve got to go.... Ellie you look
terribly pale.”
“It’s just a little hot in here.... Whee, what a relief.... I hate
arguments anyway. I never can think of anything to say.”
“That bunch does nothing but chew the rag night after night.”
Eighth Avenue was full of fog that caught at their throats. Lights
bloomed dimly through it, faces loomed, glinted in silhouette and
faded like a fish in a muddy aquarium.
 “Feel better Ellie?”
“Lots.”
“I’m awfully glad.”
“Do you know you’re the only person around here who calls me
Ellie. I like it.... Everybody tries to make me seem so grown up since
I’ve been on the stage.”
“Stan used to.”
“Maybe that’s why I like it,” she said in a little trailing voice like a
cry heard at night from far away along a beach.
Jimmy felt something clamping his throat. “Oh gosh things are
rotten,” he said. “God I wish I could blame it all on capitalism the way
Martin does.”
“It’s pleasant walking like this ... I love a fog.”
They walked on without speaking. Wheels rumbled through the
muffling fog underlaid with the groping distant lowing of sirens and
steamboat whistles on the river.
“But at least you have a career.... You like your work, you’re
enormously successful,” said Herf at the corner of Fourteenth Street,
and caught her arm as they crossed.
“Dont say that.... You really dont believe it. I dont kid myself as
much as you think I do.”
“No but it’s so.”
“It used to be before I met Stan, before I loved him.... You see I
was a crazy little stagestruck kid who got launched out in a lot of
things I didnt understand before I had time to learn anything about
life.... Married at eighteen and divorced at twentytwo’s a pretty good
record.... But Stan was so wonderful....”
“I know.”
“Without ever saying anything he made me feel there were other
things ... unbelievable things....”
 “God I resent his craziness though.... It’s such a waste.”
“I cant talk about it.”
“Let’s not.”
“Jimmy you’re the only person left I can really talk to.”
“Dont want to trust me. I might go berserk on you too some day.”
They laughed.
“God I’m glad I’m not dead, arent you Ellie?”
“I dont know. Look here’s my place. I dont want you to come up....
I’m going right to bed. I feel miserably....” Jimmy stood with his hat off
looking at her. She was fumbling in her purse for her key. “Look
Jimmy I might as well tell you....” She went up to him and spoke fast
with her face turned away pointing at him with the latchkey that
caught the light of the streetlamp. The fog was like a tent round
about them. “I’m going to have a baby.... Stan’s baby. I’m going to
give up all this silly life and raise it. I dont care what happens.”
“O God that’s the bravest thing I ever heard of a woman doing....
Oh Ellie you’re so wonderful. God if I could only tell you what I....”
“Oh no.” Her voice broke and her eyes filled with tears. “I’m a silly
fool, that’s all.” She screwed up her face like a little child and ran up
the steps with the tears streaming down her face.
“Oh Ellie I want to say something to you ...”
The door closed behind her.
Jimmy Herf stood stockstill at the foot of the brownstone steps.
His temples throbbed. He wanted to break the door down after her.
He dropped on his knees and kissed the step where she had stood.
The fog swirled and flickered with colors in confetti about him. Then
the trumpet feeling ebbed and he was falling through a black
manhole. He stood stockstill. A policeman’s ballbearing eyes
searched his face as he passed, a stout blue column waving a
nightstick. Then suddenly he clenched his fists and walked off. “O
God everything is hellish,” he said aloud. He wiped the grit off his lips
with his coatsleeve.
 She puts her hand in his to jump out of the roadster as the ferry
starts, “Thanks Larry,” and follows his tall ambling body out on the
bow. A faint riverwind blows the dust and gasoline out of their
nostrils. Through the pearly night the square frames of houses along
the Drive opposite flicker like burnedout fireworks. The waves slap
tinily against the shoving bow of the ferry. A hunchback with a violin
is scratching Marianela.
“Nothing succeeds like success,” Larry is saying in a deep
droning voice.
