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ADVANCES IN QUANTUM CHEMICAL
TOPOLOGY BEYOND QTAIM
ADVANCES
IN QUANTUM
CHEMICAL
TOPOLOGY
BEYOND QTAIM
Edited By
JUAN I. RODRÍGUEZ
Instituto Politecnico Nacional, Mexico
FERNANDO CORTÉS-GUZMÁN
Universidad Nacional Autónoma de Mexico, Mexico
JAMES S.M. ANDERSON

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Contributors
Ricardo Almada-Monter Instituto de Quı́mica, Mark E. Eberhart Department of Chemistry,

Universidad Nacional Autónoma de Mexico, Colorado School of Mines, Golden, CO, United
Mexico City, Mexico States
Omar A. Álvarez-Gonzaga Escuela Superior de Alberto Fernández-Alarcón Instituto de
Fı́sica y Matemáticas, Instituto Politecnico Quı́mica, Universidad Nacional Autónoma de
Nacional, Mexico City, Mexico Mexico, Mexico City, Mexico
James S.M. Anderson Instituto de Quı́mica, Evelio Francisco Departamento de Quı́mica
Universidad Nacional Autónoma de Mexico, Fı́sica y Analı́tica, Facultad de Quı́mica,
Mexico City, Mexico Universidad de Oviedo, Oviedo, Spain
Paul W. Ayers Department of Chemistry, Marco Antonio Garcia-Revilla Department of
McMaster University, Hamilton, Canada Chemistry, Natural and Exact Sciences Divi-
Jose E. Barquera-Lozada Instituto de Quı́mica, sion, University of Guanajuato, Guanajuato,
Mexico City, Mexico Carlo Gatti CNR-SCITEC, Istituto di Scienze e
Yoshio Barrera Instituto de Quı́mica, Tecnologie Chimiche “Giulio Natta”; Istituto
Universidad Nacional Autónoma de Mexico, Lombardo, Accademia di Scienze e Lettere,
Mexico City, Mexico Milano, Italy
Giovanna Bruno Dipartimento di Chimica, Rosa M. Gómez-Espinosa Centro Conjunto de
Università degli Studi di Milano, Milano, Investigación en Quı́mica Sustentable
Italy UAEM-UNAM, Toluca, Estado de Mexico,
Mexico
Pablo Carpio-Martı́nez Instituto de Quı́mica,
Universidad Nacional Autónoma de Mexico, e M. Guevara-Vela Departamento de
Jos
Mexico City, Mexico Quı́mica Fı́sica Aplicada, Universidad
Autónoma de Madrid, Madrid, Spain
Julia Contreras-Garcı́a Sorbonne Universite,
CNRS, Laboratoire de Chimie Theorique, Paris, Jesús Hernández-Trujillo Departamento de
France Fı́sica y Quı́mica Teórica, Facultad de Quı́mica,
UNAM, Mexico City, Mexico
Fernando Cortes-Guzmán Instituto de
Quı́mica, Universidad Nacional Autónoma de Jesús Jara-Cort es Unidad Academica de
Mexico, Mexico City, Mexico Ciencias Básicas e Ingenierı́as, Universidad
Autónoma de Nayarit, Tepic, Mexico
Aurora Costales Departamento de Quı́mica
Fı́sica y Analı́tica, Facultad de Quı́mica, Samantha Jenkins Key Laboratory of Chemical
Universidad de Oviedo, Oviedo, Spain Biology and Traditional Chinese Medicine
Research and Key Laboratory of Resource Na-
Emiliano Dorantes-Hernández Escuela Supe-
tional and Local Joint Engineering Laboratory
rior de Fı́sica y Matemáticas, Instituto
for New Petro-chemical Materials and Fine
Politecnico Nacional, Mexico City, Mexico
ix
x Contributors
Utilization of Resources, College of Chemistry Eduardo Orozco-Valdespino Instituto de

and Chemical Engineering, Hunan Normal Quı́mica, Universidad Nacional Autónoma de
University, Changsha, Hunan, People’s Mexico, Mexico City, Mexico
Republic of China Ángel Martı́n Pendás Departamento de
Laurent Joubert Normandy University, COBRA Quı́mica Fı́sica y Analı́tica, Facultad de Quı́mica,
UMR, Universite de Rouen, INSA Rouen, Universidad de Oviedo, Oviedo, Spain
CNRS, Mont St Aignan Cedex, France David I. Ramı́rez-Palma Instituto de Quı́mica,
Airi Kawasaki Department of Chemistry, Grad- Universidad Nacional Autónoma de Mexico,
uate School of Science, Tokyo Metropolitan Mexico City, Mexico
University, Tokyo, Japan Tomás Rocha-Rinza Instituto de Quı́mica,
Steven R. Kirk Key Laboratory of Chemical Universidad Nacional Autónoma de Mexico,
Biology and Traditional Chinese Medicine Mexico City, Mexico
Research and Key Laboratory of Resource Na- Juan I. Rodrı́guez CICATA-Queretaro, Instituto
tional and Local Joint Engineering Laboratory Politecnico Nacional, Queretaro, Mexico;
for New Petro-chemical Materials and Fine Escuela Superior de Fı́sica y Matemáticas,
Utilization of Resources, College of Chemistry Instituto Politecnico Nacional, Mexico City,
and Chemical Engineering, Hunan Normal Mexico
University, Changsha, Hunan, People’s
Shant Shahbazian Department of Physics,
Republic of China
Shahid Beheshti University, Tehran, Iran
Bruno Landeros-Rivera Departamento de
David C. Thompson Chemical Computing
Fı́sica y Quı́mica Teórica, Facultad de Quı́mica,
Group, Montreal, QC, Canada
UNAM, Mexico City, Mexico
Vincent Tognetti Normandy University, CO-
Cherif F. Matta Department of Chemistry and
BRA UMR, Universite de Rouen, INSA Rouen,
Physics, Mount Saint Vincent University, Hali-
CNRS, Mont St Aignan Cedex, France
fax, Nova Scotia, Canada
Ismael Vargas-Rodrı́guez Department of
Hector D. Morales-Rodrı́guez Escuela Superior
Chemistry, Natural and Exact Sciences Divi-
de Fı́sica y Matemáticas, Instituto Politecnico
sion, University of Guanajuato, Guanajuato,
Nacional, Mexico City, Mexico
Mexico
Amanda Morgenstern Chemistry and Biochem-
Timothy R. Wilson Department of Chemistry,
istry Department, University of Colorado,
Colorado School of Mines, Golden, CO, United
Colorado Springs, CO, United States
States
Aldo de Jesús Mortera-Carbonell Departamento
Tianlv Xu Key Laboratory of Chemical Biology
de Fı́sica y Quı́mica Teórica, Facultad de
and Traditional Chinese Medicine Research
Quı́mica, UNAM, Mexico City, Mexico
and Key Laboratory of Resource National
Xing Nie Key Laboratory of Chemical Biology and Local Joint Engineering Laboratory for
and Traditional Chinese Medicine Research New Petro-chemical Materials and Fine Utili-
and Key Laboratory of Resource National zation of Resources, College of Chemistry
and Local Joint Engineering Laboratory for and Chemical Engineering, Hunan Normal
New Petro-chemical Materials and Fine University, Changsha, Hunan, People’s
Utilization of Resources, College of Chemistry Republic of China
and Chemical Engineering, Hunan Normal
Yong Yang Key Laboratory of Chemical
University, Changsha, Hunan, People’s
Biology and Traditional Chinese Medicine
Republic of China
Contributors xi
Research and Key Laboratory of Resource Na- and Chemical Engineering, Hunan Normal
tional and Local Joint Engineering Laboratory University, Changsha, Hunan, People’s
for New Petro-chemical Materials and Fine Republic of China
Utilization of Resources, College of Chemistry
C H A P T E R
20
Photochemistry: A topological
perspective
Marco Antonio Garcia-Revilla and Ismael Vargas-Rodrı́guez
Department of Chemistry, Natural and Exact Sciences Division, University of Guanajuato,
Guanajuato, Mexico
1. Introduction
The study subjects of Photochemistry are the phenomena associated with the absorption
and emission of electromagnetic radiation by chemical systems. Among such processes are
the following [1]:
• Spectroscopic phenomenon as fluorescence and phosphorescence.
• Luminescent chemical reactions, as the combustion and bioluminescence, for instance the
plankton luminescence and the flashlights of fireflies.
• Photo promoted chemical reactions, as the photosynthesis [1] and the retinal reaction of the
human vision [1].
• Nonlinear optical properties, related to the nonlinear behavior of the induced polarization
of the charge distribution by the interaction of a substance with the electromagnetic
radiation. This phenomenon has become of great importance in telecommunications,
computing, optical devices, microscopy, among others.
Photochemical reactions (PR) are chemical transformations in which an excited state is
reached because of the incidence of electromagnetic radiation, in these reactions the excitation
degree of reactants can be easily controlled using a monochromatic beam of the required
wavelength. Hence, PR are preferred over the thermal reactions, also known as dark
reactions. Besides, thermal reactions deal with a Maxwell-Boltzman distribution of ground
state energies of translational, vibrational, rotational, electronic, and nuclear contributions,
for this reason, the probability of causing a chemical reaction is lower than in the photochem-
ical case [2]. In addition, there are many new synthetic routes to obtain organic compounds
which are not possible to be synthesized by thermal reactions [3].
Advances in Quantum Chemical Topology Beyond QTAIM 515 Copyright # 2023 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-323-90891-7.00015-3
516 20. Photochemistry: A topological perspective
The Stark-Einstein law of photochemical equivalence stablishes that one light-quantum is

absorbed by one molecule promoting a chemical reaction [4], and that is all, there is not a con-
tinuous molecular absorption of light during a photochemical transformation. The efficient
absorption of a light-quantum causes an electronic excitation, for this reason the characteri-
zation of the ground and excited states is fundamental for the understanding of the effects of
the electromagnetic radiation in a substance. An electronic excited state is a solution of the
electronic Schr€ odinger equation with a superior energy than the ground electronic state
[5], the quality of the description of the excited state is related to the chosen electronic struc-
ture method. The following are examples of processes in which excited states are reached
from ground states:
• Elemental particle bombing.
• Alternate current or fire heating exposure.
• Electromagnetic radiation exposure.
The processes experienced by substances induced by electromagnetic radiation can be
viewed as the succession of two phenomena: the excitation of the ground state reaching an
excited state, and the deactivation of the excited state. Some photochemical processes return
to the starting point, the ground state of the substance. Nevertheless, there are some chemical
transformations caused by deactivation of excited states.
1.1 Excitation of the ground state

An excited state is reached after the absorption of electromagnetic radiation, fulfilling the
Frank-Condon principle [4] and the selection rules [4]. Fig. 20.1 shows the Jablonski diagram,
which is a general scheme of the electronic structure related to photochemical processes [4].
The molecule initially relies in the ground state, let’s say a singlet state S0, above the S0 there
are successive singlet excited states S1, S2, …, the consecutive numbering is related to the in-
creasing order in energy. Nevertheless, some molecules hold ground states with different
multiplicity, that is the case of the oxygen molecule in the gas phase at 1 atm and 25°C
displaying a triplet ground state, 3Σ. The singlet excited states are extremely relevant for pho-
tochemical processes, several molecules of chemical interest display singlet ground states. Be-
sides, selection rules stablished that the permitted excitations are those with the same
Vibrational relaxation Vibrational relaxation
Internal conversion
Cross between systems
Absorption
Fluorescence
External conversion
Phosphorescence
FIG. 20.1 Jablonski diagram.

1. Introduction 517
multiplicity [4]. Meanwhile, excited states with multiplicities different than singlets are lo-
cated above the ground state, among such excited states are the triplet states, T1, T2, …, which
are of special interest because of the crucial role of triplet states in phosphorescence. For this
reason, a commonly used Jablonski diagram display S0, S1, S2, …, and T1, T2, … electronic
states. Besides, accordingly to Hund rules, the triplet states hold lower energy than the excited
singlet states. In addition, the quantized vibrational structure is embedded in each electronic
state, the vibrational normal modes are represented as sublevels of each electronic state.
1.2 Deactivation mechanisms of excited states

Once an excited state is reached, deactivation of such excited state takes place. Deactivation
processes can be classified as external (induced by collisions), nonradiative (isoenergetic) and
radiative (luminescence) displayed in Scheme 20.1.
Regarding external processes, the deactivation process could happen through:
I. Vibrational relaxation (VR), in which the molecules in the S1 excited state vibrate and
collide each other dispersing the energy of the system, arriving to the lower vibrational
state of S1. The time to perform this process is about 1012 s.
II. An external conversion (EC), in which the molecule travels from the lower vibrational
mode of S1 to the fundamental singlet state.
III. Chemical Reaction (CR), in which the potential energy surface profile of the singlet and
excited state changes, causing breaking and forming chemical bonds.
CR deactivation processes, represented in Fig. 20.2, show a vertical excitation reaching an
excited state with a vibrational energy large enough to overcome the activation energy to
reach a secondary minimum in the excited state profile. This could drive changes in the con-
nectivity (molecular graph), modifications in binding properties and consequently chemical
SCHEME 20.1 Deactivation processes classification.

