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This work presents a detailed account of one of the most mysterious problems in science - whether ordinary magnetic fields can exert an appreciable influence on chemical and biochemical reactions. The first aim of the book is to introduce this research, through theoretical and dynamic spin chemistry, to graduate students and researchers, by means of detailed theoretical and experimental descriptions. The second aim is to review typical recent investigations, which will stimulate new interest and applications in the 21st century. Because dynamic spin chemistry is based on established science, it is expected to provide a guide for all situations in which radicals, radical pairs, and higher spin species occur, including the effects of environmental electromagnetic fields on the human body.
E-Book Content
Introduction to Dynamic Spin Chemistry Magnetic Field Effects on Chemical and Biochemical Reactions
WORLD SCIENTIFIC LECTURE AND COURSE NOTES IN CHEMISTRY Editor-in-charge: S. H. Lin
VOl. 1:
Monte Carlo Methods in Ab lnitio Quantum Chemistry B. L. Hammond, W. A. Lester, Jr. & P. J. Reynolds
VOl. 2:
Quantum chemistry Aided Design of Organic Polymers: An Introduction to the Quantum Chemistry of Polymers and Its Applications J. -M. Andre, J. Delhalle & J. -L. Bredas
VOl. 4:
The Physical Chemistry of Biopolymer Solutions: Application of Physical Techniques to the Study of Proteins and Nuclei Acids R. F. Steiner& L. Garone
VOl. 5:
Theoretical HeterogeneousCatalysis R. A. van Santen
Vol. 6:
Density Matrix Method and Femtosecond Processes S. H. Lin, R. Alden, R. Islampour, H. Ma & A. A. Villaeys
VOl. 7:
Spectroscopy and Dynamics of Orientationally Structured Adsorbates V. M. Rozenbaum & S. H. Lin
voi. a:
Introduction to Dynamic Spin Chemistry: Magnetic Field Effects on Chemical and Biochemical Reactions H. Hayashi
World Scientific Lecture and Course Notes in Chemistry - Vol. 8
Introduction to Dynamic Spin Chemistry Magnetic Field Effects on Chemical and Biochemical Reactions
Hisaharu Hayashi RII = ml)I,m 3 ,
PII,m p = J I ( I + 1) - m, (m, + 1) 1 , m+l>,
(1- 4 0 ~ )
r(I,ml>= J ~ ( ~ + l ) - m , ( m , - l ) ~ , m ~ l > .
(1-40d)
Table 1-1 shows the g N values of typical nuclei together with their I values and natural abundance. It is worth while to remark from this table that many nuclei such as I2C and I6C have no spin ( I = 0). The isotopes with and without spin, therefore, are called “magnetic and non-magnetic isotopes”, respectively. Even now, it is very difficult to explain theoretically the observed I and g N values. This is one of the frontiers of modem physics.
Solutions to the Problems 1-1. From Eq. (1-24), b ] = [g [Sl= [A m21. 1-2. [I] = [ r m,v] = [m] [kg] [ d s ] = [kg m2 s-*] [s] = [J s]. 1-3.
,uB
=-
eA
2m.
=
1 . 6 0 2 1 8 ~ 1 0 - ’ ~*C1 . 0 5 4 5 7 ~ 1 0 Js - ~ ~= 9.2740x10-24 Jcs/kg. 2 9.10939 x kg
Using [C] = [As], [JCsikg] = [JAs’ikg]. Using [A] = [kg/s2Tl from Eq. (1-6b), [JAs2/kgl = [Jl [kg/s2Tl [s2/kgl = [J T-’]. Thus, ,UB = 9 . 2 7 4 ~ 1 0J-T-I. ~~
1-4.
If‘m, of the above p~ calculation is replaced by mp (= 1.67262 X lO-”kg), the pNvalue can be obtained to be 5 . 0 5 0 7 9 ~ 1 0 ~ ~T-I. ’J
7
Table 1-1. Nuclear spin properties. Isotope
Natural
Spin
(4
(gN)
99.985 0.015
112 1
5.58570 0.85744
98.90 1.10
0
-
Abundance (%)
'H *H I2C
l3C
__
g-factor
112 1 112 ______
1.40482 0.40376 4.56638
I4N 'N
99.634 0.366
l6O
99.762 0.038 0.20