“Oh if you knew how little I cared about anything just now you
wouldnt go on teasing me with all these words.... You know,
marriage, success, love, they’re just words.”
“But they mean everything in the world to me.... I think you’d like it
in Lima Elaine.... I waited until you were free, didnt I? And now here I
am.”
“We’re none of us that ever.... But I’m just numb.” The riverwind is
brackish. Along the viaduct above 125th Street cars crawl like
beetles. As the ferry enters the slip they hear the squudge and
rumble of wheels on asphalt.
“Well we’d better get back into the car, you wonderful creature
Elaine.”
“After all day it’s exciting isnt it Larry, getting back into the center
of things.”

Beside the smudged white door are two pushbuttons marked

Night Bell and Day Bell. She rings with a shaky finger. A short
broad man with a face like a rat and sleek black hair brushed straight
back opens. Short dollhands the color of the flesh of a mushroom
hang at his sides. He hunches his shoulders in a bow.
 “Are you the lady? Come in.”
“Is this Dr. Abrahms?”
“Yes.... You are the lady my friend phoned me about. Sit down my
dear lady.” The office smells of something like arnica. Her heart
joggles desperately between her ribs.
“You understand ...” She hates the quaver in her voice; she’s
going to faint. “You understand, Dr. Abrahms that it is absolutely
necessary. I am getting a divorce from my husband and have to
make my own living.”
“Very young, unhappily married ... I am sorry.” The doctor purrs
softly as if to himself. He heaves a hissing sigh and suddenly looks
in her eyes with black steel eyes like gimlets. “Do not be afraid, dear
lady, it is a very simple operation.... Are you ready now?”
“Yes. It wont take very long will it? If I can pull myself together I
have an engagement for tea at five.”
“You are a brave young lady. In an hour it will be forgotten.... I am
sorry.... It is very sad such a thing is necessary.... Dear lady you
should have a home and many children and a loving husband ... Will
you go in the operating room and prepare yourself.... I work without
an assistant.”
The bright searing bud of light swells in the center of the ceiling,
sprays razorsharp nickel, enamel, a dazzling sharp glass case of
sharp instruments. She takes off her hat and lets herself sink
shuddering sick on a little enamel chair. Then she gets stiffly to her
feet and undoes the band of her skirt.
The roar of the streets breaks like surf about a shell of throbbing
agony. She watches the tilt of her leather hat, the powder, the rosed
cheeks, the crimson lips that are a mask on her face. All the buttons
of her gloves are buttoned. She raises her hand. “Taxi!” A fire engine
roars past, a hosewagon with sweatyfaced men pulling on rubber
coats, a clanging hookandladder. All the feeling in her fades with the
dizzy fade of the siren. A wooden Indian, painted, with a hand raised
at the streetcorner.
“Taxi!”
“Yes ma’am.”
“Drive to the Ritz.”
Third Section
I. Rejoicing City That Dwelt Carelessly

T
here are flags on all the flagpoles up
Fifth Avenue. In the shrill wind of history
the great flags flap and tug at their
lashings on the creaking goldknobbed poles
up Fifth Avenue. The stars jiggle sedately
against the slate sky, the red and white
stripes writhe against the clouds.
In the gale of brassbands and trampling
horses and rumbling clatter of cannon,
shadows like the shadows of claws grasp at
the taut flags, the flags are hungry tongues
licking twisting curling.
Oh it’s a long way to Tipperary ... Over there! Over there!
The harbor is packed with zebrastriped
skunkstriped piebald steamboats, the
Narrows are choked with bullion, they’re
piling gold sovereigns up to the ceilings in
the Subtreasury. Dollars whine on the radio,
all the cables tap out dollars.
There’s a long long trail awinding ... Over there! Over there!
In the subway their eyes pop as they spell
out Apocalypse, typhus, cholera, shrapnel,
insurrection, death in fire, death in water,
death in hunger, death in mud.