FIG. 20.2 Energetic profiles of photochemical processes causing chemical reactions.
transformation. Fig. 20.2B shows the case in which a vertical excitation hits an excited state
with no energy barrier, in such case the chemical transformation occurs straightforward.
A nonradiative process takes place through an isoenergetic energy transference, such pro-
cesses are classified as:
I. Internal Conversion (IC), which happens through an isoenergetic transference from the
S1 excited state to a high energetic vibrational mode of S0, followed by a full vibrational
relaxation of the ground state.
II. Intersystem Crossing (ISC), which is performed though an isoenergetic transference
from a vibrational mode of S1 excited state to a vibrational mode of a tripled state,
let’s say to the T1 triplet state.
Radiative processes are classified as:
I. Normal Fluorescence, which is observed when a full vibrational relaxation along the S1
vibrational modes is followed by a S1 ➔ S0 emissive transition.
II. Resonant Fluorescence, which is observed through a S1➔ S0 emissive transition from
the initial vibrational mode of S1 to the S0 ground state.
Lifetime of Fluorescence processes is about 107 s.
III. Phosphorescence, which is observed when a ISC is followed by a transition between
electronic states of different multiplicity, T1 ➔ S0. Lifetime of T1 is about 105 s and
the transition probability to S0 is low. This is the reason why this process is slower than
the fluorescence.
The radiative processes discussed above are the basis of the fluorescence spectroscopy in
instrumental analysis [6], green fluorescent protein as in vivo marker in genetics [7], tumor
markers in anticancer treatment [8], among others.
2. Theory 519
Another relevant phenomenon is the Chemiluminescence, which is the light emission
caused by a chemical reaction forming a excited state followed by the deactivation of this ex-
cited state to the ground state [9]. The bioluminescence phenomena are those in which bio-
chemical reactions are involved in the formation of the referred excited states, such reactions
are commonly catalyzed by enzymes [10]. There are several applications of chemilumines-
cence, for instance, the luminol reaction in forensic chemistry, the understanding of luciferase
activity in fireflies, the use of oxidation reactions of tetracene in light bars, among others.
2. Theory
A semiclassical approach is useful to study the photophysical phenomena causing chem-

ical transformations in a substance by the interaction with electromagnetic radiation. The
mentioned approach deals with the substance in question using the quantum mechanics,
meanwhile, the electromagnetic radiation is treated through the classic electromagnetism
theory.
From the wave-behavior approach, the electromagnetic radiation is defined as an elec-
tromagnetic oscillating field which propagates as a wave. The classic picture states that
an electromagnetic radiation is produced when a charge q experiences acceleration, for in-
stance, an alternate current circuit and the collision of a proton beam. The electric and mag-
netic fields generated by any charge and current distribution are determined by the
Maxwell equations [4],
ρ
r FðEÞ ¼ (20.1)
E0
r B ¼ 0, (20.2)
∂B
rF¼ , (20.3)
∂t
∂F
r B ¼ μ0 J + μ0 0 , (20.4)
∂t
where F and B represent the electric and magnetic vectors, respectively; E0 and μ0 are the per-
mittivity (E0¼ 8.85 * 1012 C2N1 m2) and permeability (μ0 ¼ 1.25 * 106 NS2C2) vacuum
constants, respectively. The Gauss laws for electric and magnetic fields are presented in
Eqs. (20.1) and (20.2). Eq. (20.1) shows that an electric field is produced by a charge distribu-
tion, meanwhile, Eq. (20.2) shows that the net magnetic flux of a space enclosed by a surface is
zero. The consequence of this law is that there are not magnetic monopoles, at variance whit
electric counterpart in which the electric monopole is possible. The Faraday electromagnetic
induction law is placed in Eq. (20.3), which states that a temporary variation of a magnetic
field generates an electric field. Finally, Eq. (20.4) is the Ampere Law, which indicates that
an electric current and the variation of an electric field generates a magnetic field. The solu-
tions of the four Maxwell equations are electromagnetic waves, in which the energy is
transported through the space. The electric and magnetic field are perpendicular each other
and oscillate during propagation forming a right angle with the propagation direction.
FIG. 20.3 Plane electromagnetic wave.
Electromagnetic plane waves (Fig. 20.3) are of special interest because its simplicity, they
propagate in a single direction having a plane wavefront, the points of the wave packet
are in the same phase forming a plane. In addition, the electric and magnetic fields oscillate
each one in a plane as well, forming a linear polarized electromagnetic wave.
The expressions for the electric and magnetic field of such a wave are
FðEÞ ¼ iFx ¼ iF0x cos ðwt kzÞ, (20.5)
B ¼ jBy ¼ jB0y cos ðwt kzÞ, (20.6)
where F0x and B0y are the amplitudes of the electric and magnetic field, respectively, and w
and k are the wave frequency and wave number, respectively. An extra simplification can be
made, the spatial contribution of the electric field and the entire magnetic component can be
neglected,
FðEÞ ¼ iFx ¼ iF0x cos ðwtÞ, (20.7)
for the case of interaction of electromagnetic waves with organic compounds. Such approx-
imation is based on (a) the fact that the magnitude of the electric field is larger than the mag-
nitude of the magnetic field. The correlation between electric and magnetic field magnitudes
is given by F(E) ¼ cB, where c is the speed of light; and (b) the wave lengths of the electromag-
netic radiation are 3 orders of magnitude, 103 Å, larger than the size of a molecular system.
Nevertheless, such approximation is not valid for metallic systems, in which the electric
bands, and therefore the respective wavelengths, are close to the size of the metal.
There are two correlated phenomena experienced by a molecule during the interaction
with an electromagnetic wave: the vertical excitation, and the charge density polarization.
QCT is a useful tool to study such phenomena.
The quality of the wavefunction describing the ground and excited states is related to the
choice of the electronic structure method to solve the electronic Schr€ odinger equation. There
is a large variety of methods to address such issue. As a matter of fact, the multiconfi-
gurational (MC) methods display the best agreement with experimental measurements.
2. Theory 521
Nevertheless, MC implementations scaling, and the resulting computational cost becomes
prohibitive for the characterization of systems of chemical interest, however, MC results
are used as a reference. For large systems with chemical interest, a way to afford this problem
is using the Time Depending Density Functional Theory [11].
Two issues must be studied during a photochemical process:
1. Polarization of the charge density.
2. Transition probabilities between possible excited states.
2.1 Polarization
The electric field, F, of the photonic incident beam interact with the substance charge dis-
tribution and produce the forces fi ¼ qiE [12], where q is the charge. The induced polarization
during the electric field interaction is observed in Fig. 20.4A. The polarization can be defined
as the change in the charge distribution in a substance due to the interaction with the electro-
magnetic radiation. Any modification in the charge configuration between nuclei and the
electron density in a molecular system induces polarization (Fig. 20.4B). There are two types
of polarization that can be observed: linear (Fig. 20.4), and nonlinear (Fig. 20.5). The linear
polarization happens when the polarization behaves as a linear function of the electric field
(Fig. 20.4C). Besides, induced polarization in macroscopic scale can be expressed as [12,13]:
P ¼ χ ð1Þ F, (20.8)
where P is the induced polarization, F is the electric field and χ (1) is the coefficient of linear
susceptibility.
Linear polarization is observed when a material interacts with a moderate electric field,
nevertheless, when the intensity of the electric field is relatively large, the polarization could
behave in a nonlinearly manner. Observe the nonlinear behavior in induced polarization as a
function of time (Fig. 20.5A), modifications in the charge distribution (Fig. 20.5B) and in the
induced polarization as a function of the applied electric field (Fig. 20.5C), in comparison with
the linear counterpart.
FIG. 20.4 Linear polarization, (A) light beam electric field (solid curve) as a function of time, induced polarization
(solid curve) as a function of time, (B) polarization of a material as a function of time, (C) linear induced polarization as
a function of the applied electric field. Reprinted with permission from M. Pinnow, Materials for nonlinear optics: Chemical
perspectives. ACS symposium series no. 455. Edited by S. R. Marder, J. E. Sohn and G. D. Stucky. ISBN 0-8412-1939-7. Amer-
ican Chemical Society, Washington, DC, 1991. US $ 129.95. Acta Polym. 44 (1993) 112–112. https://doi.org/10.1002/actp.1993.
010440216. Copyright 2022 American Chemical Society.
LINEAR
INDUCED POLARIZATION
–
CHARGE
ELECTRIC FIELD
–
–
DISTRIBUTION + + +
t0 t1 t2
INDUCED
• NONLINEAR
POLARIZATION
t0 t1 t2 APPLIED FIELD
TIME
(a) (b) (c)
FIG. 20.5 Nonlinear polarization, (A) light beam electric field (solid curve) as a function of time, nonlinear-induced
polarization (solid curve) as a function of time, (B) polarization of a material with nonlinear optical activity as a func-
tion of time, (C) nonlinear-linear behavior of second order induced polarization as a function of the applied electric
field. Reprinted with permission from M. Pinnow, Materials for nonlinear optics: Chemical perspectives. ACS symposium series
no. 455. Edited by S. R. Marder, J. E. Sohn and G. D. Stucky. ISBN 0-8412-1939-7. American Chemical Society, Washington,
DC, 1991. US $ 129.95. Acta Polym. 44 (1993) 112–112. https://doi.org/10.1002/actp.1993.010440216. Copyright 2022 Amer-
ican Chemical Society.
The mathematical expression of the macroscopic nonlinear polarization is unknown. Nev-

ertheless, the following Taylor series expansion can be used because the induced polarization
is a continuous function of the electric field [13],
P ¼ P0 + χ ð1Þ F + χ ð2Þ FF + χ ð3Þ FFF + …, (20.9)
where χ (1), χ (2) and χ (3) are the susceptibility coefficients of first, second and third order, re-
spectively. F is the electric field, P is the induced polarization and P0 is the charge distribution
polarization in the absence of the electric field. Linear optical properties (refraction, reflection,
and absorption, among others) are related to the magnitude of χ (1). Second order nonlinear
optical properties (second harmonic generation, frequency mixing, amplification, electro-
optic effect) are related to the magnitude of χ (2). Third-order nonlinear optical properties
(third harmonic generation, frequency mixing, optic bio-stability) are related to the magni-
tude of χ (3), and so on. Some examples in which the nonlinear optical properties are applied
in technology follow: lithium niobate third order properties in telecommunications [14],
processing of optical signaling [15], optical devices [16]. Furthermore, in a biological system
the phase changes are proportional to the radiative intensity changes, getting a clear cell im-
aging without the use of staining substances [17], this phenomenon is used to visualize the
heat waves produced by materials.
From the microscopic perspective, the quantum analog to the induced polarization is the
induced dipolar moment μ [12,13] given by a Taylor series expansion as
1 1
μ ¼ μ0 + αF + βFF + γFFF…:, (20.10)
2 6
where μ is the induced dipolar moment, μ0 is the dipolar moment in absence of the electric
field F, α is defined as the polarizability, β is the first hyperpolarizability and γ is the second
hyperpolarizability. Comparing expressions of macroscopic and microscopic frameworks, α,
β and γ are the microscopic analogs to the first χ (1), second χ (2)and third χ (3) order suscepti-
bility coefficients, respectively.
2. Theory 523
The application of the Quantum Chemical Topology to the characterization of the linear
and nonlinear optical properties needs a deep understanding of the microscopic polarizabil-
ities and hyperpolarizabilities. The energy of the interaction of a charge distribution ρ(r) with
an electric potential Φ(r) can be calculated as follows [18]:
ð
E ¼ ρðrÞΦðrÞdr, (20.11)
The electric field, defined as F ¼ ∂Φ

∂r , is uniform at the molecular framework, for this rea-
son the energy can be expressed by the multipolar expression
1
E ¼ qΦ μF QF0 …, (20.12)
2
where q is the net charge or monopole, μ is the dipolar moment and Q is the quadrupole mo-
ment. Using the last equation, the dipolar moment can be expressed as
∂E
μ¼ , (20.13)
∂F
In the absence of an external electric field, the dipolar and quadrupole moments are cal-
culated from the wavefunction |ψi,
μ0 ¼ hψjrjψ i, (20.14)

Q0 ¼ ψjrrt jψ , (20.15)
where r is the position vector and rt is its transpose. Moreover, the presence of an electric field
conduces to an induced dipolar moment, which is expressed with Eq. (20.10). Besides, for a
homogeneous electric field the total energy is expressed as a Taylor series, where the deriv-
atives are evaluated in F ¼ 0.

