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Advances in Quantum Chemistry 56 1st Edition John R.
Sabin And Erkki Brändas (Eds.) Digital Instant
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Author(s): John R. Sabin and Erkki Brändas (Eds.)
ISBN(s): 9780123747808
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Year: 2009
Language: english
 EDITORIAL BOARD

Guillermina Estiú (University Park, PA, USA)

Frank Jensen (Aarhus, Denmark)
Mel Levy (Greensboro, NC, USA)
Jan Linderberg (Aarhus, Denmark)
William H. Miller (Berkeley, CA, USA)
John Mintmire (Stillwater, OK, USA)
Manoj Mishra (Mumbai, India)
Jens Oddershede (Odense, Denmark)
Josef Paldus (Waterloo, Canada)
Pekka Pyykkö (Helsinki, Finland)
Mark Ratner (Evanston, IL, USA)
Adrian Roitberg (Gainesville, FL, USA)
Dennis Salahub (Calgary, Canada)
Henry F. Schaefer III (Athens, GA, USA)
Per Siegbahn (Stockholm, Sweden)
John Stanton (Austin, TX, USA)
Harel Weinstein (New York, NY, USA)
 Advances in
QUANTUM CHEMISTRY
VOLUME
56
Editors

JOHN R. SABIN
Quantum Theory Project
University of Florida
Gainesville, Florida

ERKKI BR˜NDAS
Department of Quantum Chemistry
Uppsala University
Uppsala, Sweden

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 PREFACE

Advances in Quantum Chemistry publishes articles and invited reviews by

leading international researchers in quantum chemistry and neighboring
interdisciplinary fields. Quantum chemistry is a subject concerned with the
quantum mechanical description and dynamics of atoms, molecules, and
condensed matter, with important contributions to human activities like
advanced computer and data communications, atmospheric science, not to
mention recent developments in genomic information and diagnostics in
medicine. Volume 56 invites our reader to six chapters of recent advances of
quantum theoretical methods and applications. There are theoretical appli-
cations to photophysical and photochemical processes where the calcula-
tions indicate the importance of relativistic effects on the photodissociations
of heavy atomic molecules (Liu-Fang). Another theoretically interesting
report (Nooijen) discusses variations on the HohenbergKohn construction
of in principle exact density functionals and the foundations and physical
implications of density functional theory. The chapter by Nalewajski dis-
cusses ‘‘Communication Theory of Chemical Bonds,’’ which concerns the
use of information theoretic concepts to deal with several classical issues in
electronic structure such as single versus multiple bonds, hybridization, and
the like.
In a fundamental theoretical paper, Tapia discusses the contradiction
between the standard BornOppenheimer approach and generalized dia-
batic models carrying the logics of the exact operator time evolution. In the
end, we offer two chapters linked to important application to diagnostics in
oncology and in medical developments related to hadron radiotherapy in
medicine (Belkic). The Fast Padé Transform for Magnetic Resonance Spec-
troscopy is demonstrated, in the first review, to perform full validation of
exact noise separation, which is of critical relevance in clinical oncology.
The second contribution concerns the full treatment of inelastic collisions
between bare nuclei and hydrogen-like atoms of fundamental importance to
particle transport physics in general and heavy ions in medicine in particu-
lar. Finally, we want to thank all authors for their help and willingness to
share their unique insights of quantum chemistry at the state-of-the-art.

John R. Sabin and Erkki Brändas

ix
 CONTRIBUTORS

Numbers in parentheses indicate the pages where the authors’ contributions

can be found.

Dževad Belkić (95, 251)

Karolinska Institute, P.O. Box 260, S-171 76 Stockholm, Sweden

Wei-Hai Fang (1)

College of Chemistry, Beijing Normal University, Beijing 100875, China

Ya-Jun Liu (1)

College of Chemistry, Beijing Normal University, Beijing 100875, China

Roman F. Nalewajski (217)

Department of Theoretical Chemistry, Jagiellonian University, R. Ingardena
3, 30-060 Cracow, Poland

Marcel Nooijen (181)

Department of Chemistry, University of Waterloo, Waterloo N2L 3G1,
Ontario, Canada

O. Tapia (31)
Department of Physical Chemistry and Analytical Chemistry, Uppsala
University, P.O. Box 259, 75105 Uppsala, Sweden

xi
 CHAPTER
1
Multireference and Spin–Orbit
Calculations on
Photodissociations of
Hydrocarbon Halides

Ya-Jun Liu and Wei-Hai Fang

Contents 1. Introduction 1
2. Computational Methods 3
3. Photodissociation of Aryl Halides 4
3.1. Monohalobenzenes and heavy atomic effect 4
3.2. Bromobenzene, dibromobenzene, and 1,3,5-tribromobenzene
and bromine substituent effect 7
3.3. Photon energy effect on the dissociation channels:
chlorobenzene dissociation at 193, 248, and 266 nm 8
3.4. Chlorobenzene, chlorotoluene, and methyl substituent
and rotation effects 11
4. Photodissociation Processes of Halomethane 14
4.1. Bromoiodomethane (CH2BrI) 14
4.2. Dichloromethane (CH2Cl2) 19
4.3. Diiodomethane (CH2I2) 21
5. Conclusions 25
Acknowledgments 26
References 26


College of Chemistry, Beijing Normal University, Beijing 100875, China

Advances in Quantum Chemistry, Vol. 56 Ó 2009 Elsevier Inc.

ISSN: 0065-3276, DOI: 10.1016/S0065-3276(08)00401-2 All rights reserved

1
2 Y.-J. Liu and W.-H. Fang

1. INTRODUCTION

Mechanistic photodissociation of a polyatomic molecule has long been

regarded as an intellectually challenging area of chemical physics [1]. It
draws long-standing interest of both experimental and theoretical chemists
mainly by three reasons. First, the practical importance for the environment
and atmosphere [2–6] and biological systems [7]. Second, their functions in
organic synthesis [8–11] and others [12,13]. Third, pure academic point of
view for understanding the fundamental photochemical reaction mechan-
isms following laser excitation. A detailed understanding of the initial
dynamics is a condition for the possibility of actively intervening with and
ultimately controlling the outcome of a chemical reaction. Recent advances
in femtosecond laser techniques make the deep and detailed understanding
of photodissociation dynamics possible [14–16]. In concert with the experi-
mental research, theoretical study on photochemistry also has made a great
leap due to the development of computer and computational methodologies
[17–22]. Photochemical and photophysical processes are complicated,
besides radiation transition, excited-state vibrational relaxation (VR), inter-
nal conversion (IC), intersystem crossing (ISC), and direct reactions along
excited- or ground-state pathways are generally included. Theoretically, the
VR, IC, and ISC processes can be treated by quantum mechanics through
solving Schrödinger equation for nuclear motion on the multiple potential
energy surfaces (PESs). Actually, this is only available to very small mole-
cules. High-quality calculated potential energy curves (PECs) can provide
much useful information for a detailed understanding of the dissociation
dynamics following excitation at a specific wavelength. However, accurate
PESs are hard or even impossible to obtain from first principles for polya-
tomic molecules. Nowadays, state-of-the-art ab initio methods, complete
active space self-consistent field (CASSCF), CASSCF with second-order
perturbation (CASPT2), and multistate CASPT2 (MS-CASPT2), are power-
ful tools to build accurate PECs [23–25]. The accurate PECs are necessary for
considering conical intersection, which plays an important role in nonadia-
batic dynamics of photodissociation [26–32]. We have done a series of
theoretical studies on photodissociations of hydrocarbon halides [33–41].
Below is a rough summary on their photodissociation mechanisms.
The photodissociation channels of aryl halides could be categorized into
four types. (i) Direct dissociation along a repulsive PES when the photon
creates a single quantum state in the upper electronic state; (ii) electronic
predissociation (Herzberg type I predissociation): the molecule undergoes a
radiationless transition from the binding to the repulsive state and subse-
quently decays; (iii) vibrational predissociation (Herzberg type II predisso-
ciation): the photon creates a quasi-bound state in the potential well which
decays by tunneling or by internal energy redistribution; (iv) hot molecular
decay: the photon creates a bound level in the upper electronic state which
 Multireference and Spin–Orbit Calculations 3

subsequently decays as a result of radiationless transition to the ground

state. Besides the practical importance in atmospheric chemistry and synthesis
of many commercial carbohydrate halide derivatives [42–48], organohalide
compounds especially halomethanes serve as examples for understanding
different photodissociation mechanisms, since they are relatively small and
easy to be considered by high-level calculations including spin–orbit and
relativistic effects [38,40,41].
The theoretical study on the photodissociations of all kinds of hydro-
carbon halides is quite a big topic. The photodissociations on aliphatic and
aryl halides are representative and distinctive. This chapter will focus on
mechanistic photodissociations of aliphatic and aryl halides by state-of-
the-art ab initio calculations. The mainly targeted aryl halides are mono-
halobenzenes including chlorobenzene (ClBz), bromobenzene (BrBz), and
iodobenzene (IBz); dibromobenzene including o-, m-, and p-dibromoben-
zene (o-, m-, and p-diBrBz); 1,3,5-tribromobenzene (1,3,5-triBrBz); and
chlorotoluene including o-, m-, and p-chlorotoluene (o-, m-, and p-ClT). The
mainly targeted aliphatic halides are bromoiodomethane (CH2BrI), dichlor-
omethane (CH2Cl2), and diiodomethane (CH2I2). The below effects on the
photodissociation channels and mechanisms of hydrocarbon halides will be
discussed in detail. The heavy atomic effect, substituent effect, employed
photon energy effect, methyl rotation effect, and relativistic effect.

