# Ab initio molecular orbital-configuration interaction based quantum master equation (MOQME) approach to the dynamic first hyperpolarizabilities of asymmetric π-conjugated systems

## Abstract

In this study, we apply the ab initio molecular orbital - configuration interaction based quantum master equation (MOQME) approach to the calculation and analysis of the dynamic first hyperpolarizabilities (β) of asymmetric π-conjugated molecules. In this approach, we construct the excited state models by the ab initio configuration interaction singles method. Then, time evolutions of system reduced density matrix ρ(t) and system polarization p(t) are calculated by the QME approach. Dynamic β in the second harmonic generation is calculated based on the nonperturbative definition of nonlinear optical susceptibility, using the frequency domain system polarization p(ω). Spatial contributions of electrons to β are analyzed based on the dynamic hyperpolarizability density map, which visualizes the second-order response of charge density oscillating with a frequency of 2ω. We apply the present method to the calculation of the dynamic β of a series of donor/acceptor substituted polyene oligomers, and then discuss the applicability of the MOQME method to the calculation and analysis of dynamic NLO properties of molecular systems.

- Authors:

- Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka 560-8531 (Japan)

- Publication Date:

- OSTI Identifier:
- 22390932

- Resource Type:
- Journal Article

- Resource Relation:
- Journal Name: AIP Conference Proceedings; Journal Volume: 1642; Journal Issue: 1; Conference: ICCMSE-2010: International Conference of Computational Methods in Sciences and Engineering 2010, Kos (Greece), 3-8 Oct 2010; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)

- Country of Publication:
- United States

- Language:
- English

- Subject:
- 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ASYMMETRY; CHARGE DENSITY; CONFIGURATION INTERACTION; DENSITY MATRIX; ELECTRONS; EXCITED STATES; HARMONIC GENERATION; MOLECULAR ORBITAL METHOD; NONLINEAR PROBLEMS; POLARIZATION; QUANTUM MECHANICS

### Citation Formats

```
Kishi, Ryohei, Fujii, Hiroaki, Minami, Takuya, Shigeta, Yasuteru, and Nakano, Masayoshi.
```*Ab initio molecular orbital-configuration interaction based quantum master equation (MOQME) approach to the dynamic first hyperpolarizabilities of asymmetric π-conjugated systems*. United States: N. p., 2015.
Web. doi:10.1063/1.4906735.

```
Kishi, Ryohei, Fujii, Hiroaki, Minami, Takuya, Shigeta, Yasuteru, & Nakano, Masayoshi.
```*Ab initio molecular orbital-configuration interaction based quantum master equation (MOQME) approach to the dynamic first hyperpolarizabilities of asymmetric π-conjugated systems*. United States. doi:10.1063/1.4906735.

```
Kishi, Ryohei, Fujii, Hiroaki, Minami, Takuya, Shigeta, Yasuteru, and Nakano, Masayoshi. Thu .
"Ab initio molecular orbital-configuration interaction based quantum master equation (MOQME) approach to the dynamic first hyperpolarizabilities of asymmetric π-conjugated systems". United States.
doi:10.1063/1.4906735.
```

```
@article{osti_22390932,
```

title = {Ab initio molecular orbital-configuration interaction based quantum master equation (MOQME) approach to the dynamic first hyperpolarizabilities of asymmetric π-conjugated systems},

author = {Kishi, Ryohei and Fujii, Hiroaki and Minami, Takuya and Shigeta, Yasuteru and Nakano, Masayoshi},

abstractNote = {In this study, we apply the ab initio molecular orbital - configuration interaction based quantum master equation (MOQME) approach to the calculation and analysis of the dynamic first hyperpolarizabilities (β) of asymmetric π-conjugated molecules. In this approach, we construct the excited state models by the ab initio configuration interaction singles method. Then, time evolutions of system reduced density matrix ρ(t) and system polarization p(t) are calculated by the QME approach. Dynamic β in the second harmonic generation is calculated based on the nonperturbative definition of nonlinear optical susceptibility, using the frequency domain system polarization p(ω). Spatial contributions of electrons to β are analyzed based on the dynamic hyperpolarizability density map, which visualizes the second-order response of charge density oscillating with a frequency of 2ω. We apply the present method to the calculation of the dynamic β of a series of donor/acceptor substituted polyene oligomers, and then discuss the applicability of the MOQME method to the calculation and analysis of dynamic NLO properties of molecular systems.},

doi = {10.1063/1.4906735},

journal = {AIP Conference Proceedings},

number = 1,

volume = 1642,

place = {United States},

year = {Thu Jan 22 00:00:00 EST 2015},

month = {Thu Jan 22 00:00:00 EST 2015}

}