∂E 1 ∂2 E 1 ∂3 E 1 ∂4 E
EðFÞ ¼ Eð0Þ + F + F2
+ F3
+ F4 …:, (20.16)
∂F F¼0 2 ∂F2 F¼0 6 ∂F3 F¼0 24 ∂F4 F¼0
this expression can be used to evaluate the induced dipolar moment as

∂E ∂E ∂2 E 1 ∂3 E 1 ∂4 E
μ¼ ¼ F F
2
F3 …, (20.17)
∂F ∂F F¼0 ∂F2 F¼0 2 ∂F3 F¼0 6 ∂F4 F¼0
Comparing with Eq. (20.10), the following expression are deduced:

∂E
μ0 ¼ , (20.18)
∂F F¼0

∂ 2 E
α ¼ 2 , (20.19)
∂F F¼0

∂3 E
β ¼ 3 , (20.20)
∂F F¼0

∂4 E
γ ¼ 4 , (20.21)
∂F F¼0
2.2 Theory of transition probabilities

The interaction of the electric field of an electromagnetic radiation can be studied as a per-
turbation of the time-independent Hamiltonian, such perturbation is a function of the posi-
tion and time. This enables us to use the time-independent Schr€ odinger equation in the study
of the mater-radiation interaction, a time-dependent phenomenon. Let H b ð0Þ be the electronic
Hamiltonian of a molecule and ψ (0) n the wavefunction of the nth stationary state of such sys-
tem, the result eigen value set of equations are
b ð0Þ ðrÞψ ð0Þ ðrÞ ¼ Eð0Þ ψ ð0Þ ðrÞ,

H n ¼ 1,2,3…, (20.22)
n n n
where E(0)
n is the electronic energy of the nth state. The zero super index stablishes the equiv-
alence of the electronic Hamiltonian with the unperturbed Hamiltonian of this approach, for
this reason ψ (0) (0)
n is the wavefunction of the nth unperturbed system and En the energy of the
unperturbed nth state. The inclusion of the perturbation gets the Hamiltonian
b ð0Þ ðrÞ + H
b ðr, tÞ ¼ H
H b 0 ðr, tÞ, (20.23)
If the system initially is in the state ψ (0)
n (r) and, over the effect of electromagnetic radiation
represented by the perturbation, evolves to a different electronic state ψ (0) m (r) the transition
probability Pn!m(t) is a relevant quantity to calculate, because the most probable transitions
are those observed in a spectroscopic experiment.
In first place, the solution of the time-dependent Schr€ odinger equation for this perturbed
system is needed, using a wavefunction Ψ(r, t) the equation to solve is
∂Ψðr, tÞ b h ð0Þ i
iħ ¼ Hðr, tÞΨðr, tÞ ¼ H b ðrÞ + H b 0 ðr, tÞ Ψðr, tÞ, (20.24)
∂t
Expanding the wavefunction Ψ(r, t) as a linear combination of the unperturbed systems ψ (0)
n ,
X ð 0Þ
iE t
Ψðr, tÞ ¼ cn ðtÞψ ðn0Þ e n =ħ , (20.25)
n
And solving for a particular m state with a small perturbation the transition probability is
ð 0 2
1 t b 0 iωmn t0 0
Pn!m ðtÞ ¼ 2 Hmn e dt , (20.26)
ħ 0
D E
b 0 ¼ ψ ðm0Þ jH
b 0 ðr, tÞjψ ðn0Þ and ωmn ¼ Em En . The perturbation considered in the inter-
ð 0Þ ð 0Þ
where H mn ħ
action of electromagnetic radiation with mater is just the temporal contribution of the electric
field, and the interaction of such electric field is given by:
V int ¼ μ F, (20.27)
P
where the μ is the electric dipolar moment of the molecule (μ ¼ qi ri) and F is the temporal
i
contribution to the electric field (F ¼ Fox cos (wt)). For this reason, in the framework of the di-
polar approximation, the perturbative Hamiltonian is written as
b 0 ðtÞ ¼ μx Fox cos ðwtÞ,
H (20.28)
3. QTAIM-photochemistry 525
P
where μx ¼ i q i xi . Substituting this expression in the transition probability, we get
D E2
ð0Þ ð0Þ 2
jFox j2 ψ m jμx jψ n ð t0
0 iωmn t 0
0
Pn!m ðtÞ ¼ cos ð wt Þe dt , (20.29)
ħ2 0
It is of special interest for the QCT community to compute the functional group contribu-
tions of such probabilities.
3. QTAIM-photochemistry
3.1 Polarizabilities and transition probabilities

Bader and co-workers [19,20] address the partition of the polarizability, transition proba-
bilities and dipolar moment of diatomic and polyatomic molecules through the Quantum the-
ory of Atoms in Molecules. Such work is based on the perturbation theory approach,
demonstrating that the polarizability, transition probabilities and dipolar moment can be
expressed as a function of charge transference and polarization components. In addition,
the shape and volume of the atomic basin is modified for the electric field because of the
charge transference. The main conclusion of this work is that the total polarizability, transi-
tion probabilities and dipolar moment are determined by the atomic polarizability and the
charge transference between topological atoms. Furthermore, is demonstrated that a func-
tional group contribution to the total optical properties studied can be defined. A more de-
tailed description of this contribution follows.
Within the dipole approximation and considering a weak field, the transition Pn!k probabil-
ity between n and k states is defined by Eq. (20.29), a simple rearrangement of the equation is
2 ð 0 3 2
t
0 iωmn t0 0
j j ð Þe 7
E2 6
D Fox cos wt dt
ð0Þ 6 0 7
ð0Þ 6 7 ,
Pn!k ðtÞ ¼ ψ m jμx jψ n ∙6 7 (20.30)
4 ħ 5
where the time-independent contribution to the transition probability is the first term of the
product, Pn!k. Following with the time-independent term, it can be written in the integral
form
"ð ! #2
X N
∗
Pn!k ¼ dτψ n er i ψ k , (20.31)
i
where (eri) is the dipole operator of the ith electron and the sum is over all the N electrons of
the system. Due to the multiplicative properties of the dipolar moment operator, the proba-
bility can be written as
ð 2
Pn!k ¼ N dτψ ∗n ðer Þψ k , (20.32)
where the integration is over all N electronic coordinates. Defining a transition density
ð
N dτ0ðψ n ψ k +ψ k ψ n Þ
∗ ∗
ρnk ðrÞ ¼ , (20.33)

2
where the primed integrand means an integration over all spin and spatial coordinates except
for the spatial coordinates of electron 1. The probability is written as
ð 2
Pn!k ¼ N drðer Þρnk ðrÞ ¼ jMnk j2 , (20.34)
where Mnk is the transition moment.

Considering the unperturbed and first perturbative correction to the wave function, ψ (0) n
and ψ (1)
n , respectively, the expressions to the first and second energy corrections to an atomic
basin, Ω, energy are
D E ð ð ð
ð1Þ ð0Þ b 0 ð0Þ 0 ð0Þ∗ b 0 ð0Þ
En ðΩÞ ¼ ψ n jH jψ n ¼ N dr dτ ψ n H ψ n ¼ drHðn1Þ ðrÞ, (20.35)
Ω Ω Ω
ð ð
D E b 0 ψ ð1Þ + ψ ð1Þ∗ H
dr dτ0 ψ ðn0Þ∗ H b 0 ψ ð0Þ ð
n n n
b 0 jψ ð1Þ
Eðn2Þ ðΩÞ ¼ ψ ðn0Þ jH ¼ Ω
¼ drHðn2Þ ðrÞ, (20.36)
n
Ω 2 Ω
where H(1) (2)

n (r) and Hn (r) are the first- and second-order perturbation densities, respectively.
This perturbation modifies the interatomic surface of an atom in a molecule, for this reason
it is important to consider this shift in the surface, δS, in the evaluation of the second order
energy. Whit this regard, the energy contribution to the second order energy due to the first-
order change density should be evaluated,
þ
Eðns2Þ ðΩÞ ¼ dSHðn1Þ ðrÞ δS, (20.37)
The first-order change in the density is evaluated by

D E
ð0Þ b 0 ð0Þ
X ψ n jH jψ n
ρðn1Þ ðrÞ ¼ ρnk ðrÞ, (20.38)
k6¼n
½ En Ek
Hence, the first polarizability, αn(r), using the dipolar approximation, considering the per-
b 0 ¼ eF r, is written in terms of the first order change in the density as
turbation H
ð
αn ðrÞ ¼ erρðn1Þ ðrÞ ¼ eN dτ0 ψ ðn0Þ∗ b
r ψ ðn1Þ + ψ ðn1Þ∗b
r ψ ðn0Þ , (20.39)
X Mnk
αn ðrÞ ¼ e rρ ðrÞ, (20.40)
k6¼n
½En Ek nk
3. QTAIM-photochemistry 527
Integration of such polarizability in an atomic basin gives the atomic polarizability
ð
αbn ðΩÞ ¼ αn ðrÞdr, (20.41)
Ω
The sum of all atomic first polarizabilities is the molecular polarizability

X
α n ðrÞ ¼ αbn ðΩÞ, (20.42)
Ω
One of the main problems of the atomic polarizabilities, αn(r), is the origin dependence be-
cause of the position vector r. Nevertheless, to solve this origin dependence a substitution of
r 5 rΩ +XΩ is used to build the following expression of the total first polarizability
2 3
X6 ð ð
7 X
h i
αðrÞ ¼ 4e dr rΩ ρð1Þ ðrÞ e dr ρð1Þ XΩ 5 ¼ αp ðΩÞ + qð1Þ ðΩÞXΩ , (20.43)
Ω Ω
Ω Ω
where the atomic polarization is defined as

D E
ð ð ð0Þ b 0 ð0Þ
X ψ n jH jψ n
αp ðΩÞ ¼ e dr rΩ ρð1Þ ðrÞ ¼ e dr rΩ ρnk ðrÞ, (20.44)
k6¼n
½En Ek
Ω Ω
ð X Mnk
αp ðΩÞ ¼ e dr rΩ ρ ðrÞ, (20.45)
k6¼n
½En Ek nk
Ω
The integration of over the atomic basin gives

X Mkn Mnk ðΩÞ
α p ð ΩÞ ¼ , (20.46)
k6¼n
½ En Ek
where the atomic moment Mnk(Ω) is obtained with the following integration:
ð
Mnk ðΩÞ ¼ e dr rΩ ρnk ðrÞ, (20.47)
Ω
Besides, it is possible to regroup the nuclear coordinate terms into contributions propor-
tional to the charge transferred from an atomic basing (Ω) to a neighboring atomic basin (Ω0 ).
With this regard, the atomic polarizability gets two contributions one that comes from the
polarization, αp(Ω), and the second one by the charge transference between neighboring
atomic basins, αc(Ω).
X
αðΩÞ ¼ αp ðΩÞ + αc ðΩÞ ¼ αp ðΩÞ + ½Xc ðΩjΩ0 Þ XΩ qð1Þ ðΩ0 Þ, (20.48)
Ω0
The transition probability density can be constructed in analogy with Eqs. (20.38) and
(20.44),
Pn!k ðrÞ ¼ Mnk Mkn ðrÞ ¼ Mkn ∙ðerÞρnk ðrÞ, (20.49)
where Mkn(r) is determined by the respective transition density. Once again, the substitution
of r 5 rΩ +XΩ and subsequent integration gives the expression
ð X
Pn!k ¼ dr Pn!k ðrÞ ¼ Mnk ðΩÞ + qnk ðΩÞXΩ , (20.50)
Ω
Ð
where Mnk(Ω) is the atomic transition dipole, and qnk ðΩÞ ¼ e dr ρnk ðrÞ is the induced atomic
Ω
charge produced by charge density polarization. As in the case of the polarization, it is pos-
sible to solve the origin-dependent problem replacing the sum of nuclear coordinates by a set
of terms describing the dipolar contribution to the charge, qnk(Ω), which is induced by the
polarization between a neighboring atomic basin, Ω0 .
" #
X
0 0
Pn!k ¼ Mnk ∙ Mnk ðΩÞ + ½X ðΩjΩ Þ XΩ qnk ðΩ Þ ,
c
(20.51)
Ω0
At first order, the electronic polarizability is written in the form

