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Biomedical subjects

S H Lin

Publications and source records attributed to S H Lin.

At least 289 records · Page 16Linked to original sources

Collisional energy transfer and quenching of electronic excitation.

The purpose of this paper has been to explore in a preliminary way the nature and mechanism of collisional energy transfer and quenching of electronic excitation. For this purpose, the Born approximation has been used, and the triplet-triplet and singlet-singlet transfer, and the triplet-triplet and singlet-singlet quenching have been studied. It has been shown theoretically that (i) the singlet-singlet transfer constants (or cross sections) are always larger than the triplet-triplet transfer constants (or cross sections) for the same system of donor and acceptor; (ii) for the singlet-singlet transfer, the observed cross section varies linearly with respect to the spectral overlap between the donor emission and the acceptor absorption; (iii) the reason that the quenching constants (or cross sections) are always smaller than the energy transfer constants (or cross sections) is due to the fact that for the quenching the vibration of the acceptor hardly participates in accepting the electronic excitation and for the energy transfer only part of the excited electron energy of the donor is converted into the energy of nuclear motion; and (iv) the polar acceptor molecules are better quenchers than nonpolar acceptor molecules.

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Magnetic Circular Dichroism of Molecules in Dense Media: Relation Between Magnetic Circular Dichroism and Hammett's Constants.

The linear relation between the magnetic circular dichroism (benzene (1)A(1g) --> (1)B(2u) transition) of monosubstituted and 1,4-disubstituted benzenes and the substituent constants sigma and sigma(R) are compared. In all cases, better linear correlations were found between the magnetic circular dichroism and sigma(R). Three series of 1,4-disubstituted benzenes, XC(6)H(4)I, XC(6)H(4)NO(2), and XC(6)H(4)CO(2)H, have been chosen for the magnetic circular dichroism measurements.

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Effect of chemical substitution on absorption spectra and magnetic circular dichroism of molecules in dense media.

The purpose of this paper has been to study the effect of chemical substitution on the magnetic circular dichroism and absorption spectra for the parent molecule which has the C(2v) symmetry. Four electronic transitions, A(1) --> A(1), A(1) --> B(1), A(1) --> B(2), and A(1) --> A(2) have been considered. In each case, the intensity changes in magnetic circular dichroism and absorption spectra due to substitution have been expressed in terms of number of substituents and positions of substitution.

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Study of the franck-condon and herzberg-teller approximations.

Using the Born-Oppenheimer parameter lambda = (m/M)(1/4) as a perturbation parameter, we find that for allowed transitions, the zeroth order approximation of the spectral intensity gives rise to the Condon approximation, the first order vibronic coupling and anharmonic effect appear in the first order approximation of the spectral intensity, which gives us the non-Condon scheme, and only the intensity of the transitions of totally-symmetric modes with nonvanishing normal coordinate displacements is affected by the inclusion of the first order vibronic coupling and anharmonic effect. For symmetry-forbidden but vibronic-allowed transitions, the first nonvanishing term of the spectral intensity is second order with respect to lambda and the B-O couplings do not appear in the calculation of the spectral intensity until the fourth order approximation with respect to lambda; in this case, other high order vibronic couplings and anharmonic effect are competing with the B-O couplings.

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A statistical study of optical rotation for synthetic d,l-copolypeptide solutions.

The right-handed helical fraction H(L) in a D,L-copolypeptide chain is evaluated by a simple probability theory for each L-fraction, p. The curves of optical rotation at a single wavelength against p for poly(gamma-benzyl-D,L-glutamate) and D,L-copolyleucine of a series of different D:L ratios in several positive helix-solvents are calculated with a modified semi-empirical Moffitt equation. From the comparison between the rotations calculated by us and observed by Downie et al., it is shown that to reproduce the observed rotations, the minimum number of right-handed helical nuclei or sequences of L-residues appropriate to the Moffitt equation are eight and four for degrees of polymerization 320 and 1860, respectively.

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Investigation of the composition and formation constant of molecular complexes.

It has been the purpose of the present paper to investigate and explore the conditions under which the linear relation between Delta/C(D) (0) and Delta in the Hanna-Ashbaugh-Foster-Fyfe equation for the evaluation of equilibrium constants holds, (C(D) (0) is initial concentration of a donor and Delta is the observed chemical shift relative to the chemical shift of the acceptor) to obtain the equation representing the exact linear relation between Delta/C(D) (0) and Delta, when the linear relation between Delta/C(D) (0) and Delta holds, and to discuss how to use the Job method in nuclear magnetic resonance measurements to determine the stoichiometry of molecular complexes. We have found that the conventional belief that C(D) (0) should always be chosen to be much greater than C(A) (0) (initial concentration of acceptor) is not necessarily always true and the exact linear relation between Delta/C(D) (0) and Delta is represented by the equation Delta/C(D) (0) = K(1)Delta(0)/(1 + K(1)C(A) (0)) - K(1)Delta/(1 + K(1)C(A) (0))(2), where K(1) is the formation constant of the complex. It is shown that in the Job method of nuclear magnetic resonance measurements one has to plot DeltaC(A) (0) against the mole fraction, and the mole fraction at the maximum should give us the composition of the complex. Theoretical results have been verified experimentally on the weak interaction between naphthalene and methyl iodide.

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Study of vibronic and born-oppenheimer couplings.

The purpose of this paper has been to develop a systematic approach for classifying and distinguishing the relative orders of approximation of various types of couplings like the vibronic (Herzberg-Teller) couplings and Born-Oppenheimer couplings, and for studying the importance of the anharmonicity in the quantitative calculation of the spectral intensity and electronic relaxation. It will be shown that the perturbation parameter introduced by Born and Oppenheimer in separating the electronic and nuclear motion involved in the molecular Schrödinger equation, lambda = (m/M)(1/4), can be used for this purpose by expanding wavefunctions and energies in power series of lambda.

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Application of the singular perturbation method to reaction kinetics.

The purpose of this paper is to show how to apply the singular perturbation method to the rate equations in reaction kinetics that involve different time scales. The Lindemann scheme has been chosen for illustration, and the steady-state and equilibrium approximations used in the Lindemann scheme are discussed.

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Stochastic Model of Unimolecular Reactions and the RRKM Theory.

A stochastic model of unimolecular reactions has been adopted for investigation of the validity and limitation of the RRKM theory. The error caused by the steady-state approximation for distribution of energized molecules is small, while the assumption of the internal energy equilibration of energized molecules might cause serious errors for reactions of low activation energies.

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Magnetic circular dichroism of molecules in dense media: benzene.

This paper presents some calculated results on the vibrational structuring of the magnetic circular dichroism of the benzene (1)A(1g)"(1)B(2u) transition. The good agreement between the experimental and calculated relative intensities of the B-bands (positive magnetic circular dichroism bands) indicates that these bands are mainly induced by the e(2g) 1596 cm(-1) mode. The unfavorable results obtained by comparison of the theoretical results with experimental results for the A-bands (negative magnetic circular dichroism bands) is presumably due to neglect of the contribution from the e(2g) 3056 cm(-1) mode, from hot bands, and from the transitions of normal modes other than the A(1g) 992 cm(-1) mode. It should be noticed that while the e(2g) 608 cm(-1) mode plays a dominating role in the ultraviolet spectrum of benzene, in the magnetic circular dichroism of benzene, the e(2g) 1596 cm(-1) mode is, if not more important, at least as important as the e(2g) 608 cm(-1) mode.

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