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I. The Electronic States of Heavily-doped Molecular Crystals - Naphthalene: I. Theoretical. II. Experimental. II. Lowest Singlet and Triplet Excited States of Pyrazine


Hong, Hwei-Kwan (1970) I. The Electronic States of Heavily-doped Molecular Crystals - Naphthalene: I. Theoretical. II. Experimental. II. Lowest Singlet and Triplet Excited States of Pyrazine. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/fwyp-yw14.



The energy spectrum of heavily-doped molecular crystals was treated in the Green’s function formulation. The mixed crystal Green’s function was obtained by averaging over all possible impurity distributions. The resulting Green’s function, which takes the form of an infinite perturbation expansion, was further approximated by a closed form suitable for numerical calculations. The density-of-states functions and optical spectra for binary mixtures of normal naphthalene and deuterated naphthalene were calculated using the pure crystal density-of-state functions. The results showed that when the trap depth is large, two separate energy bands persist, but when the trap depth is small only a single band exists. Furthermore, in the former case it was found that the intensities of the outer Davydov bands are enhanced whereas the inner bands are weakened. Comparisons with previous theoretical calculations and experimental results are also made.


The energy states and optical spectra of heavily-doped mixed crystals are investigated. Studies are made for the following binary systems: (1) naphthalene-h8 and d8, (2) naphthalene--h8 and αd4, and (3) naphthalene--h8 and βd1, corresponding to strong, medium and weak perturbations. In addition to ordinary absorption spectra at 4˚K, band-to-band transitions at both 4˚K and 77˚K are also analyzed with emphasis on their relations to cooperative excitation and overall density-of-states functions for mixed crystals. It is found that the theoretical calculations presented in a previous paper agree generally with experiments except for cluster states observed in system (1) at lower guest concentrations. These features are discussed semi-quantitatively. As to the intermolecular interaction parameters, it is found that experimental results compare favorably with calculations based on experimental density-of-states functions but not with those based on octopole interactions or charge-transfer interactions. Previous experimental results of Sheka and the theoretical model of Broude and Rashba are also compared with present investigations.


The phosphorescence, fluorescence and absorption spectra of pyrazine-h4 and d4 have been obtained at 4˚K in a benzene matrix. For comparison, those of the isotopically mixed crystal pyrazine-h4 in d4 were also taken. All these spectra show extremely sharp and well-resolved lines and reveal detailed vibronic structure.

The analysis of the weak fluorescence spectrum resolves the long-disputed question of whether one or two transitions are involved in the near-ultraviolet absorption of pyrazine. The “mirror-image relationship” between absorption and emission shows that the lowest singlet state is an allowed transition, properly designated as 1B3u1A1g. The forbidden component 1B2g, predicted by both “exciton” and MO theories to be below the allowed component, must lie higher. Its exact location still remains uncertain.

The phosphorescence spectrum when compared with the excitation phosphorescence spectra, indicates that the lowest triplet state is also symmetry allowed, showing a strong 0-0 band and a “mirror-image relationship” between absorption and emission. In accordance with previous work, the triplet state is designated as 3B3u.

The vibronic structure of the phosphorescence spectrum is very complicated. Previous work on the analysis of this spectrum all concluded that a long progression of v6a exists. Under the high resolution attainable in our work, the supposed v6a progression proves to have a composite triplet structure, starting from the second member of the progression. Not only is the v9a hydrogen-bending mode present as shown by the appearance of the C-D bending mode in the d4 spectrum, but a band of 1207 cm-1 in the pyrazine in benzene system and 1231 cm-1 in the mixed crystal system is also observed. This band is assigned as 2v6b and of a1g symmetry. Its anonymously strong intensity in the phosphorescence spectrum is interpreted as due to the Fermi resonance with the 2v6a and v9a band.

To help resolve the present controversy over the crystal phosphorescence spectrum of pyrazine, detailed vibrational analyses of the emission spectra were made. The fluorescence spectrum has essentially the same vibronic structure as the phosphorescence spectrum.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:(Chemistry and Physics)
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Minor Option:Physics
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Robinson, G. Wilse
Thesis Committee:
  • Unknown, Unknown
Defense Date:6 October 1969
Additional Information:Title varies in 1970 Commencement Program: "I. The Electronic States of Heavily-doped Molecular Crystals - Naphthalene. II. and the Electronic Spectra of Pyrazine"
Funding AgencyGrant Number
Army Research OfficeUNSPECIFIED
Record Number:CaltechTHESIS:09012015-081452587
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:9127
Deposited On:01 Sep 2015 17:07
Last Modified:02 Aug 2021 23:32

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