μ ¼ μ0 + αF, (20.52)
Which can be rearranged as
μ μ0 ¼ Δμ ¼ αF, (20.53)
Considering a system of a system with nuclear charges Za and position vectors Xa the di-
pole moment is written as
X ð
μ¼ Za Xa rρðrÞdτ, (20.54)
a
Imposing the QTAIM partitioning the dipolar moment is written as

X
μ¼ ½qðΩÞXΩ + MðΩÞ ¼ μc + μp , (20.55)
Ω
where the XΩ is the position vector of the nuclear attractor of the topological atom Ω, μc and μp
are the charge transfer and polarization terms, respectively. In addition, the atomic charge is
defined as
ð
qðΩÞ ¼ ZΩ ρ0 ðrÞdτ ¼ ZΩ N ðΩÞ, (20.56)
Ω
and the first moments M(Ω) are calculated with the following equation:
ð
MðΩÞ ¼ r Ω ρ0 ðrÞdτ, (20.57)
Ω
where the electronic position vector with origin at the nuclear attractor of the topological atom
Ω is rΩ 5r 2 XΩ. Hence, the change in the dipolar moment of such system is calculated by
X ð
Δμ ¼ Za ΔXa rρðn1Þ ðrÞdτF, (20.58)
a
4. QTAIM applications in photochemistry 529
where the topological expression of μ and 4μ are independent of the choice of the origin for a
neutral molecule. With the corresponding form using the QTAIM partitioning
X
Δμ ¼ f½ΔqðΩÞX Ω + ZΩ ΔXΩ + ΔMðΩÞg ¼ Δμc + Δμp , (20.59)
Ω
As in the case of Polarizabilities and transition probabilities it is possible to solve the origin
dependence considering regrouping terms involving nuclear position vectors, as a result the
dipolar moment origin independent is calculated as the sum of atomic dipolar moment con-
tributions in the following manner:
( )
X X X
0 0
μnk ¼ μnk ðΩÞ ¼ Mnk ðΩÞ + ½X ðΩjΩ Þ XΩ qn ðΩ Þ ,
c
(20.60)
Ω Ω Ω0
4. QTAIM applications in photochemistry
A relevant correlation between the ellipticity and the photophysical properties was
reported by Presselt and co-workers [21], where the relation between π-conjugation and ex-
citation efficiency is used to study optical efficiency of Phenyl-Terpyridine Ru(II) and Zn(II)
complexes (Fig. 20.6). Presselt and co-workers analyzed the correlation between π-conjuga-
tion, ellipticity and electronic transition energies of pyridyl-phenyl ligands of such com-
plexes, the lowest transitions are related to a Metal-to-ligand charge transfer dominated by
HOMO-LUMO excitations. The changes in the ellipticity are performed changing the substit-
uent (R) at the para position of phenyl group. The conclusion was that the HOMO-LUMO en-
ergy gap decreases with increasing pyridyl-phenyl ellipticity, therefore it is possible to get a
desirable photophysical properties tunning pyridyl-phenyl ellipticity.
In 2012, J.N. Latosinska and co-workers [22] analyzed the photodegradation of nifedipine
(NIF), an antihypertensive drug, such molecule is highly sensitive to the electromagnetic ra-
diation and degrades to nitrosoniphelipine (NO-NIF), which is not an antihypertensive mol-
ecule but an antioxidative agent. In a combined experimental-computational study,
FIG. 20.6 Schematic representation of the ligands (tpy-ph-R, left), the homoleptic Zn(II) complexes ([Zn(tpy-ph-
R)2]2+, middle), and the heteroleptic Ru(II) complexes ([(tert-butyl-tpy)Ru(tpy-ph-R)]2+, right) as well as the various
substituents R in the 4-ph position. Reprinted with permission from M. Presselt, B. Dietzek, M. Schmitt, S. Rau, A.
Winter, M. J€
ager, et al., A concept to tailor electron delocalization: applying QTAIM analysis to phenylterpyridine compounds.
J. Phys. Chem. A 114 (50) (2010) 15163–74. Copyright 2021 American Chemical Society.
Latosinska and co-workers detected nifedipine photodegradation products by means of

1H-14N Nuclear Quadrupole Double Resonance (NQDR). Besides, a DFT/QTAIM study
was performed to validate the computational capability to predict such photodegradation
products. The computational reactivity criterion was based on the topological QTAIM
Charges and the Laplacian of the electron density at the bond critical pointr2ρ(r)bcp, and
the electron density at the bond critical point ρ(r)bcp. A relevant observation is that r2ρ(r)bcp,
ρ(r)bcp display the largest values at the bonds that break because of irradiation. Hence,
r2ρ(r)bcp, ρ(r)bcp are proper descriptors of the bond susceptibility to be broken by irradiation.
In a recent publication, Chavez-Calvillo and Hernández-Trujillo studied the temporal evo-
lution of the electron density topological properties in the QTAIM framework [23]. The mo-
lecular weave function is represented as a combination of electronic states, in agreement with
the superposition of sates principle,
X
n
ΨðX, x, tÞ ¼ χ i ðX, tÞψ i ðx; XÞ, (20.61)
i
where χ i(X, t) is the time-dependent nuclear wave packet, and χ i(X, t) is the ith electronic state.
Ψ(X, x, t) is calculated through the solution of the time-dependent Schr€ odinger equation, at
the same time the set of adiabatic states {ψ ai } is obtained together with their respective eigen-
values, {Eai }, and nuclear wave packets {Xai }. The time evolution of the average of some prop-
erties of the electron density is characterized by means of the QTAIM partitioning. The time
evolution of the electron density itself can be expressed as
ð X n
χ i ðX, tÞ∗ χ j ðX, tÞρX ðrÞ,
ij
hρðrÞi ¼ dX (20.62)
ij
ij
where ρX(r) is the transition density between ith and jth states. In the same way, the time evo-
lution of the atomic charge is calculated with the expression
ð ð
hqðΩÞiðtÞ ¼ ZΩ N dr dτ0 jΨj2 , (20.63)
Ω
ð X
n
χ i ðX, tÞ∗ χ j ðX, tÞqX ðΩÞ,
ij
hqðΩÞiðtÞ ¼ ZΩ dX (20.64)
ij
The reactive scattering of H+3 and the photodissociation of LiF is studied based on the time
evolution of the atomic charges. An important conclusion is that the time evolution of the
atomic charges is consistent with the adiabatic and diabatic nature of the studied processes.
5. Alternative topological approaches
A molecular graph MG is defined as the set of critical points and flux lines connecting these
critical points [24], among such set is the bond path which is the conjunction of bond critical
points (BCP) and flux lines connecting such BCP with nonboring nuclei. The characterization
of the evolution of the molecular graph along a chemical transformation is a commonly used
tool to get insight of a chemical reaction. Besides, the quantity and type of critical points and
5. Alternative topological approaches 531
paths linking such critical points serve as a qualitative characterization of the connectivity in a
molecule. Changes in molecular graphs along a chemical reaction display qualitative infor-
mation about breaking and forming chemical interactions. In addition, in QTAIM it is possi-
ble to quantitatively measure the bond-path curvature (BPC) separating two bonded nuclei
using the ratio
BPL GBL
BPC ¼ , (20.65)
GBL
where BPL is the bond path length and GBL is the geometric bond length defined as the
internuclear separation. Nevertheless, molecular graphs and BPC did not show significant
changes during electronic state excitations, MG and BPC are qualitatively the same in the
ground and excited states at a particular molecular configuration. For this reason, molecular
graphs cannot be used to track the evolution of a molecule that experiences photochemical
transformations, a similar situation happens for some chemical descriptors of QTAIM. For
instance, the Laplacian of the electron density at the bond critical point (r2ρ(r)bcp) get an av-
erage of the total curvature of the electron density, collapsing in a scalar the information of the
charge accumulation of each spatial direction. So, 2-D(MG) and 1-D (r2ρ(r)bcp) topological
descriptors are unsuccess in the study of photochemical transformations, there are some ap-
proaches to solve this problem: the New Generation QTAIM and the stress tensor approaches.
The New Generation QTAIM methods (NG-QTAIM) is presented as a re-interpretation of
topological aspects of the chemical bonding, a “bond-path framework set” (B) is defined and
it can be used to differentiate the topology of the electron density of excited states from the
ground state. Such set is built by three linkages p, q and r, which are related to the eigenvalues
of the hessian matrix e1, e2 and e3, respectively. The path r is the orthodox QTAIM bond path
where e3 is the eigenvector with the positive eigenvalue, the direction of depletion of charge
density. Furthermore, e1, e2 are the second and first preferred directions in which the charge is
accumulated, respectively. The p and q paths are constructed as the collection of tip path
points defined by the expressions
pi ¼ ri + εi e1,i
(20.66)
qi ¼ ri + εi e2:i
where ri is the ith point at the r path, εi is the ellipticity evaluated in ri, e1, i and e2, i are the
eigenvectors of the accumulative charge density at ri. Such eigenvectors are weighted by
the ellipticity εi, this permit to track the changes in the charge accumulation pattern not only
at the BCP, but in all the bond path. There is no sense to define the path r in terms of the el-
lipticity because the eigenvector e3 is independent of the eigenvalues defining the ellipticity.
This approach is an alternative to the characterization of the Laplacian of the electron density,
in which the information of each curvature collapses at the moment of the evaluation of the
trace of the hessian matrix at the BCP or at any point along the bond path. An important ob-
servation is that p, q and r paths are orthogonal each other because are constructed using or-
thogonal eigenvectors e1,i, e2,i and e3,i. The p and q are used to define the path lengths
Xn1
H∗ ¼ p p , (20.67)
i¼1 i+1 i
Xn1
H¼ q qi , (20.68)
i¼1 i+1
The path lengths are related to the behavior of the charge accumulation along the bond
path. In the limit of zero ellipticity, H path length is equal to the bond path length of r.
The simplicity of this approach is useful to characterize bonding in excited states of photo-
chemical processes.
An useful quantity to characterize the covalency of a chemical bond is the local energy den-
sity defined as [24]:
Hðrb Þ ¼ Gðrb Þ + V ðrb Þ, (20.69)
where G(rb) and V(rb) are the local kinetic and potential energy densities at the bond critical
point, respectively. H(rb) < 0 of closed shell interactions (r2ρ(rb) > 0) show a covalent interac-
tion, for the same closed shell interaction H(rb) > 0 means a lack of covalent character. A strong
shared shell interaction displays r2ρ(rb) < 0 and H(rb) < 0, for example, such situation corre-
sponds to CdC and CdH bonds.
5.1 Stress tensor