Oh it’s a long way to Madymosell from
Armenteers, over there! The Yanks are
coming, the Yanks are coming. Down Fifth
Avenue the bands blare for the Liberty Loan
 drive, for the Red Cross drive. Hospital ships
sneak up the harbor and unload furtively at
night in old docks in Jersey. Up Fifth Avenue
the flags of the seventeen nations are flaring
curling in the shrill hungry wind.
O the oak and the ash and the weeping willow tree
And green grows the grass in God’s country.
The great flags flap and tug at their
lashings on the creaking goldknobbed poles
up Fifth Avenue.

C
aptain James Merivale D.S.C. lay with his eyes closed while
the barber’s padded fingers gently stroked his chin. The lather
tickled his nostrils; he could smell bay rum, hear the drone of an
electric vibrator, the snipping of scissors.
“A little face massage sir, get rid of a few of those blackheads sir,”
burred the barber in his ear. The barber was bald and had a round
blue chin.
“All right,” drawled Merivale, “go as far as you like. This is the first
decent shave I’ve had since war was declared.”
“Just in from overseas, Captain?”
“Yare ... been making the world safe for democracy.”
The barber smothered his words under a hot towel. “A little lilac
water Captain?”
“No dont put any of your damn lotions on me, just a little
witchhazel or something antiseptic.”
The blond manicure girl had faintly beaded lashes; she looked up
at him bewitchingly, her rosebud lips parted. “I guess you’ve just
landed Captain.... My you’ve got a good tan.” He gave up his hand to
her on the little white table. “It’s a long time Captain since anybody
took care of these hands.”
“How can you tell?”
 “Look how the cuticle’s grown.”
“We were too busy for anything like that. I’m a free man since
eight o’clock that’s all.”
“Oh it must have been terr ... ible.”
“Oh it was a great little war while it lasted.”
“I’ll say it was ... And now you’re all through Captain?”
“Of course I keep my commission in the reserve corps.”
She gave his hand a last playful tap and he got to his feet.
He put tips into the soft palm of the barber and the hard palm of
the colored boy who handed him his hat, and walked slowly up the
white marble steps. On the landing was a mirror. Captain James
Merivale stopped to look at Captain James Merivale. He was a tall
straightfeatured young man with a slight heaviness under the chin.
He wore a neat-fitting whipcord uniform picked out by the insignia of
the Rainbow Division, well furnished with ribbons and service-
stripes. The light of the mirror was reflected silvery on either calf of
his puttees. He cleared his throat as he looked himself up and down.
A young man in civilian clothes came up behind him.
“Hello James, all cleaned up?”
“You betcher.... Say isnt it a damn fool rule not letting us wear
Sam Browne belts? Spoils the whole uniform....”
“They can take all their Sam Browne’s belts and hang them on the
Commanding General’s fanny for all I care.... I’m a civilian.”
“You’re still an officer in the reserve corps, dont forget that.”
“They can take their reserve corps and shove it ten thousand
miles up the creek. Let’s go have a drink.”
“I’ve got to go up and see the folks.” They had come out on
Fortysecond Street. “Well so long James, I’m going to get so drunk
... Just imagine being free.” “So long Jerry, dont do anything I
wouldnt do.”
 Merivale walked west along Fortysecond. There were still flags
out, drooping from windows, waggling lazily from poles in the
September breeze. He looked in the shops as he walked along;
flowers, women’s stockings, candy, shirts and neckties, dresses,
colored draperies through glinting plateglass, beyond a stream of
faces, men’s razorscraped faces, girls’ faces with rouged lips and
powdered noses. It made him feel flushed and excited. He fidgeted
when he got in the subway. “Look at the stripes that one has.... He’s
a D.S.C.,” he heard a girl say to another. He got out at
Seventysecond and walked with his chest stuck out down the too
familiar brownstone street towards the river.
“How do you do, Captain Merivale,” said the elevator man.
“Well, are you out James?” cried his mother running into his arms.
