Abstract
Theoretical descriptions of the molecular polarizability and second hyperpolarizability (α and γ) of the linear quadrupolar molecule are presented. By using a valence-bond and two charge-transfer states, three eigenfunctions of a quadrupolar molecule are obtained as linear combinations of these basis states. The analytic expressions for α and γ are obtained, and the physical picture on the nonlinear optical (NLO) response of the quadrupolar molecule is presented. By introducing the bond-length-alternation coordinates into the model Hamiltonian, the relationships of various vibrational characteristics, such as IR, Raman, and hyper-Raman intensities and vibrational frequencies, with respect to the molecular structure are established. The vibrational second hyperpolarizability is also compared with the electronic one, and the two quantities show similar trends as the charge-transfer character changes. A number of distinctive features are discussed by comparing the results with those of the linear push-pull polyene. The NLO properties of a series of quadrupolar molecules are calculated by using the ab initio method, and also a few more examples of quadrupolar molecules are suggested.
| Original language | English |
|---|---|
| Pages (from-to) | 8221-8229 |
| Number of pages | 9 |
| Journal | Journal of Physical Chemistry B |
| Volume | 103 |
| Issue number | 39 |
| Publication status | Published - 1999 Sep 30 |
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All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Surfaces, Coatings and Films
- Materials Chemistry
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Nonlinear Optical Properties of the Linear Quadrupolar Molecule : Structure-Function Relationship Based on a Three-State Model. / Hahn, Sangjoon; Kim, Dongho; Cho, Minhaeng.
In: Journal of Physical Chemistry B, Vol. 103, No. 39, 30.09.1999, p. 8221-8229.Research output: Contribution to journal › Article
TY - JOUR
T1 - Nonlinear Optical Properties of the Linear Quadrupolar Molecule
T2 - Structure-Function Relationship Based on a Three-State Model
AU - Hahn, Sangjoon
AU - Kim, Dongho
AU - Cho, Minhaeng
PY - 1999/9/30
Y1 - 1999/9/30
N2 - Theoretical descriptions of the molecular polarizability and second hyperpolarizability (α and γ) of the linear quadrupolar molecule are presented. By using a valence-bond and two charge-transfer states, three eigenfunctions of a quadrupolar molecule are obtained as linear combinations of these basis states. The analytic expressions for α and γ are obtained, and the physical picture on the nonlinear optical (NLO) response of the quadrupolar molecule is presented. By introducing the bond-length-alternation coordinates into the model Hamiltonian, the relationships of various vibrational characteristics, such as IR, Raman, and hyper-Raman intensities and vibrational frequencies, with respect to the molecular structure are established. The vibrational second hyperpolarizability is also compared with the electronic one, and the two quantities show similar trends as the charge-transfer character changes. A number of distinctive features are discussed by comparing the results with those of the linear push-pull polyene. The NLO properties of a series of quadrupolar molecules are calculated by using the ab initio method, and also a few more examples of quadrupolar molecules are suggested.
AB - Theoretical descriptions of the molecular polarizability and second hyperpolarizability (α and γ) of the linear quadrupolar molecule are presented. By using a valence-bond and two charge-transfer states, three eigenfunctions of a quadrupolar molecule are obtained as linear combinations of these basis states. The analytic expressions for α and γ are obtained, and the physical picture on the nonlinear optical (NLO) response of the quadrupolar molecule is presented. By introducing the bond-length-alternation coordinates into the model Hamiltonian, the relationships of various vibrational characteristics, such as IR, Raman, and hyper-Raman intensities and vibrational frequencies, with respect to the molecular structure are established. The vibrational second hyperpolarizability is also compared with the electronic one, and the two quantities show similar trends as the charge-transfer character changes. A number of distinctive features are discussed by comparing the results with those of the linear push-pull polyene. The NLO properties of a series of quadrupolar molecules are calculated by using the ab initio method, and also a few more examples of quadrupolar molecules are suggested.
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M3 - Article
AN - SCOPUS:0000401123
VL - 103
SP - 8221
EP - 8229
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
SN - 1520-6106
IS - 39
ER -