Stress tensor connects, through Virial theorem, the quantum information and the clas-
sical picture of mechanical forces equilibria in a molecular system. Such forces are the
Ehrenfest forces experienced by a system, this approach gives a justification of the small
frequencies of the normal modes related to intramolecular rearrangements [24]. The char-
acterization of the eigenvectors of the stress tensor is a useful tool to characterize the
changes in the electron distribution during photochemical processes, such changes are
not observed in traditional QTAIM approaches (molecular graph, Laplacian of electron
density at the bond critical point, etc.). In the QTAIM framework, the stress tensor is de-
fined as
" ! #
1 ∂2 ∂2 ∂2 ∂2 0
σ ðrÞ ¼ + 0 γ ðr, r Þ , (20.70)
2 ∂ri ∂r0j ∂ri ∂rj ∂ri ∂rj ∂r0i ∂r0j 0
r¼r
0
where γ(r, r ) is the first order density matrix. The principal electronic stresses, Πxx, Πyy and
Πzz, are obtained by the diagonalization of σ(r), which are equivalent to the stress tensor ei-
genvalues λ1σ , λ2σ and λ3σ related to the corresponding eigenvectors e1σ , e2σ and e3σ . A negative
stress tensor eigenvalue λ1σ means a compression in the direction of the e1σ eigenvector. Be-
sides, the stress tensor eigenvector trajectories Tσ(s) are constructed as the set of shifts dr(s)
with step s at a BCP [25]. The ordered set of shifts in the eigenvector projection space Uσ are
direction vectors defined by dr0 (s) ¼ {dr e1σ , dr e2σ, dr e3σ }, related to the direction vectors in
the real space dr(s) ¼ {dr e1, dr e2, dr e3} which are related to the follow of the Intrinsic Reac-
tion Coordinate (IRC) from the transition state to the related minima. The respective trajectory
length in the stress tensor projection space Uσ is defined as
X
Lσ ¼ jdr0 ðs + 1Þ dr0 ðsÞj, (20.71)
s¼0
At the real space, the longitude of Tσ(s) is given by
X
l¼ jdrðsÞj, (20.72)
s
Lσ ¼ 0 when the magnitude of BCPs shift and the direction of dr0 (s) are constant.
Using NG-QTAIM, Huang and co-workers [26] studied the photoisomerization of the dou-
ble bond of fulvene at the ground and excited states, with the objective of finding a topological
representation of the chemical bond that differentiates the ground and excited states binding
properties. Besides, an exhaustive exploration of the Potential Energy Surface (PES) was
performed, connecting the Frank-Condon point with the conical intersections occurring
through the torsional coordinate (TC) and the Bond Length Alternation (BLA). Those findings
reveal that traditional QTAIM bond paths cannot differentiate between the binding proper-
ties of ground and excited states. Nevertheless, the bond-framework set B¼¼ [26] was suc-
cessful to reveal binding differences, the path longitude H displays clear differences for both
states in the deactivation of excited state through the BLA and TC see Fig. 20.7.
Tian and co-workers [27] have analyzed the photochemical ring aperture of 1,3-
cyclohexadiene (CGD) at 1,3,5-hezatriene (HT), an archetypical ring rupture mediated by
electromagnetic radiation relevant in biochemistry and in organic chemistry. One of the most
relevant experimental fact is an observed ratio between CHD and HT of (70:30), Tian and
co-workers proposed a rationalization of such ratio based on NG-QTAIM results. The calcu-
lated mechanism at the SSR/ωPBE/6-31G* show a ratio CHD/HT of (60:40), elemental steps
of such mechanism are: The photoexcitation is a π-bonding π-antibonding electronic promo-
tion of a S0 ground state (11A) to a S1 excited state (11B in the C2 symmetry);, where upon the
3.20
c2v C2-C6(S0)
3.10 c2v C2-C6(S1)
3.00
2.90
H
2.80
2.70
2.60
2.50
–0.25 –0.20 –0.15 –0.10 –0.05 0.00 0.05 0.10 0.15 0.20
BLA
FIG. 20.7 The corresponding variations of length H of the eigenvector-following path. The variation of the BPL
with the BLA coordinate is consistent with the variation of the H(rb) values in that the BPL decreases increase in the
BLA coordinate showing the weakening of the C2–C6 BCP. Reprinted with permission from W.J. Huang, R. Momen, A.
Azizi, T. Xu, S.R. Kirk, M. Filatov, S. Jenkins, Next-generation quantum theory of atoms in molecules for the ground and excited
states of fulvene, Int. J. Quantum Chem. 118 (2018) e25768. https://doi.org/10.1002/qua.25768.
nuclear wave-packet slides down the steep slope on the S1 PES and the character of the state
changes from 11B to 21A (a π to σ * transition). After that, the nuclear wave-packet continues to
move on the S1 PES and reaches an S1/S0 conical intersection (CI), where it switches to the S0
state. Having switched to the S0 state, the nuclear wave-packet splits into two branches, one
traveling back to CHD and another propagating forward to HT. The latest gas phase exper-
imental measurements yield 70:30 CHD:HT branching ratio, which is generally consistent
with 60:40 ratio for the reaction in solution, see Fig. 20.8. The authors demonstrate that the
dynamic correlation is extremely important to optimize the conical intersections. The analysis
of the NG-QTAIM of C5dC6 bonds along the minimum energetic profile shows that, before
reaching the conical intersection, H(rb), λ3σ and ε display values indicating a large covalent
stability of the C5dC6 bond at the S0 state compared with the S1.
The latter is a plausible explanation of the (70:30) CHD/HT experimental ratio. A similar
example of the rationalization of photochemical process by NG-QTAIM is the reported by Bin
and co-workers [28], in which the oxirane photochemical ring-opening is modeled and char-
acterized by 3-D topological paths.
Light-driven molecular motors are systems suitable to perform unidirectional rotary
motion, in which a double bond photoisomerization is the driving force of such movement
[29–32]. The photoexcitation breaks a π-bond, resulting in a rotary motion of a molecular moi-
ety in the direction dictated by the properties of the potential energy surface of the return to
the ground state. It is known that such photoisomerization occurs through a conical intersec-
tion S1/S0 [33–35]. Wang and co-workers have studied the topological properties of 3-[(2S)-2-
fluoro-2-methyl-1-indanylidene]-1-methyl-2-methyl-indole (F-NAIBP) along non adiabatic
molecular dynamic trajectories [36,37]. This study deals with the characterization of two types
of dynamic trajectories, Fast (F) and Slow (s). Topological and NG-QTAIM properties were
calculated at conformations along F and S trajectories with the goal of get chemical insight
relative to the speed of such dynamic trajectories. Wang conclude that the bond-path frame-
work set, together with H and H* trajectories, are better descriptors than MG and BPC, pro-
viding a better explanation of the preference of S1 over S0 to activate the rotary molecular
S2
(21A)
S1
(11B)
C.I.
S1 C.I.
(11B)
S0
HT
(11A)
CHD
FIG. 20.8 Scheme of photochemical ring-opening reaction of CHD. Reprinted with permission from T. Tian, T. Xu, S.R.
Kirk, M. Filatov, S. Jenkins, Next-generation quantum theory of atoms in molecules for the ground and excited state of the ring-
opening of cyclohexadiene, Int. J. Quantum Chem. 119 (2019) e25862. Copyright 2021.
motor. In addition, there is a fluorine-hydrogen bond path (F13-H36) that is present only in
the S dynamic trajectory, such interaction displays a covalent character that stuck the molec-
ular rotor. Furthermore, the set of one of the main conclusions is that traditional 2-D molec-
ular graphs and local descriptors are not sufficient to make clear correlations between
topological properties and trajectory speed. Nevertheless, Wang present the stress tensor
trajectory for dynamic trajectories of the reaction pathway, such stress tensor trajectory
can be used to explain the different lifetimes of dynamic trajectories. Along the F trajectory,
up the conical intersection, the components of the stress tensor in the real space are isotro-
pic, this means that a spherical trajectory is expected with an efficient rotation. Meanwhile,
at the S trajectory the t3 component (t3 ¼ e3σ dr) is significantly larger than the rest. Besides,
t3 show large positive values, which indicates important translational movements along the
bond path additional to the torsion, this situation is interpreted as an inefficient rotatory
movement.
The Interacting Quantum Atoms Approach (IQA) is a modern tool to obtain a partition of
the total energy of a molecular system, the contributions to the energy of a system in IQA hold
great physical significance and are used to interpret chemical information of reactivity of mol-
ecules. Pendás and co-coworkers have defined a partitioning of energy using the QTAIM
partitioning of the real space through the density matrix formulation of the average of the
total energy of a Quantum System [38]. In IQA, the total energy of a system can be expressed
ΩΩ0
as a sum of intra-basing energy components, EΩ net, and an inter-basin term, Eint .
X X 0
E¼ EΩ
net + EΩΩ
int , (20.73)
Ω Ω>Ω0
where the EΩ net includes the electronic kinetic energy, electron-nucleus attraction, and
0
electron-electron repulsion at the Ω basin. Meanwhile, EΩΩ
int takes account of electron-nucleus,
electron-electron, and nucleus-nucleus interactions between basins Ω and Ω0 [38]. In addition,
the inter-basin terms can be separated in two, the classical and the exchange-correlation
contributions.
0 0 0
EΩΩ ΩΩ ΩΩ
int ¼ Eclass + Exc , (20.74)
0
EΩΩ
classtakes account of Coulomb-like nucleus-nucleus and electron-electron potential, for
0
this reason it is used as the ionic contribution to a chemical interaction. In addition, EΩΩ
xc is
the quantum counterpart of an interaction, commonly related to a covalent-like contribution
to a chemical bond. In addition, the deformation energy is defined as
EΩ Ω Ω
def ¼ Enet Enet,0 , (20.75)
where EΩ
net, 0 is the reference state, usually the isolated moiety of a molecular system. EΩ def be-
comes a useful quantity to evaluate the change in energy from a reference state to the
studied one.
In a recent contribution, Fernández-Alarcón and co-workers [39] show the capability of
IQA to reveal the effect of intermolecular interactions in excitation energies of molecular
clusters, for the case of the solvatochormic effect in the water dimer. In the first place, authors
reveal the changes in the interatomic surfaces and the dipolar moment of water monomer
because of the S0 ➔ S1 excitation. Besides, such changes affect the energetic contributions,
Another random document with
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his trial for burglary and murder. Mr. George was quite a notable
cracksman in his day, which was one pretty remote from ours in
everything but the conservatism of the law. He was ‘housebreaker’ in
the indictment; he was arrested by the Tombland patrol; and he was
carried to court in a ‘chair,’ attended by a party of the City Guard.
“George, says the story, was an elegant figure of a man, and not
at all regardless of the modes. Dark blue coat with brass buttons,
fancy vest, black satin breeches, white silk stockings, hair full
dressed and a brooch in his bosom—that was how he appeared
before his judges.
“The facts were simple enough. On a night of November, a shot
and a screech had been heard in Mr. Browbody’s house in Unthank,
a ward of the city; an entrance had been made through a window,