2. COMPUTATIONAL METHODS
For the aryl halides (FBz, ClBz, BrBz, IBz, o-, m-, and p-diBrBz, 1,3,5-triBrBz,
and o-, m-, and p-ClT), the geometries of the ground state, as well as some
excited states, were optimized using the CASSCF method [49]. The MS-
CASPT2 method [50,51] was used to calculate the vertical excitation
energies (Tv) of the low-lying singlet and triplet states. Ground- and
excited-state PECs along the halogen–carbon bond distances of the aryl
halides were calculated using the MS-CASPT2 method. The phenyl geome-
tries of the excited states were kept equal to the respective relaxed CASSCF
optimized ground-state geometry. All these PECs were drawn adiabatically,
and part of them was also drawn diabatically. The selection of active
electrons and active orbitals is 12-in-10 for FBz, ClBz, BrBz, and IBz;
14-in-12 for o-, m-, and p-diBrBz; and 16-in-13 for 1,3,5-triBrBz. For all the
monobromobenzenes, dibromobenzenes, and 1,3,5-tribromobenzene, the
cc-pVDZ basis set [52] was used for C and H, and the relativistic ab initio
model potential (AIMP) and effective core potential (ECP) of Barandiaran
and Seijo [53] was used for I with 17 valence electrons and Br, Cl, and F with
7 valence electrons. For o-, m-, and p-ClT, the Tv and oscillator strengths ( f )
of the spin-coupled states were also evaluated by the MS-CASPT2 with
spin–orbit interaction through complete active space state (MS-CASPT2/
4 Y.-J. Liu and W.-H. Fang

CASSI-SO) approach [54] in conjunction with atomic mean-field integral

(AMFI) approximation [55]. The selected active space comprises 12 electrons
in 10 orbitals. The relativistic basis sets of the atomic natural orbital type,
ANO-RCC [56], were used with a double zeta- type contraction (denoted as
ANO-VDZP henceforth).
For halomethanes, CH2BrI, CH2Cl2, and CH2I2, the geometries and har-
monic vibrational frequencies of the ground states, transition states (TSs),
and excited states were calculated using both the CASSCF and the CASPT2
[57,58] methods. The Tv and f values of the spin-free states were calculated
using the MS-CASPT2 method. The spin-coupled states were computed by
the MS-CASPT2/CASSISO approach in conjunction with the AMFI approx-
imation. The scalar relativistic effect was considered by the so-called
second-order Douglas–Kroll–Hess (DKH2) type of transformation [59,60].
The selection of active electrons and active orbitals for CH2Cl2, CH2I2,
CH2BrI, and related isomers are 12-in-10, 16-in-12, 16-in-12, and so on, respec-
tively. For the optimizations, an ANO-VDZP basis set was used. Single-point
energies were recalculated by MS-CASPT2 (for spin-free states) or MS-
CASPT2//RASSI-SO (for spin-coupled states) methods with a triplet zeta-
type contraction of ANO-RCC basis set (referred as ANO-VTZP henceforth).
All calculations of halomethanes and chlorotoluenes were performed
using the MOLCAS 6.2 [61] quantum chemistry software. Others were
performed using the MOLCAS 5.4 [62].

3. PHOTODISSOCIATION OF ARYL HALIDES

3.1. Monohalobenzenes and heavy atomic effect

There are rich experimental reports on the photodissociation of IBz [63–75],
BrBz [75–78], and ClBz [64,75,76,79–81]. Density functional theory [82] and
spin–orbit (SO)-MCQDPT [83–85] calculations have been used to study the
photodissociations of IBz. Hartree-Fock [77] and CASSCF [78] calculations
were performed for the photodissociation of BrBz. The studies revealed two
reaction mechanisms of IBz: a direct dissociation caused by excitation to an
antibonding (n,) state and an indirect dissociation caused by a transition
to a (,) state of the phenyl ring that is predissociated by the (n,) state.
However, there is only one photodissociation mechanism for BrBz and
ClBz: an indirect dissociation via ISC between a (,) and a (n,) state.
High-level calculation is still needed for clearly interpreting the fast photo-
dissociation processes of IBz, BrBz, and ClBz observed by experiments and
making reliable comparisons between the different molecules. For example,
it may be possible to clarify to what extent observed differences in photo-
dissociation rates are caused by subtle differences in the predissociation
barriers of the excited states and how the heavy atomic effect affect the
dissociation channels.
 Multireference and Spin–Orbit Calculations 5

The PECs of the lowest singlet and triplet states of C6H5X (X is Cl, Br,
or I) were calculated by the MS-CASPT2//CASSCF method as described in
Section 2. As far as possible, these curves are drawn diabatically so that they
follow a particular electronic configuration through avoided crossings
between two states of the same symmetry. Here we only focus on those
possible states related to the experimentally observed photodissociation
channels at 266 nm. Their PECs were included in one figure (Figure 1.1)
for comparison. For details of the adiabatic and diabatic PECs, see Ref. [34].
All experimental investigations of the photodissociation of BrBz at
266 nm have indicated decay via a single fast photodissociation channel
[75,77,78]. Kadi et al. [75] measured its time constant to be 28 ps. According
to our calculations, the only singlet excited state that 266 nm could reach is
the bound S1-B2 state, which is reached by a (,) transition. The S1-B2 state

S1-B2(CIBz)

S1-B2(BrBz)

S2-B2(IBz)

T5-B1(CIBz)
ΔE

T4-B1(BrBz)
S0-A1(CIBz)
S1-B1(IBz)
S0-A1(BrBz)
T2-B2(IBz)

S0-A1(IBz)

R(X–C)

Figure 1.1 Schematic MS-CASPT2 diabatic PECs along the XC bond distance of ClBz, BrBz,
and IBz, illustrating their fast photodissociation channels at 266 nm.
6 Y.-J. Liu and W.-H. Fang

crosses a repulsive triplet state T4-B1, which is reached by a (n,) transition.

The Tv value is about 4.91 eV at the crossing point, which is near the 266 nm
(4.66 eV) used in the experiments [75,77,78]. As errors in CASPT2-computed
excitation energies are typically less than 0.3 eV [86], we assign the dissocia-
tion with 28 ps lifetime to a Herzberg’s type I predissociation, with strong
coupling between the bound S1-B2 state and the repulsive T4-B1 state leading
to dissociation, as shown in Figure 1.1.
According to Figure 1.1, the photodissociation situation of ClBz is similar
to that of BrBz. The bound S1-B2 state, of (,) origin, crosses a repulsive
T5-B1 state, of (n,) origin. But the Tv value at the crossing point is 0.49 eV
higher than the 266 nm excitation energy used in the experiments [75,79].
This difference exceeds the anticipated CASPT2 calculation errors. In fact,
the crossed molecular beam technique did not detect such a fast photodis-
sociation at 266 nm. The photodissociation studies using femtosecond
pump-probe spectroscopy upon excitation at 266 nm detected a slow dis-
sociation for ClBz with 1 ns time constant [75]. This slow photodissociation
is not caused by a Herzberg’s type I predissociation, with coupling between
the bound S1-B2 state and the repulsive T5-B1 state. The photodissociation
mechanism of ClBz at different wavelength will be discussed in Section 3.3.
The photodissociation of IBz is different from that of BrBz and ClBz. The
experimental investigations [65,68,75,82] at 266 nm detected two photodis-
sociation channels for IBz. The femtosecond pump-probe spectroscopy gave
the two time constants of 700 and 350 fs [75]. El-Sayed and coworkers
[65,67,71] as well as Zewail and coworkers [87] proposed that the faster
dissociation is due to a direct dissociation of the repulsive triplet (n,) state,
and the slower dissociation is due to a spin–orbit-induced crossing from the
triplet (,) state to the repulsive singlet (n,) state. Previous calculations
using density functional theory (DFT) and (SO)-MCQDPT methods [82,84]
supported this explanation. According to the present calculations, the first
triplet excited state of IBz is not a repulsive state. However, the first singlet
excited state, S1-B1, is a repulsive (n,) state with 4.5 eV Tv, which is 0.16 eV
lower than 266 nm. So, the fast dissociation, 350 fs, was assigned to a direct
dissociation of S1-B1. The first bound singlet excited state of IBz is a S2-B2 state
with a Tv of 4.60 eV. From Figure 1.1, the lowest repulsive triplet excited state
that the bound (,) S2-B2 state crosses is T2-B2. The Tv value of the crossing
point is 4.33 eV. This energy is lower than the 266 nm excitation used in the
experiments. So, we assign the other fast photodissociation, 700 fs, to a
Herzberg type I predissociation, with the strong couplings between the
bound S2-B2 state and the repulsive T2-B2 state leading to dissociation. As
shown in Figure 1.1, the crossing point between the S2-B2 and the T2-B2 states
is very low in energy and close to the minimum of this S2-B2 state.
To conclude, ClBz, BrBz, and IBz all have Herzberg’s type I predissocia-
tions with a (,) bound singlet state crossing a repulsive (n,) triplet state.
For ClBz, the spin–orbit coupling occurs between the S1-B2 state and the
 Multireference and Spin–Orbit Calculations 7