He nodded and kissed her. She looked pale and wilted in her
black dress. Maisie, also in black, came rustling tall and rosycheeked
behind her. “It’s wonderful to find you both looking so well.”
“Of course we are ... as well as could be expected. My dear we’ve
had a terrible time.... You’re the head of the family now, James.”
“Poor daddy ... to go off like that.”
“That was something you missed.... Thousands of people died of
it in New York alone.”
He hugged Maisie with one arm and his mother with the other.
Nobody spoke.
“Well,” said Merivale walking into the living room, “it was a great
war while it lasted.” His mother and sister followed on his heels. He
sat down in the leather chair and stretched out his polished legs.
“You dont know how wonderful it is to get home.”
Mrs. Merivale drew up her chair close to his. “Now dear you just
tell us all about it.”
 In the dark of the stoop in front of the tenement door, he reaches
for her and drags her to him. “Dont Bouy, dont; dont be rough.” His
arms tighten like knotted cords round her back; her knees are
trembling. His mouth is groping for her mouth along one cheekbone,
down the side of her nose. She cant breathe with his lips probing her
lips. “Oh I cant stand it.” He holds her away from him. She is
staggering panting against the wall held up by his big hands.
“Nutten to worry about,” he whispers gently.
“I’ve got to go, it’s late.... I have to get up at six.”
“Well what time do you think I get up?”
“It’s mommer who might catch me....”
“Tell her to go to hell.”
“I will some day ... worse’n that ... if she dont quit pickin on me.”
She takes hold of his stubbly cheeks and kisses him quickly on the
mouth and has broken away from him and run up the four flights of
grimy stairs.
The door is still on the latch. She strips off her dancing pumps and
walks carefully through the kitchenette on aching feet. From the next
room comes the wheezy doublebarreled snoring of her uncle and
aunt. Somebody loves me, I wonder who.... The tune is all through
her body, in the throb of her feet, in the tingling place on her back
where he held her tight dancing with her. Anna you’ve got to forget it
or you wont sleep. Anna you got to forget. Dishes on the tables set
for breakfast jingle tingle hideously when she bumps against it.
“That you Anna?” comes a sleepy querulous voice from her
mother’s bed.
“Went to get a drink o water mommer.” The old woman lets the
breath out in a groan through her teeth, the bedsprings creak as she
turns over. Asleep all the time.
Somebody loves me, I wonder who. She slips off her party dress
and gets into her nightgown. Then she tiptoes to the closet to hang
up the dress and at last slides between the covers little by little so
the slats wont creak. I wonder who. Shuffle shuffle, bright lights, pink
blobbing faces, grabbing arms, tense thighs, bouncing feet. I wonder
who. Shuffle, droning saxophone tease, shuffle in time to the drum,
trombone, clarinet. Feet, thighs, cheek to cheek, Somebody loves
me.... Shuffle shuffle. I wonder who.

The baby with tiny shut purplishpink face and fists lay asleep on
the berth. Ellen was leaning over a black leather suitcase. Jimmy
Herf in his shirtsleeves was looking out the porthole.
“Well there’s the statue of Liberty.... Ellie we ought to be out on
deck.”
“It’ll be ages before we dock.... Go ahead up. I’ll come up with
Martin in a minute.”
“Oh come ahead; we’ll put the baby’s stuff in the bag while we’re
warping into the slip.”
They came out on deck into a dazzling September afternoon. The
water was greenindigo. A steady wind kept sweeping coils of brown
smoke and blobs of whitecotton steam off the high enormous
blueindigo arch of sky. Against a sootsmudged horizon, tangled with
barges, steamers, chimneys of powerplants, covered wharves,
bridges, lower New York was a pink and white tapering pyramid cut
slenderly out of cardboard.
“Ellie we ought to have Martin out so he can see.”
“And start yelling like a tugboat.... He’s better off where he is.”
They ducked under some ropes, slipped past the rattling
steamwinch and out to the bow.