opportunely open, by the Watch as opportunely handy, and the
housebreaker had been discovered, a warm pistol in his hand,
standing over the body of old Nicholas, who lay dead on the floor
with his head blown in.
“The burglar was found standing, I say, like as in a stupor; the
room was old Browbody’s study; the door from it into the passage
was open, and outside was discovered the body of a girl, Miss Ellen,
lying, as it were, in a dead faint. There you have the situation dashed
in broad; and pretty complete, you’ll agree, for circumstantial
evidence.”
“Wait, my friend,” began Brindley, putting up a fat pompous hand.
“Circumstantial, I think you said?”
“Yes, I said it,” answered the Deputy Clerk coolly; “and if you’ll
listen, you’ll understand—perhaps. I said the girl was in a faint, as it
were, for, as a matter of fact, she never came out of it for seven
months.”
He leant back, thumbing the ashes into his pipe, and took no heed
while the murmurs of incredulity buzzed and died down.
“Not for seven months,” he repeated, then. “They called it a
cataleptic trance, induced by fright and shock upon witnessing the
deed; and they postponed the trial, waiting for this material witness
to recover. But when at last the doctors certified that they could put
no period to a condition which might, after all, end fatally without real
consciousness ever returning, they decided to try Mr. Hussey; and
he was tried and condemned to be hanged.”
“What! he made no defence?” said a junior contemptuously.
“Well, sir, can you suggest one?” asked the other civilly.
“Suicide, of course.”
“With the pistol there in the burglar’s own hand?”
“Well, he made none, you say.”
“No, I don’t say it. He declared it was ridiculous attempting a
defence, while he lacked his one essential witness to confirm it. He
protested only that the lady would vindicate him if she could speak.”
“O, of course!”
“Yes, of course; and of course you say it. But he spoke the truth,
sir, for all that, as you’ll see.
“He was lodged in Norwich Jail, biding the finish. But, before the
hangman could get him—that time, at least—he managed to break
out, damaging a warder by the way. The dogs of the law were let
loose, naturally; but, while they were in full cry, Mr. Hussey, if you’ll
believe me, walks into a local attorney’s office with Miss Ellen on his
arm.”
Brindley turned in his chair, and gave a little condescending laugh.
“Incredible, ain’t it?” said the Deputy Clerk. “But listen, now, to the
affidavits of the pair, and judge for yourselves. We’ll take Miss Ellen’s
first, plain as I can make it:—
“ ‘I confess,’ says she, ‘to a romantic attachment to this same
picturesque magsman, Mr. Hussey. He came my way—never mind
how—and I fell in love with him. He made an assignation to visit me
in my guardian’s house, and I saw that a window was left open for
him to enter by. My guardian had latterly been in a very odd,
depressed state. I think he was troubled about business matters. On
the night of the assignation, by the irony of fate, his madness came
to a head. He was of such methodical habits by nature, and so
unerringly punctual in his hour for going to bed, that I had not
hesitated to appoint my beau to meet me in his study, which was
both remotest from his bedroom, and very accessible from without.
But, to my confusion and terror, I heard him on this night, instead of
retiring as usual, start pacing to and fro in the parlour underneath. I
listened, helpless and aghast, expecting every moment to hear him
enter his study and discover my lover, who must surely by now be
awaiting me there. And at length I did hear him actually cross the
passage to it with hurried steps. Half demented, dreading anything
and everything, I rushed down the stairs, and reached his room door
just in time to see him put a pistol to his head and fire. With the flash
and report, I fell as if dead, and remember nothing more till the voice
of my beloved seemed to call upon me to rise from the tomb—when I
opened my eyes, and saw Hussey standing above me.’
“Now for Mr. Hussey’s statement:—
“ ‘I had an assignation with a young lady,’ says he, ‘on the night of
so-and-so. A window was to be left open for me in Unthank. I had no
intent whatever to commit a felony. I came to appointment, and had
only one moment entered when I heard rapid footsteps outside, and
a man, with a desperate look on him, hurried into the room, snatched
a pistol from a drawer, put it to his head, and, before I could stop
him, fired. I swear that, so far from killing him, I tried to prevent him
killing himself. I jumped, even as he fell, and tore the pistol from his
hand. Simultaneous with his deed, I heard a scream outside. Still
holding the weapon, I went to the door, and saw the form of her I had
come to visit lying in that trance from which she has but now
recovered. As I stood stupefied, the Watch entered and took me.
From that time I knew that, lacking her evidence, it was hopeless to
attempt to clear myself. After sentence I broke prison, rushed
straight to her house, found her lying there, and called out upon her
to wake and help me. She answered at once, stirring and coming out
of her trance. I know no more than that she did; and there is the
whole truth.’ ”
The Deputy Clerk stopped. No one spoke.
“Now, gentlemen,” said he, “I don’t ask you to pronounce upon
those affidavits. In the upshot the law accepted them, admitting a
miscarriage of justice. What I ask your verdict on is this: Could the
law, after quashing its own conviction, hold the man responsible for
any act committed by him during, and as the direct result of, that
wrongful imprisonment?”
This started the ball, and for minutes it was tossed back and forth.
Presently the tumult subsided, and Brindley spoke authoritatively for
the rest—
“Certainly it could, and for any violence committed in the act.
Provocation may extenuate, but it don’t justify. Prison-breaking, per
se, is an offence against the law; so’s being found without any visible
means of subsistence, though your pocket may just have been
picked of its last penny. Any concessions in these respects would
benefit the rogue without helping the community. I won’t say that if
he hadn’t, by assaulting the warder, put himself out of court——”
“That was where he wanted to put himself,” interrupted the Deputy
Clerk. It was certain that he was deplorably flippant.
Brindley waved the impertinence by.
“The offence was an offence in outlawry,” he said.
“But how could it be,” protested the Clerk, “since, by the law’s own
admission, he was wrongfully convicted? If he hadn’t been, he
couldn’t have hurt the warder. If you strike me first, mayn’t I hit you
back? I tell you, the law acknowledged that it was in the wrong.”
“Not at all. It acknowledged that the man was in the right.”
“Isn’t that the same thing?”
“O, my friend! I see you haven’t got the rudiments. Hussey was a
prisoner; a criminal is a prisoner; ergo, Hussey was a criminal.”
“But he was a prisoner in error!”
“And the law might very properly pardon him that; but not his
violence in asserting it.”
The Deputy Clerk shrugged his shoulders hopelessly.
“Well, it was all the same in the end,” said he; “for it hanged him
for pointing out its error to it, and so spoiled a very pretty romance.
The lady accompanied him to the scaffold, and afterwards died mad.
Sic itur ad astra. I will cap your syllogism, sir. An ass has long ears;
the law has long ears; ergo, the law is an ass.”
“Young man,” said Brindley, with more good humour than I
expected, “you have missed your vocation. Take my advice, and go
to writing for the comic papers.”
“What!” cried the Deputy Clerk. “Haven’t I been a law reporter all
my life!”
THE FIVE INSIDES
I’ll example you with thievery.—“Timon of Athens.”
The dear old lady was ninety, and it was always Christmas in the
sweet winter of her face. With the pink in her cheeks and the white of
her hair, she came straight from the eighteenth century in which she
was born. They were not more at odds with nature than are the hips
and the traveller’s joy in a withered hedge; and if at one time they
paid to art, why it was a charitable gift to a poor dependent—nothing
more, I’ll swear.
People are fond of testing links with the past. This sound old
chatelaine had played trick-track, and dined at four o’clock. She had
eaten battalia pie with “Lear” sauce, and had drunk orgeat in Bond
Street. She had seen Blücher, the tough old “Vorwärts,” brought to
bay in Hyde Park by a flying column of Amazons, and surrendering
himself to an onslaught of kisses. She had seen Mr. Consul
Brummell arrested by bailiffs in the streets of Caen, on a debt of so
many hundreds of francs for so many bottles of vernis de Guiton,
which was nothing less than an adorable boot-polish. She had heard
the demon horns of newspaper boys shrill out the Little Corporal’s
escape from Elba. She had sipped Roman punch, maybe;—I trust
she had never taken snuff. She had—but why multiply instances?
Born in 1790, she had taken just her little share in, and drawn her full
interest of, the history, social and political, of all those years,
fourscore and ten, which filled the interval between then and now.
Once upon a time she had entered a hackney-coach; and, lo!
before her journey was done, it was a railway coach, moving ever
swifter and swifter, and its passengers succeeding one another with
an ever more furious energy of hurry-scurry. Among the rest I got in,
and straight fell into talk, and in love, with this traveller who had
come from so far and from scenes so foreign to my knowledge. She
was as sweet and instructive as an old diary brought from a bureau,
smelling of rose-leaves and cedar-wood. She was merry, too, and
wont to laugh at my wholly illusory attachment to an age which was
already as dead as the moon when I was born. But she humoured
me; though she complained that her feminine reminiscences were
sweetmeats to a man.
“You should talk with William keeper,” she said. “He holds on to the
past by a very practical link indeed.”
It was snowy weather up at the Hall—the very moral of another
winter (so I was told) when His Majesty’s frigate “Caledonia” came
into Portsmouth to be paid off, and Commander Playfair sent
express to his young wife up in the Hampshire hills that she might
expect him early on the following morning. He did not come in the
morning, nor in the afternoon, nor, indeed, until late in the evening,
when—as Fortune was generous—he arrived just at the turn of the
supper, when the snow outside the kitchen windows below was
thawing itself, in delirious emulation of the melting processes going
on within, into a rusty gravy.
“You see,” said Madam, “it was not the etiquette, when a ship was
paid off, for any officer to quit the port until the pennant was struck,
which the cook, as the last officer, had to see done. And the cook
had gone ashore and got tipsy; and there the poor souls must bide
till he could be found. Poor Henry—and poor little me! But it came
right. Tout vient à qui sait attendre. We had woodcocks for supper. It
was just such a winter as this—the snow, the sky, the very day. Will
you take your gun, and get me a woodcock, sir? and we will keep the
anniversary, and you shall toast, in a bottle of the Madeira, the old
French rhyme.”
I had this rhyme in my ears as I went off for my woodcock—
Le bécasseau est de fort bon manger,