T5-B1 state. For BrBz, it occurs between the S1-B2 state and the T4-B1 state.
However, for IBz, the spin–orbit coupling instead takes place between the
S2-B2 state and the T2-B2 state. The relative energies of the crossing points
(connected to the predissociation barriers) to the experimentally employed
266 nm wave-length photon are 0.49 eV for ClBz, 0.25 eV for BrBz, and
–0.33 eV for IBz. This clearly shows that the spin–orbit coupling is becoming
stronger from ClBz to BrBz to IBz for heavy atomic effect. The presence of an
atom of high atomic number enhances the rate of a spin-forbidden process,
which results in a spin–orbit coupling enhancement. For IBz, it even opens
another direct photodissociation channel via S1-B1 state.

3.2. Bromobenzene, dibromobenzene, and 1,3,5-tribromobenzene

and bromine substituent effect
The PECs of some lowest singlet and triplet states of BrBz; o, m, and p-diBrBz;
and 1,3,5-triBrBz were calculated by the MS-CASPT2//CASSCF method.
Please see Ref. [33] for detailed adiabatic and diabatic PECs. These four
molecules have photodissociation mechanism in similarities and differences.
In order to compare their photodissociation mechanism, a schematic figure of
PECs, Figure 1.2, was employed. The experimentally [75,88] employed 266 nm

T4, T5, or T6 (n,σ ∗)

S1(π,π∗)

T2
ΔE

S0
266 nm

R(Br–C)

Figure 1.2 Schematic diabatic PECs along the BrC bond distance of BrBz, o-, m-, and
p-diBrBr, and 1,3,5-triBrBz, illustrating their photodissociation channels at 266 nm.
8 Y.-J. Liu and W.-H. Fang

wave-length photon can reach the S1 state of all the four molecules. All these S1
states are (,) bound ones and cannot dissociate themselves. For each mole-
cule, the (,) bound S1 state crosses with the PEC of a repulsive (n,) triplet
state and results in a Herzberg’s type I predissociation, as shown in Figure 1.2.
The repulsive (n,) triplet state is T4-B1 for BrBz, T6-A0 for o-diBrBz, T4-A0 for
m-diBrBz, T5-B1 for p-diBrBz, and T5-B1 for 1,3,5-triBrBz. The position of the
crossing point is getting lower from BrBz to p-diBrBz to m-diBrBz to o-diBrBz
and to 1,3,5-triBrBz (see Ref. [33] for details), which roughly reflect their
dissociation rate, 36, 18.2, 13.3, 7.5, and 1 ps, respectively. The rate of this
process increased with the number of bromine atoms on the ring and also
with decreasing distance between the bromine atoms, as expected for a process
mediated by spin–orbit interaction. Another important state is T2 in Figure 1.2,
which is a quasi-bound state for all the four molecules. The saddle point of the
T2 state is unreachable by 266 nm photon for BrBz, p-diBrBz, and 1,3,5-triBrBz.
o- and m-diBrBz have lower barrier for the T2 state, and their saddle points are
lower than the corresponding crossing point of the above Herzberg’s type I
predissociation. So the experimentally employed 266 nm photon can easily
reach the saddle point of the o- and m-diBrBz T2 state. This results in the
other faster dissociation channels for o- and m-diBrBz via Herzberg’s type II
predissociation. Moreover, as the potential barrier is lower in o-diBrBz than in
m-diBrBz, this mechanism agrees with the observation that the second disso-
ciation rate of o-diBrBz is smaller [88]. As discussed above, the additional
bromine atoms increased the dissociation rates through the increasing spin–
orbit interaction, and the different substituent position also caused the differ-
ence in the dissociation of dibromobenzenes.

3.3. Photon energy effect on the dissociation channels:

chlorobenzene dissociation at 193, 248, and 266 nm
Experimentally, the photodissociation dynamics of ClBz has been studied at
266 [75,79], 248 [80], and 193 nm [64,80,89]. It was concluded that the
photodissociation of the CCl bond in ClBz at 193 nm takes place through
three different dissociation channels with probabilities of similar magni-
tudes. The first channel was assigned to a direct dissociation or very fast
predissociation, the second channel is via vibrationally excited triplet levels,
and the third dissociation channel is via highly excited vibrational levels of
the ground electronic state (hot molecules). The photodissociation of ClBz at
248 nm was proposed to occur dominantly via the second and third of the
above-mentioned channels. The photodissociation at 266 nm has been given
alternative explanations. On the one hand, it was proposed to be due to a
hot molecule mechanism by Wang et al. [79] On the other hand, Kadi et al.
[75] assigned it to the decay of an initially excited (,) state to a repulsive
triplet (n,) state due to spin–orbit coupling, and they observed its time
constant to be 1 ns [75].
 Multireference and Spin–Orbit Calculations 9

The MS-CASPT2 PECs of 12 singlet and 12 triplet states of ClBz was

calculated. The shortest excitation wavelength employed in the experiments
was 193 nm, and we therefore focus mainly on the excited singlet states with
Tv under or near 193 nm and the repulsive triplet states that are likely to
interact with these singlet states. These are the S0-A1, S1-B2, S2-A1, S3-B2,
S4-B1, and T5-B1 states (see Ref. [36] for details). There is one avoided
crossing between S1-B2 and S3-B2. We extracted the PECs of these states
from the diabatic PECs of the 12 singlet and 12 triplet states and included them
in Figure 1.3. From Figure 1.3 and the transition characteristics, S1, S2, and S3

9.5

8.5

7.5

6.5

5.5
ΔE/eV

4.5

3.5

2.5
S0-A1 S1-B2

1.5 S2-A1 S3-B2

S4-B1 T5-B1
193 nm 248 nm
0.5
266 nm

–0.5
1.3 1.7 2.1 2.5 2.9 3.3 3.7 4.1
R(Cl–C1)/Å

Figure 1.3 The MSCASPT2 diabatic potential energy curves along the ClC bond distance
of one triplet and five singlet states of ClBz. The horizontal dashed lines indicate the
193-, 248-, and 266-nm excitation energy used in previous experiments.
10 Y.-J. Liu and W.-H. Fang

are bound (,) states, whereas S4 and T5 are repulsive (n,) states. S4-B1, with
6.59 eV Tv, is the highest singlet excited state that the photon of 193-nm
wavelength could reach. It is a repulsive state that will dissociate directly on
a very short time scale. This direct dissociation should contribute to the fastest
of the three channels observed in Ref. [80]. As shown in Figure 1.3, S3-B2 is a
quasi-bound state with a barrier that blocks immediate dissociation. The
energy gap between its saddle point and the minimum of the ground state is
about 6.6 eV. It is possible that molecules excited by 193 nm photons can over-
come the predissociation barrier if the MS-CASPT2 error of 0.3 eV is taken into
account. If so, its lifetime will depend on the tunneling rate. This process
would proceed via Herzberg’s type II predissociation. This fast predissociation
could then also contribute to the fastest dissociation channel as proposed in
Ref. [80]. From Figure 1.3, the PEC of S3-B2 crosses the repulsive (n,) T5-B1
state. The ClC1 bond distance at the crossing point is about 1.82 Å. It is also
about 0.2 eV lower than 193 nm. So, we assign the second experimentally
observed channel as the ISC from the bound (,) S3-B2 state to the repulsive
(n,) T5-B1 state. The complex will ultimately decay with a rate that depends
on the coupling between the two electronic states. This is a Herzberg’s type I
predissociation. The third photodissociation channel is slower than the first
two channels and was suggested to take place via IC to highly excited vibra-
tional levels of the ground state [80]. From Figure 1.3, it appears likely that the
S3-B2 state first undergoes IC to the S1-B2 state. The lowest vibrational state of S1
is much closer in energy to the dissociation limit of S0, and thereby makes IC
from S1 to S0 more likely. This mechanism is compatible with the third
observed photodissociation channel with lower rate.
The highest singlet excited state the photon with 248-nm [80] wavelength
can reach is S1-B2, whose Tv is 4.50 eV. S1 is a bound (,) state, which
cannot dissociate by itself. However, the S1-B2 state can undergo an ISC to
the repulsive (n,) T5-B1 state. The ClC calculated bond distance at the
crossing point is about 2.02 Å. The energy gap between this point and the
minimum of the ground state is about 5.0 eV. The complex will ultimately
decay due to spin–orbit coupling between the two electronic states. So, the
first channel of photodissociation of ClBz at 248 nm is the ISC from S1-B2 to
T5-B1, and it is a Herzberg’s type I predissociation. From Figure 1.3, the PEC
of S1-B2 also undergoes an IC with the repulsive (n,) S4-B1 state. The ClC
bond distance at the crossing point is about 2.06 Å. The energy gap between
this point and the minimum of the ground state is about 5.15 eV. If the 248-
nm wavelength photon used in the experiment overcomes this energy
barrier, then the complex will ultimately decay by IC. So, the first channel
of photodissociation of ClBz at 248 nm is also possibly via the IC from S1-B2
to S4-B1. The second slower photodissociation channel observed experimen-
tally is again possibly dissociation via the highly vibrational levels of the
ground state, S0. As discussed above, S0 could be produced by IC from the
S1 state. The 266-nm wavelength photon can also reach the S1-B2 state. As
 Multireference and Spin–Orbit Calculations 11

