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I begato recognize the importance of studying Ramaintensity as I encountered surface enhanced Ramascattering (SERS) back to 1980's. SERS is a surface phemethat as a molecule, especially the nitrogecontaining molecule, is adsorbed othe metal surface, iparticular the silver electrode, its Ramacross sectiocabe amplified up to a milliofold. More interesting is that the Ramamode intensities of the adsorbed molecule are applied voltage dependent. The questiotheimy mind was: what is the physical picture behind this Ramaintensity variation? Iorder to solve this issue, we therefore established aalgorithm to retrieve the so-called bond polarizabilities from the Ramamode intensities ia systematic way. This leads to a nice harvest, showing that this approach is aadequate direction, albeit the algorithm is semi-classical. This attracted much of my intentioi1980's.
During that time, I also thought of the fields of Ramaoptical activity (ROA) and phase transition. These two fields involve Ramaintensity variatioas well. Iparticular, ROA shows that for a chiral molecule under right and left circularly polarized light scatterings, its respective Ramaintensities are different, though the difference is very small, only l0-3to 10-4 of its Ramaintensity. The differential Ramaintensity is called the ROA spectrum.
Our work othe phase transitions of the systems with very low degree of doping (ranging from 10-2 to 10-4) seemed to be a success. The rate of mode intensity variatioas a functioof temperature shows a power law. The exponent of the power law is very sensitive to the doping degree and bears the informatioof the doping effects.
Among the doping effects, the self-similarity by doping which is characterized by the scaling factor, with d the separatiobetweethe doping ions and M their mass is most impressive.
However, our work oROA turned out to be a maze, but t a loss. I hence was acquainted with the idea of ROA and proposed a classical formula for predicting the ROA mode signatures. Though with this formula, the predictiowas t so successful due to the reasothat, at that time, we did t have a clear picture concerning the Ramaexcited virtual state from the retrieved bond polarizabilities.
A clear picture of the Ramaexcited virtual state sparked us i2006 whewe ticed that the bond polarizabilities retrieved from Ramamode intensities were definitely ivariatiowith the bond electronic densities ithe ground state. This hints that bond polarizabilities bear the informatioof the excited/disturbed charges during the Ramaprocess, i. e., the electronic structure of the Ramavirtual state! With this breakthrough, we immediately came into the detailed study othe Ramavirtual state and extended the bond polarizability algorithm to retrieve the differential bond polarizabilities from ROA mode intensities. All these offered us vivid pictures of the Ramaand ROA processes. Though they are classical pictures, just because they are classical, they caprovide prehensive pictures of the Ramavirtual state and the phemena iROA, which were t kwor neglected before. Furthermore, our classical formula for ROA which was developed i1998, turns out to be a success after its re-interpretatioby the bond polarizability. Ather byproduct of this work is that we showed, probably for the first time to the best of our kwledge, that there are about 20% electrons ia molecule that are involved ithe Ramaprocess. The 14 years' waiting (from 1998 to 2012) is really worthwhile to me!
During that time, I also thought of the fields of Ramaoptical activity (ROA) and phase transition. These two fields involve Ramaintensity variatioas well. Iparticular, ROA shows that for a chiral molecule under right and left circularly polarized light scatterings, its respective Ramaintensities are different, though the difference is very small, only l0-3to 10-4 of its Ramaintensity. The differential Ramaintensity is called the ROA spectrum.
Our work othe phase transitions of the systems with very low degree of doping (ranging from 10-2 to 10-4) seemed to be a success. The rate of mode intensity variatioas a functioof temperature shows a power law. The exponent of the power law is very sensitive to the doping degree and bears the informatioof the doping effects.
Among the doping effects, the self-similarity by doping which is characterized by the scaling factor, with d the separatiobetweethe doping ions and M their mass is most impressive.
However, our work oROA turned out to be a maze, but t a loss. I hence was acquainted with the idea of ROA and proposed a classical formula for predicting the ROA mode signatures. Though with this formula, the predictiowas t so successful due to the reasothat, at that time, we did t have a clear picture concerning the Ramaexcited virtual state from the retrieved bond polarizabilities.
A clear picture of the Ramaexcited virtual state sparked us i2006 whewe ticed that the bond polarizabilities retrieved from Ramamode intensities were definitely ivariatiowith the bond electronic densities ithe ground state. This hints that bond polarizabilities bear the informatioof the excited/disturbed charges during the Ramaprocess, i. e., the electronic structure of the Ramavirtual state! With this breakthrough, we immediately came into the detailed study othe Ramavirtual state and extended the bond polarizability algorithm to retrieve the differential bond polarizabilities from ROA mode intensities. All these offered us vivid pictures of the Ramaand ROA processes. Though they are classical pictures, just because they are classical, they caprovide prehensive pictures of the Ramavirtual state and the phemena iROA, which were t kwor neglected before. Furthermore, our classical formula for ROA which was developed i1998, turns out to be a success after its re-interpretatioby the bond polarizability. Ather byproduct of this work is that we showed, probably for the first time to the best of our kwledge, that there are about 20% electrons ia molecule that are involved ithe Ramaprocess. The 14 years' waiting (from 1998 to 2012) is really worthwhile to me!