Duquel la chair resueille l’appetit.
Il est oyseau passager et petit:
Est par son goust fait des vins bien juger.
I had it in my ears, and more and more despairingly, as I sought

the coverts and dead ferns and icy reed-wrecked pools, and flushed
not the little oyseau passager of my gallantry’s desires. But at last, in
a silent coomb, when my feet were frozen, and my fingers like
bundles of newly-pulled red radishes, William keeper came upon me,
and I confided my abortive wishes and sorrows to his velveteen
bosom.
He smiled, warm soul, like a grate.
“Will’ee go up to feyther’s yonder, sir,” said he; “and sit by the fire,
and leave the woodcock to me? The old man’ll be proud to entertain
ye.”
“I will go,” I said meanly. “But tell me first, William, what is your
very practical link with the past?”
He thought the frost had got into my blood; but when I had
explained, he grinned again knowingly.
“ ’Tain’t me my lady meant, sir,” he said. “ ’Tis old feyther, and his
story of how the mail coach was robbed.”
The cottage hung up on the side of the coomb, leaning its back to
an ash wood, and digging its toes well into the slope to keep itself
from pitching into the brook below. There were kennels under the
faggot stacks, a horse-shoe on the door, red light behind the
windows. It looked a very cosy corner after the white austerity of the
woods. William led me to it, and introducing me and my errand to his
father, left the two of us together by the fire.
It was a strange old shell of a man, russet and smooth yet in the
face; but his breath would sometimes rattle in him to show how dried
was the kernel within. Still his brown eye was glossy, and his voice
full and shrewd; and in that voice, speaking straight and clear out of
the past, and in an accent yet more of the roads than of the woods,
he told me presently the story of the great mail robbery.
“It ruined and it made me, sir,” said he; “for the Captain, hearing as
how the company had sacked me for neglect of duty, and knowing
something of my character, swore I’d been used damnably, and that
he’d back his opinion by making me his gamekeeper. And he did
that; and here I be, waiting confident for him to check my accounts
when I jine him across the river.”
He pointed to a dusky corner. There hung on the wall an ancient
key-bugle, and an old, old napless beaver hat, with a faded gold
band about it.
“I was twenty-five when I put they up there, and that was in the
year ’14; and not me nor no one else has fingered them since.
Because why? Because it was like as if my past laid in a tomb
underneath, and they was the sign that I held by it without shame or
desire of concealment.
“In those days I was guard to the ‘Globe’ coach, that run between
London and Brighton. We made the journey in eight hours, from the
‘Bull and Mouth’ in Aldersgate to the ‘New Inn’ in North Street—or
t’other way about; and we never stopped but for changes, or to put
down and take up. Sich was our orders, and nothing in reason to find
fault with ’em, until they come to hold us responsible to something
besides time. Then the trouble began.
“Now, sir, as you may know, the coachman’s seat was over the
fore-boot, and, being holler underneath, was often used as a box for
special parcels. So it happened that this box was hired of the owners
by Messrs. Black, South, and Co., the big Brighthelmstone bankers,
in order to ship their notes and cash, whenever they’d the mind to,
between London and the seaside, and so escape the risks and
expense of a private mail. The valiables would be slid and locked in
—coachman being in his place—with a private key; and George he’d
nothing to do but keep his fat calves snug to the door, till someun at
the other end came with a duplicate key to unlock it and claim the
property. Very well—and very well it worked till the fifteenth of
December in the year eighteen hundred and thirteen, on which day
our responsibility touched the handsome figure—so I was to learn—
of £4000 in Brighton Union bank notes, besides cash and securities.
“It was rare cold weather, much as it is now, save that the snow
was shallower by a matter of two inches, and no more bind in it than
dry sand. We was advertised to start from the ‘Bull’ at nine; and
there was booked six insides and five out. At ten minutes to the hour
up walks a couple of Messrs. Pinnick and Waghorn’s clerks from the
borough, with the cash box in whity-brown paper, looking as innocent
as a babby in a Holland pinifore. George he comes out of the
shades, like a jolly Corsican ghost, a viping of his mouth; the box is
slung up and fastened in; coachman climbs to his perch, and the five
outsides follow-my-leader arter him to theirs, where they swaddle
’emselves into their wraps strait-veskit-vise, and settin’ as miserable
as if they was waitin’ to have a tooth drawed. Not much harm there,
you’ll say—one box-seat, two behind, two with me in the dickey—all
packed tight, and none too close for observation. Well, sir, we’ll hear
about it.
“Out of the six insides, all taken, there was three already in place:
a gentleman, very short and fierce, and snarling at everything;
gentleman’s lady, pretty as paint, but a white timidious body;
gentleman’s young-gentleman, in ducks and spencer and a cap like
a concertina with the spring gone. So far so good, you’ll say again,
and no connexion with any other party, and leastways of all with the
insides as was yet wanting, and which the fierce gentleman was
blowin’ the lights out of for bein’ late.
“ ‘Guard,’ says he, goin’ on outrageous, while the lady and the
young gentleman cuddled together scared-like in a corner, ‘who are
these people who stop the whole service while they look in the shop-
vinders? If you’re for starting a minute after the stroke,’ says he,
‘dash my buttons,’ he says, ‘but I’ll raise all hell to have you
cashiered!’
“ ‘All right, sir,’ I says. ‘I knows my business better’n you can tell it
me—’ and just as I spoke, a hackney kerridge come rumbling into
the yard, and drew up anigh us.
“ ‘Globe?’ says a jolly, fat-faced man, sticking his head out of it. ‘All
right, Cato—’ and down jumps a black servant, in livery, that was on
the box, and opens the door.
“The fat man he tumbled out—for all the world like a sheetful of
washing a wallopin’ downstairs—Cato he got in, and between them
they helped from the hackney and across to the coach as rickety a
old figure as ever I see. He were all shawls and wraprascal. He’d
blue spectacles to his eyes, a travellin’ cap pulled down on ’em, his
mouth covered in; and the only evidence of flesh to be seen in the
whole of his carcass, was a nose the colour of a hyster. He shuffled
painful, too, as they held him up under the arms, and he groaned
and muttered to himself all the time he were changing.
“Now, sir, you may suppose the snarling gentleman didn’t make
the best of what he see; and he broke out just as they was a-hauling
the invalid in, wanting to know very sarcastic if they hadn’t mistook
the ‘Globe’ for a hearse. But the fat man he accepted him as good-
humoured as could be.
“ ‘It’s nothing affectionate, sir,’ says he. ‘Only paralysis, which ain’t
catching. The gentleman won’t trouble you.’
“ ‘Not for my place,’ says the fierce gentleman, bristling up like a
dog. ‘Damme, sir, not for my place. O, I can see very well what his
nose is a-pinting to, and damme if it isn’t as monstrous a piece of
coolness as ever I expeerunced. These seats, sir, are the nat’ral
perkisite of a considerate punctiality, and if your friend objects to
travelling with his back to the ’orses——’
“ ‘Now, now,’ says the fat man—‘nothing of the sort. You don’t mind
sitting with your back to the ’orses, do you, nunky?”
“ ‘Eh,’ says the old man, ’usky-like, and starting a bit forward—‘No,
no, no, no, no, no, no—’ and he sunk into the front cushions, while
Cato and the fat ’un dispodged him to his comfort.
“ ‘Time, gentlemen!’ says I.
“ ‘Wait a bit’ says snarler. ‘It can’t never be—why, surely, it can’t
never be that the sixth inside is took for a blackamoor?’
“ ‘Alfred,’ says the lady, half veeping: ‘pray let things be. It’s only as
far as Cuckfield we’re goin’, arter all.’
“ ‘A poor argiment, my dear,’ says he, ‘in favour of suffering forty
miles of a sulphurious devil.’
“ ‘Pray control yourself, sir,’ says the fat man, still very ekable.
‘We’ve booked three places, for two, just to be comfortable. Our
servant rides outside.’
“Well, that settled it; and in another minute we was off. I laughed a
bit to myself as I swung up; but I hadn’t a thought of suspicion. What
do you say, sir? Would you have? Why, no, of course not—no more
than if you was a Lyons Mail. There was the five o’ them packed in
there, and one on the roof behind the coachman—three divisions of
a party as couldn’t have seemed more unconnected with one
another, or more cat and dog at that. Yet, would you believe it, every
one of them six had his place in the robbery that follered as carefully
set for him as a figure in a sum.
“As for me, sir, I done my duty; and what more could be expected
of me? At every stage I tuk a general look round, to see as things
were snug and nat’ral; and at Croydon, fust out, I observed as how
the invalid were a’ready nodding in a corner, and the other two gents
settled to their ‘Mornin’ Postses.’
“Beyond Croydon the cold begun to take the outsides bitter; and
the nigger got into a vay of drummin’ with his feet so aggerawacious,
that at last George he lost his temper with him and told him to shut
up. Well, he shut up that, and started scrapin’ instead; and he went
on scrapin’ till the fierce gentleman exploded out of the vinder below
fit to bust the springs.
“ ‘Who’s that?’ roars he—‘the blackamoor? Damme!’ he roars, ‘if
you aren’t wus nor a badger in more ways than one,’ he roars.
“ ‘All right, boss,’ says the nigger, grinning and lookin’ down. ‘Feet
warm at last, boss,’ and he stopped his shufflin’ and begun to sing.
“Now, sir, a sudden thought—I won’t go so far as to call it a
suspicion—sent me, next stop, to examine unostentatious-like the
neighbourhood of them great boots. But all were sound there, and
the man sittin’ well tucked into his wraps. It wasn’t like, of course,
that he could a’ kicked the panels of the box in without George
knowin’ somethin’ about it. And he didn’t want to neither; for he’d
finished his part of the business a’ready. So he just sat and smiled at
me as amiable as Billy Vaters.
“Well, we went on without a hitch; and at Cuckfield the three back
insides turned out into the snow, and went for a bespoke po’-chaise
that was waitin’ for ’em there. But, afore he got in, the fierce
gentleman swung round and come blazin’ back to the vinder.
“ ‘My compliments, sir,’ says he, ‘at parting; and, if it should come
to the vorst,’ he says, ‘I’d advise you to lay your friend pretty far
under to his last sleep,’ he says, ‘or his snores’ll wake the dead.’
“ ‘Hush,’ says the fat ’un. ‘It’s the drowndin’ spirit in him comin’ up
to blow like a vale.’
“ ‘Is it?’ says the fierce gentleman. ‘Then it’s my opinion that the
outsides ought to be warned afore he gives his last heave——’ and
he went off snortin’ like a tornader.
“The fat man shook his head when he were gone. His mildness,
having sich a figger, was amazing. He sat with his arm and shoulder
for a bolster to old paralysis, who was certainly going on in style.
“ ‘Now, sir,’ says I, ‘the whole blessed inside is yourn till the end of
the journey.’
“ ‘Thank you, guard,’ says he; ‘but I won’t disturb my friend, and
we’ll stay as we are, thank you.’
“I got up then, and on we went—last stage, sir, through Clayton,
over the downs, whipping through Pyecombe and Patcham, swish
through Preston turnpike, and so into East Street, where we’d scarce
entered, when there come sich a hullabaloo from underneath as if
the devil, riding on the springs, had got his tail jammed in the brake.
Up I jumps, and up jumps the blackamoor, screeching and clawing at
George, so as he a’most dropped the ribbins.
“ ‘Eh, boss!’ he yelled. ‘De old man—down dere!—damn bad!’
“George he pulled up; and I thought he’d a bust, till I climbed over
and loosened his neckercher, and let it all out. Then down we got—
nigger and I, and one or two of the passengers—and looked in.
‘What the thunder’s up?’ says I. The fat man were goin’ on awful,
sobbin’, and hiccupin’, and holding on to old paralysis, as were sunk
back in the corner.
“ ‘I’m afraid he’s dyin’,’ he said. ‘I’m afraid he’s dyin’! O, why did I
ever give way to him, and let him come!’
“Well, we all stood pretty foolish, not knowing what to say or do,
when his great tricklin’ face come round like a leg o’ mutton on a spit,
and, seein’ the nigger, bust into hystrikes.
“ ‘O, Cato!’ he roars; ‘O Cato, O Cato! Sich a loss if he goes!’ he
roars. ‘Run on by a short cut, Cato,’ he says, ‘and see if you can find
a doctor agen our drawin’ up at the “New Inn.” ’
“That seemed to us all a good idea, though, to be sure, there was
no cut shorter than the straight road we was in. But anyhow, before
we could re’lise it, the nigger was off like a arrer; and one of the
gentlemen offered to keep the fat man company. But that he wouldn’t
listen to.
“ ‘If he should come round,’ he said, ‘the shock of a stranger might
send him off agen. No, no,’ he said: ‘leave me alone with my dying
friend, and drive on as quick as ever you can.’
“It were only a matter of minutes; but afore we’d been drawed up
half of one afore the inn, a crowd was gathered round the coach
door.
“ ‘Is he back?’ says the fat man—‘Is Cato come back with a
doctor? No, I won’t have him touched or moved till a doctor’s seen
him.’
“Then all at once he was up and out, rampageous.
“ ‘Where is he?’ he shrieks. ‘I can’t vait no longer—I’m goin’ mad—
I’ll find one myself’—and, afore you could say Jack Robinson, he
was off. I never see sich a figger run so. He fair melted away. But the
crowd was too interested in the corpse to follow him.
“Well, sir, he didn’t come back with a doctor, and no more did
Cato. And the corpse may have sat there ten minutes, and none
daring to go into it, when a sawbones, a-comin’ down the street on
his own account, was appealed to by the landlord for a verdict, seein’
as how by this time the whole traffic was blocked. He got in, and so
did I; and he bent over the body spread back with its wraps agen the
corner.
“ ‘My God!’ I whispers—‘there’s no breath comin’ from him. Is he
dead, sir?’
“The sawbones he rose up very dry and cool.
“ ‘No,’ he says, ‘there ain’t no breath comin’ from him, nor there
never will. It ain’t in natur’ to expect it from a waxworks.’
“Sir, I tell you I looked at him and just felt my heart as it might be a
snail that someun had dropped a pinch of salt on.
“ ‘Waxworks!’ I says, gaspin’. ‘Why, the man spoke and groaned!’
“ ‘Or was it the gentleman you was tellin’ me of as did it for him?’
says the sawbones, still as dry as cracknels.
“Then I took one jump and pounced on the thing, and caught it up;
—and I no sooner ’ad it in my ’ands, than I knew it were a dummy—
nothing more nor less. But what I felt at that was nothin’ to the shock
my pullin’ it away give me—for there, behind where it had set, was a
’ole, big enough for a boy to pass, cut right through the cushions and
panels into the fore boot; and the instant I see it, ‘O,’ I says, ‘the
mail’s been robbed!’ ”
The old man, who had worked himself up to a state of practised
excitement, paused a dramatic moment at this point, until I put the
question he expected.
“And it had been?”
“And it had been,” he said, pursing his lips, and nodding darkly. “In
the vinter of ’13, sir—the cleverest thing ever planned. It made a rare
stir; but the ’ole truth was never known till years arterwards, when
one o’ the gang (it was the boy as had been, now growed up) were
took on another charge, and confessed to this one. The fat man
were a ventriloquist, you see. That, and to secure the ’ole six insides
to themselves while seemin’ strangers was the cream of the job.
They cut into the boot soon arter we was clear of London, and
passed the boy through with a saw and centre-bit t’other side o’
Croydon. He set to—the young limb, with his pretty innocent ducks!
—tuk a piece clean out of the roof just under the driver’s seat, and
brought down the cash-box; while Mr. Blackamoor Cato kep’ up his
dance overhead to drown the noise of the saw. The box was opened
and emptied, and put back in the boot where it was found; and the
swag, for fear of accidents, was all tuk away at Cuckfield.”
He came to an end. I was aware of William gamekeeper, the
younger, standing silent at the door, with a couple of speckled
auburn trophies in his hand. The fire leapt and fluttered. I rose with a
sigh—then with a smile.
“Thank you, William,” I said gratefully, as I took the woodcock.
“How plump they are; and how I love these links with the past.”
THE JADE BUTTON
The little story I am about to tell will meet, I have no doubt, with a
good deal of incredulity, not to say derision. Very well; there is the
subject of it himself to testify. If you can put an end to him by any
lethal process known to man, I will acknowledge myself misinformed,
and attend your last moments on the scaffold.
Miss Belmont disapproved of Mrs. John Belmont; and Mrs. John