with the 248-nm excitation, this state cannot dissociate by itself. The PEC of
S1-B2 crosses to the PECs of T5-B1 and S4-B1 states. The photoexcitation
energies required to reach these two crossing points are about 5.0 and
5.25 eV, respectively. The 266-nm wavelength photon is unlikely to reach
either of the two points, even considering an estimated error of 0.3 eV, just
as we discussed in Section 3.1. If the predissociation channels are out of
reach, the only remaining photodissociation channel at 266 nm is again via
the highly vibrational levels of the ground state, S0, produced by the IC
from the S1 state.

3.4. Chlorobenzene, chlorotoluene, and methyl substituent

and rotation effects
Following the studies on the photodissociation of ClBz, a number of inves-
tigations [90–94] have been performed to the photodissociations of o-, m-,
and p-ClT for exploring the methyl substituent effect. The direct effect of the
methyl substituent is to decrease symmetry and increase degree of freedom.
From the theoretical viewpoint, a decrease in symmetry conduces to a
decrease in forbiddenness, and absorption is thus more intense in ClT
than in ClBz. The fluorescence quantum yield of ClBz is very low [95],
while the band origins of o-, m-, and p-ClT had been identified to be
36 863, 36 602, and 36 281 cm1, respectively [96]. Besides, Timbers et al.
[97] suggested that the methyl rotor acts as an accelerating group for
intramolecular vibrational energy redistribution (IVR). The introduction of
the methyl group to ClBz may lead to a different photochemical dynamics.
For instance, the lifetime of excited p-ClT upon excitation at 266 nm have
been determined to be 150 + 4 ps [98], which is shorter than that of ClBz
(600 ps) [99]. Upon excitation at 193 nm, experimental results show that p-ClT
has three dissociation channels [92] similar to those of ClBz as discussed in
Section 3.3 but with different probabilities. As can be seen, the methyl sub-
stituent on ClBz remarkably induces dissociation through triplet states.
Nascent Cl atoms from photolysis of p-ClT have been detected splitting into
two spin-state species, Cl(2P1/2) and Cl(2P3/2). The Cl/Cl ratio at 212.6 nm
photolysis was determined to be of the order of 0.1 by Satyapal et al. [93].
In order to deeply discuss the methyl rotation and substituent effects on
the dissociation dynamics and interpret the experimentally observed spin-
state products as well, the MS-CASPT2 and MS-CASPT2/CASSI-SO PECs
were calculated as described in Section 2 on the o-, m-, and p-ClT. According
to their MS-CASPT2 scanned PECs of o-, m-, and p-ClT along the CCl bond
(see Ref. [35] for details), the five excited states of S1-A0 , S3-A0, T1-A0 , T2-A0 ,
and T4-A0 for o- and m-ClT, and S1-A0, S2-A0 , T1-A0 , T2-A0, and T3-A0 for
p-ClT join asymptotically to the ground state at larger values of the CCl
bond distances. To detect the energy splitting between the two J states of
12 Y.-J. Liu and W.-H. Fang

Cl(2P1/2) and Cl(2P3/2), the PECs of the spin-coupled states were computed
by the MS-CASPT2/CASSI-SO approach along the dissociation coordinates
from 3.45 to 4.0 Å in steps of 0.2 Å. The PECs of the 12 spin-coupled states
were obtained from the splitting of the six spin-free states joining to the
ground state as mentioned above. The 12 spin-coupled states of all the ClTs
split into two groups. The group with lower energy is identified to be
CH3C6H4• þ Cl(2P3/2), and the upper group is assigned to CH3C6H4• þ
Cl(2P1/2). For convenient comparison, a schematic figure, Figure 1.4, was
used here.
Upon photoexcitation at 193 nm (6.42 eV), o-ClT molecules will mainly
populate in the second (,) state S2-A0 (Tv = 6.24 eV). The S2-A0 state is of
the most intensive transition with f of 5.2E-02. As shown in Figure 1.4, S2-A0
is a bound state, but it crosses with S3-A0, a repulsive (n,) state. The
S2-A0 /S3-A0 crossing point has been located near the FC region with ClC
distance of 1.710 Å. The energy gap between this point and the minimum of
the ground state is determined to be 6.24 eV by the CASPT2 calculation,
which is lower than the 193-nm photon energy. This indicates that IC is
easily to take place via the S2-A0 /S3-A0 crossing point and subsequently
leads to a fast dissociation. This Herzberg’s type I predissociation should
contribute to the fastest of the three experimentally observed channels

(π,π∗) S2(o- and m-ClT) or S3(p-ClT)

(π,π∗) S1

(n,σ∗) S3(o- and m-ClT) or S2(p-ClT)

(π,σ∗) T4(o- and m-ClT) or T5(p-ClT)

E Cl(2P1/2)
266 nm

193 nm

Cl(2P3/2)

S0 Fast
Mediate
Slow
IC

R(C–Cl)

Figure 1.4 Schematic profile of the PESs for the ClTs dissociate in 193, and 266 nm,
illustrating the mechanisms of the fast, mediate, and slow fragmentation pathways.
 Multireference and Spin–Orbit Calculations 13

[92,100]. The second (,) state S2-A0 also crosses to the repulsive (,)
T4-A0 state at nearly the same position of the S2-A0 /S3-A0 crossing point,
which was roughly described in Figure 1.4. The CASPT2 calculated energy
gap between S2-A0 /T4-A0 and the minimum of the ground state is about
6.19 eV. Under this condition, the ISC of S2-A0 /T4-A0 is also accessible in
energy at 193-nm photolysis. We assign the second experimentally
observed channel [92,100] to the predissociation via the ISC from the
bound (,) S2-A0 state to the repulsive (,) T4-A0 state. The complex
will ultimately decay with a rate that depends on the coupling between the
two electronic states. The third photodissociation channel is slowest, which
generally takes place via hot molecule mechanism. It has been found experi-
mentally that the primarily excited S2 state of benzene decays fast by IC to
the S1 and S0 states [101]. Likewise, as shown in Figure 1.4, the initially
excited o-ClT molecule in the S2-A0 state can internally convert to the S1-A0
state and subsequently to the S0-A0 state. The dissociation energy of ClC
bond is experimentally determined to be 4.2 eV [92], and the band origin of
the first excited state of o-ClT is 4.57 eV [96]. Therefore, the S0 formed by IC
from the upper (,) state possesses enough energy to overcome the dis-
sociation energy limit.
Upon photoexcitation at 266 nm, o-ClT molecule possessing internal
energy of 4.66 eV will mainly populate in the S1-A0 state. The calculated f
values suggest that the transition to S1-A0 is not as intensive as to S2-A0 . S1-A0
is a bound (,) state, and it cannot dissociate by itself. The PEC of S1-A0
crosses the PECs of S3-A0 and T4-A0 repulsive states. The ClC distance is
determined to be 2.099 and 2.046 Å at the S1-A0 /S3-A0 and S1-A0 /T4-A0
crossing points, respectively. The CASPT2 calculated energies of the cross-
ing points S1-A0 /S3-A0 and S1-A0 /T4-A0 are 5.67 and 5.49 eV higher than the
minimum of the ground state, respectively. This means that o-ClT molecule
is not able to reach these crossing points at 266 nm. Therefore, the most
possible mechanism at 266 nm is the o-ClT molecule dissociation via the hot
molecule mechanism after IC from the origin S1-A0 state, as shown in
Figure 1.4. Experiments observed that the photodissociation following
long-wavelength excitation is slow [94,98].
The diabatic PECs of m- and p-ClT are similar to those of o-ClT, and the
assignments of the observed photodissociation channels are also similar. We
summarized the photodissociation mechanism of o-, m-, and p-ClT in
Figure 1.4. At 193 nm, the photon initially excites to the second (,) singlet
state (S2 for o- and m-ClT, and S3 for p-ClT), and the experimentally
observed fast, mediate, and slow channels were assigned to (i) the fast
dissociation of a repulsive (n,) singlet state (S3 for o- and m-ClT, and S2
for p-ClT) after the IC from the photon initially excited state, (ii) dissociation
of a repulsive (,) triplet (T4 for o- and m-ClT, and T5-A0 for p-ClT) after the
ISC from the photon initially excited state, and (iii) dissociation via vibra-
tionally excited ground state S0, respectively. In the case of the photolysis of
14 Y.-J. Liu and W.-H. Fang