“God Ellie it’s the greatest sight in the world.... I never thought I’d
ever come back, did you?”
“I had every intention of coming back.”
“Not like this.”
“No I dont suppose I did.”
 “S’il vous plait madame ...”
A sailor was motioning them back. Ellen turned her face into the
wind to get the coppery whisps of hair out of her eyes. “C’est beau,
n’est-ce pas?” She smiled into the wind into the sailor’s red face.
“J’aime mieux Le Havre ... S’il vous plait madame.”
“Well I’ll go down and pack Martin up.”
The hard chug, chug of the tugboat coming alongside beat
Jimmy’s answer out of her ears. She slipped away from him and
went down to the cabin again.
They were wedged in the jam of people at the end of the
gangplank.
“Look we could wait for a porter,” said Ellen.
“No dear I’ve got them.” Jimmy was sweating and staggering with
a suitcase in each hand and packages under his arms. In Ellen’s
arms the baby was cooing stretching tiny spread hands towards the
faces all round.
“D’you know it?” said Jimmy as they crossed the gangplank, “I
kinder wish we were just going on board.... I hate getting home.”
“I dont hate it.... There’s H ... I’ll follow right along.... I wanted to
look for Frances and Bob. Hello....” “Well I’ll be ...” “Helena you’ve
gained, you’re looking wonderfully. Where’s Jimps?” Jimmy was
rubbing his hands together, stiff and chafed from handles of the
heavy suitcases.
“Hello Herf. Hello Frances. Isn’t this swell?”
“Gosh I’m glad to see you....”
“Jimps the thing for me to do is go right on to the Brevoort with the
baby ...”
“Isn’t he sweet.”
“... Have you got five dollars?”
 “I’ve only got a dollar in change. That hundred is in express
checks.”
“I’ve got plenty of money. Helena and I’ll go to the hotel and you
boys can come along with the baggage.”
“Inspector is it all right if I go through with the baby? My husband
will look after the trunks.”
“Why surely madam, go right ahead.”
“Isnt he nice? Oh Frances this is lots of fun.”
“Go ahead Bob I can finish this up alone quicker.... You convoy
the ladies to the Brevoort.”
“Well we hate to leave you.”
“Oh go ahead.... I’ll be right along.”
“Mr. James Herf and wife and infant ... is that it?”
“Yes that’s right.”
“I’ll be right with you, Mr. Herf.... Is all the baggage there?”
“Yes everything’s there.”
“Isnt he good?” clucked Frances as she and Hildebrand followed
Ellen into the cab.
“Who?”
“The baby of course....”
“Oh you ought to see him sometimes.... He seems to like
traveling.”
A plainclothesman opened the door of the cab and looked in as
they went out the gate. “Want to smell our breaths?” asked
Hildebrand. The man had a face like a block of wood. He closed the
door. “Helena doesn’t know prohibition yet, does she?”
“He gave me a scare ... Look.”
“Good gracious!” From under the blanket that was wrapped round
the baby she produced a brownpaper package.... “Two quarts of our
special cognac ... gout famille ’Erf ... and I’ve got another quart in a
hotwaterbottle under my waistband.... That’s why I look as if I was
going to have another baby.”
The Hildebrands began hooting with laughter.
“Jimp’s got a hotwaterbottle round his middle too and chartreuse
in a flask on his hip.... We’ll probably have to go and bail him out of
jail.”
They were still laughing so that tears were streaming down their
faces when they drew up at the hotel. In the elevator the baby began
to wail.
As soon as she had closed the door of the big sunny room she
fished the hotwaterbottle from under her dress. “Look Bob phone
down for some cracked ice and seltzer.... We’ll all have a cognac a
l’eau de selz....”
“Hadn’t we better wait for Jimps?”
“Oh he’ll be right here.... We haven’t anything dutiable.... Much
too broke to have anything.... Frances what do you do about milk in
New York?”
“How should I know, Helena?” Frances Hildebrand flushed and
walked to the window.