Belmont hated Miss Belmont. And the visible token of this
antagonism was a button.
It was of jade stone, and it was a talisman. For three generations it
had been the mascot of the Belmont family, an heirloom, and
symbolizing in its shining disk a little local sun, as it were, of
prosperity. The last three head Belmonts had all been men of an
ample presence. The first of them, the original owner of the stone,
having assigned it a place in perpetuity at the bottom hole of his
waistcoat (as representing the centre of his system), his heirs were
careful to substantiate a tradition which meant so much to them in a
double sense.
Indeed, the button was as good as a blister. It seemed to draw its
wearer to a head in the prosperous part of him. It was set in gold,
artfully furnished at its back with a loop and hank, and made
transferable from waistcoat to waistcoat, that its possessor for the
time being might enjoy at all seasons its beneficent influence. In
broad or long cloth, in twill or flannel, by day and by night, the button
attended him, regulating indiscriminately his business and his
digestion. In such circumstances, it is plain that Death must have
been hard put to it to find a vulnerable place; and such was the fact.
It has often been said that a man’s soul is in his stomach; how, then,
could it get behind the button? Only by one of those unworthy
subterfuges, which, nevertheless, it does not disdain. The first
Belmont lived to ninety, and with such increasing portliness that, at
the last, a half-moon had to be cut, and perpetually enlarged, out of
the dining-room table to accommodate his presence. Practically, he
was eating his way through the board, with the prospect of emerging
at the other end, when, in rising from a particularly substantial repast
one night, he caught the button in the crack between the first slab
(almost devoured) and the second, wrenched it away, and was
immediately seized with apoplexy. He died; and the Destroyer, after
pursuing his heir to threescore years and ten, looking for the heel of
Achilles, as unworthily “got home” into him. He was lumbering down
Fleet Street one dog-day when, oppressed beyond endurance by the
heat, he wrenched open—in defiance of all canons of taste and
prudence—his waistcoat. The button—the button—was burst from its
bonds in the act, though, fortunately—for the next-of-kin—to be
caught by its hank in the owner’s watch-chain. But to the owner
himself the impulse was fatal. A prowling cutpurse, quick to the
chance, “let out” full on the old gentleman’s bow-window, quenching
its lights, so to speak, for ever; and then, having snatched the chain,
incontinently doubled into the arms of a constable. The property was
recovered—but for the heir; the second Belmont’s bellows having
been broken beyond mending.
The third met with as inglorious an end, and at a comparatively
early age; for the button—as a saving clause to whatever god had
thrown it down, for the fun of the thing, among men—was possessed
with a very devil of touchiness, and always instant to resent the least
fancied slight to its self-importance. Else had Tithonus been its
wearer to this day, as——but I won’t anticipate. The third Belmont,
then, in a fit of colossal forgetfulness, sent the button, in a white
waistcoat, to the wash. The calamity was detected forthwith, but not
in time to avert itself. After death, the doctor. Before the outraged
article could be restored to its owner and victim, he had died of a
rapid dropsy, and the button became the property of Mrs. John
Belmont, his relict and residuary legatee, who——
But, for the history of the button itself? Why, in brief, as it affected
the Belmont family, it was this. Mr. Adolphus Belmont had been
Consul at one of the five treaty ports of China about the troublous
years of 1840-42. During the short time that he held office, a certain
local mandarin, Elephoo Ting by name, was reported to Peking for
high treason, and honoured with an imperial ukase, or invitation to
forestall the headsman. There was no doubt, indeed, that Elephoo
Ting had been very strenuous, in public, in combating the intrusion of
the foreign devil, while inviting him, in private, to come on and hold
tight. There is no doubt, too, that in the result Elephoo and Adolphus
had made a profitable partnership of it in the matter of opium, and
that the mandarin had formed a very high, and even sentimental,
opinion of the business capacities of his young friend. Young, that is
to say, relatively, for Adolphus was already sixty-three when
appointed to his post. But, then, of the immemorial Ting’s age no
record actually existed. The oldest inhabitant of Ningpo knew him as
one knows the historic beech of one’s district. He had always been
there—bland, prosperous, enormous, a smooth bole of a man
radiating benevolence. And now at last he was to die. It seemed
impossible.
It was impossible, save on a condition. That he confided to his odd
partner and confidant, the English Consul, during a last interview. He
held a carving-knife in his hand.
“Shall I accept this signal favour of the imperial sun?” he said.
“Have you any choice?” asked the Consul gloomily. “The decree is
out; the soldiers surround your dwelling.”
Elephoo Ting laughed softly.
“Vain, vain all, unless I discard my talisman.” He produced the jade
button from his cap. “This,” he said, “I had from my father, when the
old man sickened at last of life, desiring to be an ancestor. It renders
who wears it, while he wears it, immortal; only it is jealous, jealous,
and stands upon its dignity. Shall I, too, part with it, and at a stroke
let in the light of ages?”
He saw the incredulity in his visitor’s face, and handed him the
carving-knife.
“Strike,” he said. “I bid thee.”
“You take the consequences?”
“All.”
With infinite cynicism, Mr. Belmont essayed to tickle, just to tickle,
the creature’s infatuation with the steel point. It bent, where it
touched, like paper. He thrust hard and ever harder, until at last he
was thrashing and slicing with the implement in a sort of frenzy of
horror. The mandarin stood apathetic, while the innocuous blade
swept and rustled about his huge bulk like a harmless feather. Then
said he, as the other desisted at length, unnerved and trembling: “Art
thou convinced?”
“I am convinced,” said the Consul.
Elephoo Ting handed him the button in exchange for the knife.
“Take and wear it,” he said, “for my sake, whom you have pleased
by outwitting, on the score of benefiting, two Governments. You have
the makings of a great mandarin in you; the button will do the rest.
Would you ever escape the too-soon satiety of this stodgy life, pass
it on, with these instructions which I shall give you, to your next-of-
kin. Be ever deferential to the button and considerate of its vanity, for
it is the fetish of a sensitive but undiscriminating spirit. So long as
you cherish it, you will prosper. But the least apparent slight to itself,
it will revenge, and promptly. As for me, I have an indigestion of the
world that I would cure.”
And with the words he too became an ancestor.
Then riches and bodily amplitude came to Adolphus Belmont, until
the earth groaned under his importance. He was a spanker, and after
him Richard Belmont was a spanker, and after him John Belmont
was a very spanker of spanks, even at thirty-two, when he
committed the last enormous indiscretion which brought him death
and his fortunes almost ruin. For the outrage to the button had been
so immeasurable that, not content with his obliteration, it must
manœuvre likewise to scatter the accumulations of fortune, which it
had brought him, by involving in a common ruin most of the concerns
in which that fortune was invested, so that his widow found herself
left, all in a moment, a comparatively poor woman.
And here Mrs. John Belmont comes in.
She was a little woman, of piquancy and resource, and a very
accomplished angler of men. She could count on her pink finger-tips
the ten most killing baits for vanity. And, having once recovered the
button, she set herself to conciliating it with a thousand pretty kisses
and attentions. It lived between the bosom of her frock and the ruff of
her dainty nightgown. Yet for a long time it sulked, refusing to be
coaxed into better than a tacit staying of its devastating hand. And so
matters stood when the Assembly ball was held.
Miss Emma Belmont and Mrs. John Belmont lived in the same
town, connexions, but apart. Their visits were visits of ceremony—
and dislike. Miss Emma was Mr. John’s sister, and had always highly
disapproved of his marriage with the “adventuress.” Her very name,
she thought, bordered on an impropriety! How could any “Inez”
dissociate herself from the tradition of cigarette-stained lips and
white eyeballs travelling behind a fan like little moons of coquetry?
This one, in fact, took no trouble to. Her reputation involved them in
a common scandal; and it was solely on this account, I think, that
she so resented her sister-in-law’s appropriation of the button. She
herself was devoted to good works, and utterly content in her
mission. She did not want the button; but, inasmuch as it was a
Belmont heirloom, and Mrs. John childless, she chose to symbolize
in it the bone of contention, and to use it as a convenient bar to
amenities which would, otherwise, have seemed to argue in her a
sympathy with a mode of life with which she could not too
emphatically wish to disconnect herself.
They met at the Assembly ball. Miss Belmont, though herself
involved in the financial ebb, had considered it her duty to respect so
respectable an occasion, and even to adorn it with a silk of such
inflexibility that (I tremble as I write it) one could imagine her slipping
out of it through a trap, like the vanishing lady, and leaving all
standing. Presently Mrs. John Belmont, with a wicked look, floated
up to her.
“You here, Inez!” exclaimed Miss Emma, affecting an amazement
which, unhappily, she could not feel.
The other flirted and simpered. When she smiled, one could detect
little threads drawn in the fine powder near the corners of her mouth.
There was no ensign of widowhood about her. She ruffled with little
gaudy downs and feathers, like a new-fledged bird of paradise.
“Yes, indeed,” she said. “And I’ve brought Captain Naylor, who’s
been dining with me. Shall I introduce him to you?”
Miss Belmont’s sense of decorum left her speechless.
Inez, on the contrary, rippled out the most china-tinkling laugh.
“You dear old thing,” she tittered. “Don’t look so shocked. I knew
you’d be here to chaperon me, and——” She came a step closer.
“Yes, the button’s there, Emma. You may stare; but make up your
mind, I’m not going to part with it.”
Miss Belmont found herself, and responded quietly—
“I hope not indeed, Inez. I don’t ask or expect you. You might
multiply it to-night by a dozen, and only offend me less.”
Mrs. John laughed again, rather shrilly.
“O, fie!” she said. “Why, even you haven’t a high-necked dress,
you know.”
And then a very black and red man, in a jam-pot collar and with a
voice like a rook, came and claimed her.
“Haw, Mrs. Belmont! Aw—er, dance, I think.”
Miss Belmont, to save appearances, rigidly sat out the evening.
When at last she could endure no more, she had her fly called and
prepared to go home. She was about to get into it, when she
observed a familiar figure standing among the few midnight loafers
who had gathered without the shadow of the porch.
“Hurley!” she exclaimed.
The man, after a moment, slouched reluctantly forward, touching
his hat. He had once been her most favoured protégé—a rogue and
irreclaimable, whom she had persuaded, temporarily, from the devil’s
service to her own. He had returned to his master, but with a
reservation of respect for the practical Christian. Miss Belmont was
orthodox, but she had a way with sinners. She pitied and fed and
trusted them. She was a member of the Prisoners’ First Aid Society,
with a reverence for the law and a weakness for the lawless. Her aim
was to reconcile the two, to interpret, in a yearning charity, between
the policeman and the criminal, who at least, in the result, made a
common cause of honouring her. Inez asserted that, living, as she
did, very nervously alone on the outskirts of the town, she had
adopted this double method of propitiation for the sake of her own
security. But, then, Inez had a forked tongue, which you would never
have guessed from seeing the little scarlet tip of it caressing her lips.
Well, Miss Belmont had once coaxed Jim Hurley into being her
handy man, foreseeing his redemption in an innocent association
with flowers and the cult of the artless cabbage. He proved loyal to
her, gained her confidence, knew all about the button and other
matters of family moment. But the contiguity of the kitchen-garden

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Advances in Quantum Chemical

Topology Beyond QTAIM Juan I.

JAMES S.M. ANDERSON

For information on all Elsevier publications

Publisher: Susan Dennis

Typeset by STRAIVE, India

Ricardo Almada-Monter Instituto de Quı́mica, Mark E. Eberhart Department of Chemistry,

Utilization of Resources, College of Chemistry Eduardo Orozco-Valdespino Instituto de

The Stark-Einstein law of photochemical equivalence stablishes that one light-quantum is

1.1 Excitation of the ground state

Vibrational relaxation Vibrational relaxation

FIG. 20.1 Jablonski diagram.

1.2 Deactivation mechanisms of excited states

SCHEME 20.1 Deactivation processes classification.

FIG. 20.2 Energetic profiles of photochemical processes causing chemical reactions.

A semiclassical approach is useful to study the photophysical phenomena causing chem-

FIG. 20.3 Plane electromagnetic wave.

The mathematical expression of the macroscopic nonlinear polarization is unknown. Nev-

The electric field, defined as F ¼ ∂Φ

2.2 Theory of transition probabilities

b ð0Þ ðrÞψ ð0Þ ðrÞ ¼ Eð0Þ ψ ð0Þ ðrÞ,

3.1 Polarizabilities and transition probabilities

ρnk ðrÞ ¼ , (20.33)

where Mnk is the transition moment.

where H(1) (2)

The first-order change in the density is evaluated by

The sum of all atomic first polarizabilities is the molecular polarizability

where the atomic polarization is defined as

The integration of over the atomic basin gives

At first order, the electronic polarizability is written in the form

Imposing the QTAIM partitioning the dipolar moment is written as

4. QTAIM applications in photochemistry

Latosinska and co-workers detected nifedipine photodegradation products by means of

5. Alternative topological approaches

5.1 Stress tensor

Le bécasseau est de fort bon manger,

I had it in my ears, and more and more despairingly, as I sought

Miss Belmont disapproved of Mrs. John Belmont; and Mrs. John

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