ClTs at 266 nm, the above channel (iii) is the only accessible one. The o-, m-,
and p-ClT molecules dissociate via hot molecule mechanism after the IC
from the originally excited (,) bound S1 state. The MS-CASPT2/CASSI-
SO calculations clearly assigned the experimentally observed spin-coupled
products Cl(2P1/2) and Cl(2P3/2) and roughly indicated that photolysis of
ClTs at 193 and 266 nm mainly generate Cl(2P3/2).
Upon excitation at 193 nm, experimental results by Ichimura et al. [92]
and Lin et al. [100] show that the three channels have different dissociation
probabilities for ClTs and ClBz. Compared with ClBz, the quantum yield of
the mediate channel is much increased while the slow one is decreased for
ClT. This trend is more distinct for p-ClT. This indicates that the mediate
channel is enhanced by the methyl group substituent. The methyl internal
rotation in the S1 states of flurotoluene [97] and o-, m-, and p-methylanisole
[102] has been experimentally investigated. The general conclusion is that
methyl as a rotor can accelerate the IVR rate due to the large increased
density of coupled states by introducing the internal rotation–vibration
interaction. For our case, the methyl group enhances the ISC between the
193-nm photon initially populated bound single state (S2 for o- and m-ClT,
and S3 for p-ClT) and the repulsive triplet state (T4 for o- and m-ClT, and T5
for p-ClT). The methyl of p-ClT is almost a free rotor by the present
calculations and experiment [103]. So, the methyl rotation of p-ClT may
provide higher level density of coupled states and increase the ISC rate.
It may be the reason that the increasing quantum yield of the mediate
channel is most distinct for p-ClT among the three ClTs.

4. PHOTODISSOCIATION PROCESSES OF HALOMETHANE

Small polyhalomethanes are good examples for understanding the

fundamental reaction mechanism of photochemistry upon laser excitation.
High-level calculations can be used on them. We have calculated the
properties of excited states, assigned the photodissociation channels, and
scanned the isomerization process of CH2Cl2 [40], CH2BrI [38], and CH2I2
[41] by CASSCF, CASPT2, and MS-CASPT2//CASSI-SO methods.

4.1. Bromoiodomethane (CH2BrI)

CH2BrI with two different carbon–halogen bonds is an excellent model for
investigating selective bond dissociations upon electronic excitation. Earlier
molecular beam studies in the gas phase have shown that CH2BrI exhibits
two absorption bands, A and B, centered at 266 and 211 nm, respectively
[104,105]. Man et al. subsequently measured some time-resolved resonance
Raman spectra (TRRS) in the A- and B-band absorptions of CH2BrI in
cyclohexane solution [106]. Tarnovsky et al. studied the A-band
Other documents randomly have
different content
produced, Baron Parke said—“Such evidence was admissible
in cases of this kind, because it went to show the general
impression of the habits and feelings of a person. The
prisoner was reputed to be a kind-hearted, benevolent man.
It was admitted that he had been transported for some
offence, the nature of which they had not been told, but it
was said that it was not one to affect his character for
kindness of disposition.” The Judge then read over the
evidence to character, and left it to the jury to decide in
reference to its value to the prisoner in his present position.
On the conclusion of the Judge’s charge, which lasted
from eight in the morning until half-past eleven, the Jury
retired, and in about half an hour returned a verdict of Guilty.
In a few impressive sentences, in which he spoke of the
hypocrisy that had characterised the prisoner’s life in the
assumption of the garb of a virtuous, peaceful, benevolent,
and religious body of persons, the Judge passed on him the
dread sentence of the law, which he suffered on the 28th of
March. Previously to his execution Tawell handed a written
confession to the jail chaplain, that he committed the murder
for fear that his wife should discover his connection with the
deceased, and that the previous attempt was not made with
prussic acid. He never imagined that Sarah Hart had spoken
of him to her neighbours, to whom he believed that he was
personally unknown, and so more likely to escape detection.
At the Easter Quarter Sessions of the County, held
subsequently to the execution of Tawell, an ineffectual
attempt was made by a section of the magistrates to compel
the jail chaplain to deliver to the visiting justices this written
confession, which the chaplain refused to hand over, on the
ground of its having been received under the seal of
confession, and on the promise that it should not be
published. All that was known of it rested on the statement of
the governor of the prison, and the general admission of the
chaplain that it was a full confession of the prisoner’s guilt.
 A difficult legal question arose, after Tawell’s death, with
reference to his Australian land, which the Crown re-granted
to his widow and family, after its forfeiture by his conviction;
whether this re-grant should prevail over the claims of a
previous purchaser, a retired auctioneer, who had houses on
it, who alleged that he had purchased it for a bonâ fide
consideration, under a sufficient power of attorney, executed
before Tawell’s conviction. “The affixing the seal of the colony
to this grant by Sir W. Denison, created a serious difference
between that governor and his chief minister, Mr. Cowper. The
seal was affixed pursuant to the instructions of the Secretary
of the Colonies, who only acted in the matter in accordance
with the opinion of the Attorney and Solicitor-General of
England. A part of the sworn duty of a colonial governor is to
obey the instructions of the Secretary of State for the
Colonies.”[19] The governor, therefore, sent his private
secretary for the great seal of the colony and himself
executed the new deed. On this being done the owners of the
property found the ground cut from under their feet, and it
never came before the law courts, but it is believed that some
compromise was effected with the family of Tawell, and so
the matter ended.

TRIAL OF GEORGE BALL FOR POISONING HIS

MOTHER WITH PRUSSIC ACID.
July, 1860, Home Circuit, Lewes, before Coleridge, Chief Justice of
Common Pleas. Barrow, for the Prosecution. Serjeant Ballantine
for the Defence.