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目次
??Preface
Chapter 1 Ramaeffect
1.1 Basics: the Ramavirtual state
1.2 The classical treatment
1.3 The quantal treatment
1.4 Theory of bond polarizability by Wolkenstein
References
Chapter 2 Normal mode vibration
2.1 Born-Oppenheimer approximation
2.2 Normal mode
2.3 Normalcoordinates
2.4 Generalized coordinates and rmal mode analysis
2.5 Some useful relations among different coordinates
References
Chapter 3 The elucidatioof bond polarizabilities
3.1 Ramaintensity ithe temporal domain
3.2 The elucidatioof bond polarizabilities
3.3 Thephaseproblem
3.4 More othe coordinate choices
3.5 Theintensity measurement
3.6 The parisoto the bond electronic density
References
Chapter 4 The Ramavirtual states
4.1 The case of 2-amipyridine
4.2 More with the case of 3-amipyridine
4.3 The case of ethylene thiourea
4.4 The case of ethylene thiourea adsorbed othe silver electrode
References
Chapter 5 More applications
5.1 The case of methylviologeand its adsorptioothe silver electrode
5.2 The case of pyridine and its adsorptioothe silver electrode
5.3 The case of piperidine and its adsorptioothe silver electrode
5.4 The case of pyridazine and its adsorptioothe silver electrode
References
Chapter 6 The extensioto Ramaoptical activity
6.1 Ramapticalactivity
6.2 The differential bond polarizability
6.3 The case of (+)-(R)-methyloxirane
6.4 The case of L-alanine
6.5 The case of (S)-phenylethylamine
6.6 The case of trans-2, 3-epoxybutane
References
Chapter 7 More applications oROA
7.1 The case of (S)-2-ami-l-propa
7.2 The case of (S)-l-ami-2-propa
7.3 The case of (2R, 3R)-(-)-2, 3-Butanediol
References
Chapter 8 Intra-molecular enantiomerism
8.1 Background
8.2 The case of (R)-(+)-Limonene
8.3 The case of (S)-(-I-)-2, 2-dimethyl-l, 3-dioxolane-4-metha
8.4 More cases for intramolecular enantiomerism
Chapter 9 A unified classical theory for ROA and VCD
9.1 Background
9.2 The classical algorithm
Appendix A
Appendix B
Chapter 1 Ramaeffect
1.1 Basics: the Ramavirtual state
1.2 The classical treatment
1.3 The quantal treatment
1.4 Theory of bond polarizability by Wolkenstein
References
Chapter 2 Normal mode vibration
2.1 Born-Oppenheimer approximation
2.2 Normal mode
2.3 Normalcoordinates
2.4 Generalized coordinates and rmal mode analysis
2.5 Some useful relations among different coordinates
References
Chapter 3 The elucidatioof bond polarizabilities
3.1 Ramaintensity ithe temporal domain
3.2 The elucidatioof bond polarizabilities
3.3 Thephaseproblem
3.4 More othe coordinate choices
3.5 Theintensity measurement
3.6 The parisoto the bond electronic density
References
Chapter 4 The Ramavirtual states
4.1 The case of 2-amipyridine
4.2 More with the case of 3-amipyridine
4.3 The case of ethylene thiourea
4.4 The case of ethylene thiourea adsorbed othe silver electrode
References
Chapter 5 More applications
5.1 The case of methylviologeand its adsorptioothe silver electrode
5.2 The case of pyridine and its adsorptioothe silver electrode
5.3 The case of piperidine and its adsorptioothe silver electrode
5.4 The case of pyridazine and its adsorptioothe silver electrode
References
Chapter 6 The extensioto Ramaoptical activity
6.1 Ramapticalactivity
6.2 The differential bond polarizability
6.3 The case of (+)-(R)-methyloxirane
6.4 The case of L-alanine
6.5 The case of (S)-phenylethylamine
6.6 The case of trans-2, 3-epoxybutane
References
Chapter 7 More applications oROA
7.1 The case of (S)-2-ami-l-propa
7.2 The case of (S)-l-ami-2-propa
7.3 The case of (2R, 3R)-(-)-2, 3-Butanediol
References
Chapter 8 Intra-molecular enantiomerism
8.1 Background
8.2 The case of (R)-(+)-Limonene
8.3 The case of (S)-(-I-)-2, 2-dimethyl-l, 3-dioxolane-4-metha
8.4 More cases for intramolecular enantiomerism
Chapter 9 A unified classical theory for ROA and VCD
9.1 Background
9.2 The classical algorithm
Appendix A
Appendix B
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