“Oh well we’ll give him his food again.... He’s done fairly well on it
on the trip.” Ellen had laid the baby on the bed. He lay kicking,
looking about with dark round goldstone eyes.
“Isnt he fat?”
“He’s so healthy I’m sure he must be halfwitted.... Oh Heavens
and I’ve got to call up my father.... Isnt family life just too desperately
complicated?”
Ellen was setting up her little alcohol stove on the washstand. The
bellboy came with glasses and a bowl of clinking ice and White Rock
on a tray.
“You fix us a drink out of the hotwaterbottle. We’ve got to use that
up or it’ll eat the rubber.... And we’ll drink to the Café d’Harcourt.”
 “Of course what you kids dont realize,” said Hildebrand, “is that
the difficulty under prohibition is keeping sober.”
Ellen laughed; she stood over the little lamp that gave out a quiet
domestic smell of hot nickel and burned alcohol.

George Baldwin was walking up Madison Avenue with his light

overcoat on his arm. His fagged spirits were reviving in the sparkling
autumn twilight of the streets. From block to block through the
taxiwhirring gasoline gloaming two lawyers in black frock coats and
stiff wing collars argued in his head. If you go home it will be cozy in
the library. The apartment will be gloomy and quiet and you can sit in
your slippers under the bust of Scipio Africanus in the leather chair
and read and have dinner sent in to you.... Nevada would be jolly
and coarse and tell you funny stories.... She would have all the City
Hall gossip ... good to know.... But you’re not going to see Nevada
any more ... too dangerous; she gets you all wrought up.... And
Cecily sitting faded and elegant and slender biting her lips and hating
me, hating life.... Good God how am I going to get my existence
straightened out? He stopped in front of a flowerstore. A moist warm
honied expensive smell came from the door, densely out into the
keen steelblue street. If I could at least make my financial position
impregnable.... In the window was a minature Japanese garden with
brokenback bridges and ponds where the goldfish looked big as
whales. Proportion, that’s it. To lay out your life like a prudent
gardener, plowing and sowing. No I wont go to see Nevada tonight. I
might send her some flowers though. Yellow roses, those coppery
roses ... it’s Elaine who ought to wear those. Imagine her married
again and with a baby. He went into the store. “What’s that rose?”
“It’s Gold of Ophir sir.”
“All right I want two dozen sent down to the Brevoort
immediately.... Miss Elaine ... No Mr. and Mrs. James Herf.... I’ll write
a card.”
 He sat down at the desk with a pen in his hand. Incense of roses,
incense out of the dark fire of her hair.... No nonsense for Heaven’s
sake ...
Dear Elaine,
I hope you will allow an old friend to call on you and your
husband one of these days. And please remember that I am
always sincerely anxious—you know me too well to take this
for an empty offer of politeness—to serve you and him in any
way that could possibly contribute to your happiness. Forgive
me if I subscribe myself your lifelong slave and admirer
George Baldwin
The letter covered three of the florists’ white cards. He read it over
with pursed lips, carefully crossing the t’s and dotting the i’s. Then he
paid the florist from the roll of bills he took from his back pocket and
went out into the street again. It was already night, going on to seven
o’clock. Still hesitating he stood at the corner watching the taxis
pass, yellow, red, green, tangerinecolored.

The snubnosed transport sludges slowly through the Narrows in

the rain. Sergeant-Major O’Keefe and Private 1st Class Dutch
Robertson stand in the lee of the deckhouse looking at the liners at
anchor in quarantine and the low wharfcluttered shores.
“Look some of em still got their warpaint—Shippin Board boats....
Not worth the powder to blow em up.”
“The hell they aint,” said Joey O’Keefe vaguely.
“Gosh little old New York’s goin to look good to me....”
“Me too Sarge, rain or shine I dont care.”
They are passing close to a mass of steamers anchored in a
block, some of them listing to one side or the other, lanky ships with
short funnels, stumpy ships with tall funnels red with rust, some of