This case, really of misadventure, is reported,

briefly, as showing the carelessness with which
dangerous medicines may, no doubt most
unintentionally, be administered even by professional
men, the culpable ignorance in some of those
chemists who deal in such deadly preparations.
The accused, a medical man, but not in regular
practice, had for some time attended his mother, a
very ailing old lady, and been in the habit of giving
her small doses of prussic acid, as a remedy for
violent attacks of vomiting to which she was subject.
On the 11th of July in consequence, he purchased of
a Mr. Moswell, a chemist in Lewes, a drachm of
Scheele’s prussic acid, equal to 60 “minims,” and
gave her a dose of 4 “minims.” The result was
favourable, and the old lady went for a walk. On her
return, however, she again complained, and the
accused administered another dose of prussic acid,
evidently from its effects, a deadly quantity, as she
hardly got to her bedroom before she became
insensible, and died almost instantaneously. The
accused believed he had given her only seven drops,
the proper quantity to be given. That he gave her
seven drops was not doubted, but that the size of
drops differ under circumstances as much as the
strength of Scheele’s preparation of the acid, will be
seen from the following evidence.
Mr. Scrate, a surgeon at Lewes (who was sent for
by the accused, found the lady dead and the accused
apparently in a very distressed state of mind), said:—
 “I asked what was the matter; and the accused said he
had given her seven drops of prussic acid, and witness replied
he must have given her more.”
Chief Justice.—“Would seven drops be sufficient to cause
death?”
Witness.—“Not according to my experience; it was the
proper quantity to be given. The smallest quantity of prussic
acid on record having caused death was of nine-tenths of a
grain.”
Chief Justice.—“How many ‘minims’ would a ‘drop’
contain?”
Witness.—“That would depend upon how the drops were
obtained from the bottle. If the cork was partly in, the drop
would be larger than if it was carefully poured from the open
neck of the bottle. Some medical men made use of one
method and some of the other, but it was his practice not to
rely on ‘drops,’ but to measure ‘minims.’”
To Mr. Barrow.—“With such a deadly poison as prussic acid
I should say that it was not prudent for any medical man to
rely on ‘drops,’ but to measure ‘minims.’ The proper doses, as
marked on all bottles of Scheele’s strength, to be
administered were one, two, or the largest three ‘minims.’
Scheele’s acid was not uniform in strength: sometimes it
contained four, sometimes five, and sometimes as much as
six per cent.”
Chief Justice.—“Would not that amount to almost the
difference between life and death?”
Witness.—“It would make a very great difference certainly.
Taylor and other eminent medical men have recommended
that Scheele’s prussic acid should not be used, on account of
the very great variation of strength. I myself always use that
of the Pharmacopœia. But notwithstanding what has been
written upon the subject by many eminent men, Scheele’s
acid is generally used in the profession.”
 Chief Justice.—“Supposing the acid to be of the highest
strength you have mentioned, do you consider seven drops
would have been sufficient to cause death?”
Witness.—“I don’t believe they would.”
To Mr. Barrow.—“Six per cent. is an exceptional strength,
but I should think that it would take seventeen minims of that
strength to cause death.”
Chief Justice.—“What do you say is the difference
between a ‘drop’ and a ‘minim’?”
Witness.—“That would depend on the sort of ‘drop.’ The
prisoner afterwards gave me a bottle which contained prussic
acid. He told me he had given his mother four minims, and
2·5 minims remained. I did not test the strength of what
remained, but had no doubt the deceased died from the
effects of prussic acid.”
To Serjeant Ballantine.—“There was a broken cork in the
bottle when the accused gave it to me. In his opinion
‘seventeen minims’ was the smallest dose that would destroy
life. It was very easy to destroy life when dropping the liquid
from a bottle. When accused told him he had given seven
drops, he understood that he had given three and a half
minims. He had never heard of any instance in which the
strength of Scheele’s acid had exceeded six per cent.”
Mr. C. H. Moswell (chemist in Lewes).—“On the 11th of
July accused came to his shop and asked for some prussic
acid. Gave him a drachm, which would contain sixty minims.
Did not measure it, but gave what he considered a quarter of
the bottle.”
Cross-examined by Serjeant Ballantine.—“As you say you
really did not measure it, can you tell us how much prussic
acid you really did give?”
Witness.—“I cannot say to a drop. I am sure he had fifty
drops. I consider a ‘drop’ and a ‘minim’ synonymous. I gave
him about the quantity, but when prussic acid is dispensed by
 a medical man, he is, of course, careful as to the quantity he
uses.”
Chief Justice.—“We have been told that a ‘drop’ contains
two ‘minims,’ and this witness says he looks upon them as
synonymous.”
Serjeant Ballantine.—“If you were told to give a patient so
many ‘minims,’ should you give him so many ‘drops’?”
Witness.—“Certainly not.”
Serjeant Ballantine.—“Can you tell us the strength of the
prussic acid you sold?”
Witness.—“I don’t know what the strength was—I should
suppose about four per cent.”

Case for the prosecution closed.

The Chief Justice called the attention of the Jury
to the evidence and observed, that the fact of the
cork being broken in the bottle and defective was
certainly an important matter for their consideration,
as it admitted the possibility that the prussic acid
might have escaped from the bottle accidentally, and
then there was an absence of evidence that an
excessive dose had been administered by the
accused.
The Jury almost immediately returned a verdict of
“Not Guilty.”
If the estimate of the witness Scrate is taken for
the difference between a drop and a minim, and the
second witness, Moswell, is correct in saying that he
gave the accused at least 50 drops, equal to 25
minims, as only 2·5 minims were left in the bottle,
equal to 4¼ drops; in the two doses the accused
must have administered more than 45 drops, equal
to 22½ minims. If the cork was not broken in the
bottle when the first dose was administered, the
probability is that the dose then given did not exceed
seven drops of the size that would make them equal
to 3½ minims, thus leaving 19 minims for the second
dose. It is to be regretted that the strength of the
prussic acid was not tested.

NOTE ON TAWELL’S CASE.

In a case of the poisoning at Egglesham, near

Glasgow, by prussic acid, of a young woman, of the
name of Agnes Montgomery, by Peter Walker, a tailor,
the symptoms were thus described by one of the
witnesses, as well as the effect of prussic acid on
herself:—
“After we learnt that the moaning came from Aggie’s room,
we came up, got Clarkson’s key, and went in. (As in Tawell’s
case, the prisoner had left the girl’s room only a few minutes
before.) Aggie was sitting on a chair (in which it was probable
from other evidence that she had been placed by her
murderer), with her head leaning on the table. The body was
quite still. There was a little froth coming out of the wicks of
 her mouth. It was a little coloured with blood; and we
afterwards found she had bit her tongue and her lips. She
threw back at different times, as if in distress. Her right hand
was very firmly closed. I loosed the boot of the left foot, and
found it was swelled and quite stiff. About ten minutes after
that was another groan: the breathing was slow, and with
great oppression. She sighed six times before she died. Her
skin was getting quite cold after we got her. I thought there
was a little sweat on her face. We got hot water to bathe her
arms. The eyes were large and staring. She died about three
quarters of an hour after we got her. When we went into her
room, I found a sickening smell. I felt in my nostrils a kind of
nipping, and my throat was dry. I felt it off Aggie the moment
I came forward. I know the smell of almonds, but can’t say it
was exactly like that. On the 5th of November I saw the
superintendent of police, and others, and saw something (it
was prussic acid) put into beer. I smelt the beer; and after
some of it was poured on the floor, I recognised it as the
same smell. It affected me in the same way as before in the
nostrils and throat.”—Evidence of Mrs. M’Donald.

In this case, on a post-mortem examination of

the exhumed body, the presence of prussic acid was
clearly detected; and it was proved on the trial that
the prisoner had employed a carrier to get some
prussic acid for him, and that the bottle containing it
had been given to him on the day of the murder;
and the fragments of a glass phial were subsequently
discovered, with the key of the girl’s room, at the
root of a tree, at which the prisoner had been seen
stopping, as he returned from going for a doctor. In
this case the poison had been most probably given in
beer, as in Tawell’s, a tumbler in which beer had
been being found on the girl’s table.
The fellow, two months afterwards, tried to
poison a Mr. Mason and his wife, with whom he had
gone to lodge in Glasgow, with prussic acid, but
happily failed in his attempt.
He confessed his guilt; and at first gave as his
motive his desire to possess himself of the girl’s
money, but subsequently said he could not tell what
possessed him to do it. “Following so closely on the
case of Madeleine Smith, the probability is that her
case had had on him the same effect as Palmer’s on
Dove—exciting a morbid desire to tamper with
deadly drugs, and that the death of his victim, and
the danger of the others, was as much due to this
feeling as the desire for plunder.” He was discovered
to have been transported for robbery, and to have
been guilty of other crimes. He now confessed that
he had murdered a lad, by pushing him into a quarry
hole. He was executed at Paisley, Jan. 14, 1858.—
Annual Register for 1858.
 CHAPTER III.

CHEMICAL NOTES.

Note I.—Hydrocyanic or Prussic Acid.

Nature of—Strength of different preparations of, English and foreign

—Where found—Tests, preliminary: (1) Odour—(2) Silver—(3)
Prussian blue—(4) Sulphur—(5) Guaiacum—(6) Uranium—(7)
Picric acid—(8) Cupric sulphate—(9) Cobalt chloride—(10)
Mercuric oxide—(11) Peroxide of hydrogen—(12) Mercurous
nitrate. Test apparatus—Salts of hydrocyanic acid: (1) Potassium
cyanide—(2) Mercuric cyanide—(3) Cyanides of the heavy metals
—(4) Double cyanides—(5) Sulphocyanides—Oil of bitter almonds
—Antidotes—Fatal dose—Symptoms—Post-mortem appearances—
Drops and minims—Period after death at which hydrocyanic acid
can be discovered—Formic acid to be tested for—Processes.

Synonyms.—Cyanhydric or prussic acid, Hydric

cyanide, Hydrogen cyanide, Acidum borussicum,
Blausaüre, Berlinerblausaüre.
Formula HCN, i.e., a compound of single atoms,
of hydrogen, carbon, and nitrogen, in the proportions
by weight of 1 + 12 + 14 = 27. In its pure state
(anhydrous, or free from water), it is a feebly acid,
colourless, mobile liquid, inflammable and very
volatile. Boiling point 24·5° C. Much lighter than
water: sp. gr. ·7058. It has a characteristic
overpowering and oppressive odour, resembling
peach-blossom or laurel-water. But the anhydrous
acid, from its volatility and dangerous character is
rarely seen or made. In commerce it is always found
as a dilute aqueous solution, the varying strengths in
real HCN being:—
Per cent. HCN.
Pharmacopœia, British, Swiss, America,
Borussica, London, Norway, 2
Schräders 1·5
Pharmac. Saxony 1·9
” Austria, Baden, Batavia 2·5
” Edinburgh, Dublin 3·3
Vauquelin’s acid 3·3 to 3·5
Pharmac. Bavaria 4
Scheele’s acid 4 to 5
(rarely 6)
Duflos’s acid 9
French Pharmacopœia 10 to 10·5
Riner’s and Pfaff’s acids 10
 Hessian Pharmacopœia 18 to 20
Koller’s 25
Robiquet’s 50

In this country, only Scheele’s, and the British

Pharmacopœia (2 per cent.) acid, are usually met
with.
These numbers, however, must be regarded
merely as rough approximations for two reasons;
first, on account of the extreme volatility of the acid
—if loosely stoppered, or frequently opened, it
rapidly loses strength—second, both the anhydrous
acid and its aqueous solution are decomposed by
light, with formation of a brown matter. This change
is supposed to be retarded by a trace of mineral acid,
hence a little hydrochloric or sulphuric acid is
frequently added to the commercial solution with this
object. But the acid may even be stronger than
supposed, as the methods of preparation are
somewhat various, and the one adopted may have
been carelessly carried out. Scheele’s acid is said to
be the most popular among medical men; samples of
it obtained from different large firms and examined
by the author showed very irregular strengths, the
lowest being 2, and the highest 8 per cent. The latter
was purchased at the shop of a chemist who said he
had made it himself, and could guarantee it was of
full strength. He had evidently made allowance for
deterioration. Woodman and Tidy found 16 samples
sold in one neighbourhood as B.P. acid to contain 0·6
to 3·2 per cent. of HCN; others have found 0·25 per
cent. not infrequent. It follows that if, in a poison
case, a bottle has been found of a hydrocyanic
preparation of a definite name, or even with a
certain strength or dose marked on it, it will not be
safe to trust to such figures without actually
determining the amount. In Ball’s trial (Lewes, 1860),
the judge asked whether this variation in strength
would not make the difference between a medicinal
and a poisonous dose? It would not, as the
maximum medicinal dose, 4 grains, of even the
abnormally strong (8 per cent.) Scheele’s acid
mentioned above, would only contain 0·32 grain of
anhydrous HCN, and it requires at least half a grain
to cause death, while about 1 grain is the usual fatal
quantity. And a medical man would not even give the
maximum medicinal dose as a beginning, and
without precaution.

ACIDUM HYDROCYANICUM DILUTUM,

PHARMACOPŒIA BRITANNICA.

We shall use the abbreviation “B. P. 2 per cent.”

for this acid, which has the characteristic odour, a sp.
gr. of ·997, and a taste “at first bland and sweet,
ultimately pungent and acrid” (Thomson), “hot and
bitter” (Taylor), “cooling, with pungent bitter
aftertaste” (Watts). If pure, it only slightly and
transiently reddens litmus; if other acids have been
added to keep it, it may have a stronger reddening
effect. Also, if pure, it leaves no residue on platinum,
and gives no precipitate with barium chloride, but
with silver nitrate it gives an immediate white curdy
precipitate of silver cyanide, not blackening in
daylight as the chloride does, soluble in ammonia,
insoluble in dilute, but soluble in hot concentrated
nitric acid. It dissolves mercuric oxide, giving a
mercuric cyanide which may be obtained in white
crystals on evaporation. The vapour is said to be
more deadly than the fluid acid. The weaker the acid,
the more permanent it is. Glycerine increases its
stability (J. Williams); this might be useful if
suspected substances had to be kept a long time.
Occurrence.—Hydrocyanic acid itself has never
been found as a natural constituent of the body,
although a compound of cyanogen occurs in the
saliva (see Sulphocyanides). Hydrocyanic acid is not
formed during putrefaction, nor by heating organic
substances with chemical reagents at temperatures
up to 212° F., as in testing for poisons. The only way
in which it may be generated from animal matter is
by heating with alkalies to a red heat;[20] this cannot,
of course, happen in the ordinary process of testing
for prussic acid, though it must be remembered that
cyanide might thus be formed in an ash (by
burning), without having been present in the original
substance.
It is rather frequent, however, in the vegetable
kingdom, and consequently in a poisoning case the
defence often sets up the theory that it has been
ingested in the food (Tawell’s Trial, &c.). It is
necessary, therefore, to examine in what kind of
food, and to what amount, it may be taken.
Its principal source is the seeds, leaves, and
flowers, and sometimes the bark, of most of the
species of the sub-orders Amygdaleæ and Pomeæ of
the natural order Rosaceæ. It does not occur in them
ready-formed. There is a substance called
Amygdalin, a white bitterish crystalline body, which
may be extracted by alcohol from these plants.
Amygdalin when dissolved by itself in water does not
produce HCN, and is probably harmless, but there
exists by its side in the plant a species of ferment
called Emulsin or Synaptase, which has the power,
when macerated in water with amygdalin, of
breaking up the latter into glucose (so-called grape-
sugar), benzoyl hydride (oil of bitter almonds), and
hydrocyanic acid. In the plant the amygdalin
apparently exists in cells apart from the emulsin, but
by crushing in water, or masticating in the mouth,
the change is very rapidly effected. By long soaking
the same result may happen, as in cherry brandy;
here the diluted spirit dissolves the amygdalin, and
the emulsin then may act. But if, in the stomach, the
apple-pips or cherry-stones should be found whole, it
is almost impossible that the amygdalin should be
decomposed, protected as it is by its horny or stony
envelope. Stones and pips, in fact, pass through the
body intact, and are found in the fæces.
Yet as amygdalin and its decomposition may be
much mentioned by the defence, the following
account may be useful.
100 parts of amygdalin yield 6 parts HCN.
It has been found in the species of Rosaceæ
given below, generally in fruit, flowers, leaves,
sometimes bark, rarely root.
Pyrus malus (apple pips), domesticus (pear).
Prunus spinosa (sloe), avium (bird cherry), padus
(wild service), Virginiana or serotina (wild black
cherry), capricida, insititia (bullace), domestica
(plum, damson, &c.).
Amygdalus communis (almond), Persica (peach),
lævis (nectarine).
Armeniaca vulgaris (apricot).
 Cerasus communis (cherry), acida, laurocerasus
(cherry-laurel), Lusitanica (Portugal laurel).
Cydonia vulgaris (quince).
Sorbus aucuparia (mountain ash), torminalis,
hybrida.
Cratægus oxyacantha (hawthorn, young
branches).
Spiræa aruncus, sorbifolia, japonica (not in
herbaceous species).
Hydrocyanic acid, ready formed, has been found
in the roots of the bitter and sweet cassava
(Jatropha manihot).
If the poisonous dose of the B. P. (2 per cent.)
acid be at least 30 minims (Royle’s Mat. Med., Dr.
Harley, 6th ed.) the following table shows the
amount of some of the above which is needed.

Equal Amount
Percentage to required
Substance. of HCN for Observer.
amygdalin. per poisonous
cent. dose.
Cherry kernels 3 0·18 333 grains Gieseler.
Pips of sweet C.G.
0·45 0·027 2222 ”
apples Stewart.
Pips of bitter
0·85 0·051 1176 ” ”
apples
Wild service 1·5 0·08 750 ” Hermann
 kernels
Flowers, fruit,
1·0 0·06 1000 ” Riegel.
and bark of do.
Bitter almond
4·25 0·25 240 ” Allen.
pulp
Sweet Cassava 0·017 3500 ” Francis.
Bitter do. 0·027 2222 ” ”

Sweet almonds contain emulsin, but no

amygdalin, hence give no HCN (see Tawell’s Trial, p.
40).
According to my own experiments, 837 sweet
apples (apples weighing 135 pounds, pips about 5
oz.), would be required for a poisonous dose of HCN;
whereas 130 bitter apples, weighing 18 pounds, and
the pips about 2½ oz., would suffice. The pips of
bitter apples are bigger, more numerous, and weigh
about three times as much as those of sweet apples.
Among substances containing much more HCN,
and actually poisonous on that account, are:—
HCN.
Crude bitter almond oil 8 to 15 per cent.
Bitter almond water ¼ to 1 ”
Cherry laurel oil 2 to 3 ”
” ” water[21] ¼ to ¾ ”
Cluster cherry oil 9 to 10 ”
 (Allen, Comm. Org. Anal.) It is obvious that of
fruits an impossibly large quantity must be eaten to
produce any considerable amount of HCN. In Tawell’s
trial, Mr. Cooper, the analyst, deposed that the seeds
from 15 apples gave him an exceedingly small
quantity of Prussian blue. Whereas, Henry Thomas, a
druggist’s assistant, stated that “15 small apples
gave 2¼ grains of silver cyanide” [equal to 0·46, or
nearly ½ a grain, of anhydrous HCN, corresponding
to 25 minims of B. P. acid, nearly a poisonous dose!]
“This was done under the direction of a lecturer at
the London Hospital.” A fair sample of the erroneous
and bewildering evidence that is frequently offered in
courts of justice.
Mr. Cooper also stated “there is a great difference
between bitter and sweet apples; the bitter contain a
great deal of prussic acid, the sweet, I believe, none
at all!” This statement is misleading; no apples
contain prussic acid, but all that I have met with will
yield it by maceration, as all contain amygdalin. The
highest class of eating apples, such as Newtown
pippins, Ribstones, and Blenheims, contain only a
minute trace. These have very few pips, 3 to 5 to
each apple, while the bitter varieties, such as
“winesours,” have 9 to 13 pips.
In the arts, cyanides are used in photography,
dyeing, cleaning lace and metals, electro-plating,
removing silver stains, &c. Their solutions may cause
accidental poisoning, either by the fumes or by
absorption through the skin, especially if the latter is
abraded.
Hydrocyanic acid is also formed (1) in the
preparation of nitrous ether (sweet spirit of nitre),
(2) by distilling albumen, fibrin, casein, or gelatin,
with sulphuric acid and bichromate of potash, or
manganese peroxide, (3) by the dry distillation of
albuminous bodies. It is hardly necessary to say that
these formations could not occur in the ordinary
methods of testing.
Tests: Preliminary.—It cannot be too strongly
insisted that all operations for the detection of HCN
should be carried out as soon after death as
possible, on account of the loss from volatility, or
from secondary changes. (See Sulphocyanides.)
Allen asserts (Commercial Organic Analysis,
1879), that detection in the body is rarely possible
more than twenty-four hours after death; but Taylor
(Med. Juris., 1873, p. 368) has found it in the
stomach twelve days after, saying, however, that
“after the stomach had been exposed a few days
longer, all had disappeared.” In a dog’s stomach he
found it, after twenty-four hours’ exposure, and
washing with water. In a human stomach, success
was achieved seven days after death, where no
odour was perceptible; in another case, after twenty-
two days in the stomach, and after two months in
the spleen. It may be found in the stomach, and not
in the tissues; but in most cases it is easily detected,
soon after death, in the blood, organs, &c. The
vapour of HCN will traverse paper, wet or dry
bladder, &c., in a few minutes (Taylor), and few
stoppers are close enough to retain it. Hence care
should be taken to shut up the suspected matters at
once in glass bottles accurately stoppered; bad
stoppers are worse than corks.
The stomach should be first examined entire, to
ascertain odour, &c., noticing whether alkaline or
acid, then cut in pieces, under distilled water
sufficient to cover it, the whole measured, and one-
half (acidulated with tartaric acid, if alkaline), placed
in a capacious retort, and distilled in a bath of water
saturated with salt to raise the boiling point. The
condenser should be well supplied with cold water,
the receiver attached airtight, with a mercury valve
(a narrow glass U-tube, containing mercury), to
prevent undue pressure. A little distilled water, about
½ oz., should be placed in the receiver. The
distillation should be continued till one-third to one-
half of the original liquid has passed over. The tests
may then be applied to the distillate.
 Allen recommends us to distil with water alone
about one-half. If there is no result on testing the
distillate, continue with addition of tartaric acid.
Finally, add a considerable excess of moderately
dilute sulphuric and hydrochloric acid, and carry the
distillation nearly to dryness. In the last stage
sulpho-, ferro-and ferricyanides and mercuric cyanide
are decomposed, and give HCN. The original should
be tested for ferrocyanide, &c. This seems a process
calculated to give the clearest idea of the form in
which the HCN is present, but is open to the
objection that it is protracted, and may hence cause
loss.
Sokoloff. (Chem. Centr., 1876, 603) advises a
much more heroic treatment. “Strongly acidify with
sulphuric acid, and distil over a water bath for two or
three days, replenishing the water as evaporated.
The longer the distillation, the more accurate the
result.” He adds, that the muscles contain the greater
part of the HCN. He quotes figures in support of his
results, but I have not found such prolongation
necessary; and we must remember that HCN is
decomposed by heating with moderately strong
mineral acids.
The following modification, proposed by the
author, may be advantageous, as diminishing the risk
of loss, and also effecting concentration:—Prepare
exactly equivalent solutions of silver nitrate, and
hydrochloric acid: the silver solution may contain 17
grammes of silver nitrate, the hydrochloric solution
3·65 grammes of hydric chloride, per litre. Place in
the receiver 100 cubic centimetres of the silver
solution (= 1·70 gramme silver nitrate) before
distillation. This is allowing large excess, to provide
for exceptional quantities of HCN. If any quantity of
HCN be present, the liquid in the receiver will
become milky; if it does not, there cannot be more
than a minute trace. Transfer the distillate and
washings to a retort, provided with a thistle-funnel,
and boil down to one-third of its bulk; then add,
through the funnel, 100 cubic centimetres of the
hydric chloride solution, which will precipitate all the
silver as chloride, and liberate the HCN. Distill with
the same precautions as before: the first 25 cubic
centimetres will contain probably all the HCN. If
doubted, a further quantity may be collected and
tested. The 25 cubic centimetres of distillate may
now be subjected to the following tests, taking care
that each portion is measured before being
examined, in order that the idea of the quantity
present may be definite. For instance, in the Prussian
blue, and sulphocyanide tests, the resulting colour
may be imitated by standard solutions: in the silver
test, a standard silver solution should also be used,
and thus a triply-confirmed knowledge of the
quantity present may be attained; and little bottles,
containing the results, should be preserved, to show
in the courts of justice.
I. Odour.—All tests involving odour are affected
seriously by the remarkable differences between
different people as to their sense of smell. We hear
much of “colour-blindness;” but the analogous
olfactory defect has almost escaped remark. Yet
“smell-blindness,” as I have formerly christened it, or
“anozism,” if a Greek word be required, is
exceedingly common, and chemists and medical men
are frequently afflicted with it. I have known an
artist, who could not smell strong ammonia, yet
delighted in the odour of new paint, which he
compared to roses. Many laboratory students can
neither smell acetic acid, arseniuretted hydrogen, nor
cyanogen. An assistant was so fond of sulphuretted
hydrogen, that he was once found insensible beside
the apparatus, having narcotized himself with the
gas (he recovered); and many more such
eccentricities. In the case of prussic acid these
diversities are enormous. Some are so sensitive, that
the least trace in a room becomes rapidly
unbearable, causing headache and nausea; others
are like photographers, and can work in a heavily-
cyanogened atmosphere. Such idiosyncrasies
become of great importance in evidence; for
example:—
In Tawell’s trial, Mr. Champneys, surgeon,
testified as follows: “Have no experience in detecting
odour of prussic acid in a human subject. Should
think it may be taken without detection. Should
expect it in the mouth and breath, but there may be
exceptions. There was no odour in her [the
deceased’s] breath; but, on opening the body, I was
positive I smelt prussic acid. The other two surgeons
could not smell it.” Afterwards, when the contents of
the stomach were transferred to a jar, neither the
three surgeons, nor Mr. Cooper, the analyst, could
perceive the least odour of prussic acid, even when
the contents were boiled. Nor was it smelt in the
blood. Mr. Cooper subsequently stated: “I have no
doubt that prussic acid may exist without being
smelt: absence of smell may arise from dilution, or
from its being covered by the smell of other
substances. When I smell it, it affects spasmodically
the back of the throat. Sometimes it has produced a
spasmodic constriction about the throat without my
smelling it.” Here was a well-marked case of
intermittent smell-blindness.
There were also several questions as to whether
prussic acid might have existed in the form of an
inodorous salt. Mr. Champneys further stated that he
put ½ drachm of prussic acid into a tumbler filled
with Guinness’s porter, and the smell was scarcely
perceptible. Mr. Norblad, surgeon, deposed that he
mixed 12 grains of prussic acid with a pint of porter,
but could not then smell it. “Some of the porter
dropped on the table, and I did then smell it.” In the
same trial, Henry Thomas, druggist’s assistant, mixed
30 drops of B.P. prussic acid with 11 oz. of porter,
and found the odour of the acid slightly perceptible;
yet, when he was pouring Scheele’s acid from a
bottle, three women had to leave the room to avoid
suffocation!
In a case of suicide by cyanide of potassium
(Chem. News, 1861, p. 261), the smell of prussic
acid was not perceived by the surgeon, either
immediately after death or at the post-mortem
examination, nor by the analyst until the contents
had been distilled with dilute sulphuric acid.
To help in elucidating this matter I have made
some experiments as to the detection of the odour of
prussic acid. An acid of 2 per cent. strength (B.P.)
was used.
1. From a bottle of Guinness’s stout, freshly
opened, 3 samples of 1 fluid oz. each were
measured. To the first 1 drop of the acid was added,
to the second 2 drops, the third being left
untouched. This was done out of my sight in another
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