Optimizing Calculations of Electronic Excitations and Relative Hyperpolarizabilities of Electrooptic Chromophores
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- 作者：Lewis E. Johnson ; Larry R. Dalton ; Bruce H. Robinson
- 刊名：Accounts of Chemical Research
- 出版年：2014
- 出版时间：November 18, 2014
- 年：2014
- 卷：47
- 期：11
- 页码：3258-3265
- 全文大小：370K
- ISSN：1520-4898
文摘
Conspectus
Organic glasses containing chromophores with large first hyperpolarizabilities (尾) are promising for compact, high-bandwidth, and energy-efficient electro-optic devices. Systematic optimization of device performance requires development of materials with high acentric order and enhanced hyperpolarizability at operating wavelengths. One essential component of the design process is the accurate calculation of optical transition frequencies and hyperpolarizability. These properties can be computed with a wide range of electronic structure methods implemented within commercial and open-source software packages. A wide variety of methods, especially hybrid density-functional theory (DFT) variants have been used for this purpose. However, in order to provide predictions useful to chromophore designers, a method must be able to consistently predict the relative ordering of standard and novel materials. Moreover, it is important to distinguish between the resonant and nonresonant contribution to the hyperpolarizabiliy and be able to estimate the trade-off between improved 尾 and unwanted absorbance (optical loss) at the target device鈥檚 operating wavelength.
Therefore, we have surveyed a large variety of common methods for computing the properties of modern high-performance chromophores and compared these results with prior experimental hyper-Rayleigh scattering (HRS) and absorbance data. We focused on hybrid DFT methods, supplemented by more computationally intensive M酶ller鈥揚lesset (MP2) calculations, to determine the relative accuracy of these methods. Our work compares computed hyperpolarizabilities in chloroform relative to standard chromophore EZ-FTC against HRS data versus the same reference.
We categorized DFT methods used by the amount of Hartree鈥揊ock (HF) exchange energy incorporated into each functional. Our results suggest that the relationship between percentage of long-range HF exchange and both 尾HRS and 位max is nearly linear, decreasing as the fraction of long-range HF exchange increases. Mild hybrid DFT methods are satisfactory for prediction of 位max. However, mild hybrid methods provided qualitatively incorrect predictions of the relative hyperpolarizabilities of three high-performance chromophores. DFT methods with approximately 50% HF exchange, and especially the Truhlar M062X functional, provide superior predictions of relative 尾HRS values but poorer predictions of 位max. The observed trends for these functionals, as well as range-separated hybrids, are similar to MP2, though predicting smaller absolute magnitudes for 尾HRS.
Frequency dependence for 尾HRS can be calculated using time-dependent DFT and HF methods. However, calculation quality is sensitive not only to a method鈥檚 ability to predict static hyperpolarizability but also to its prediction of optical resonances. Due to the apparent trade-off in accuracy of prediction of these two properties and the need to use static finite-field methods for MP2 and higher-level hyperpolarizability calculations in most codes, we suggest that composite methods could greatly improve the accuracy of calculations of 尾 and 位max.
Organic glasses containing chromophores with large first hyperpolarizabilities (尾) are promising for compact, high-bandwidth, and energy-efficient electro-optic devices. Systematic optimization of device performance requires development of materials with high acentric order and enhanced hyperpolarizability at operating wavelengths. One essential component of the design process is the accurate calculation of optical transition frequencies and hyperpolarizability. These properties can be computed with a wide range of electronic structure methods implemented within commercial and open-source software packages. A wide variety of methods, especially hybrid density-functional theory (DFT) variants have been used for this purpose. However, in order to provide predictions useful to chromophore designers, a method must be able to consistently predict the relative ordering of standard and novel materials. Moreover, it is important to distinguish between the resonant and nonresonant contribution to the hyperpolarizabiliy and be able to estimate the trade-off between improved 尾 and unwanted absorbance (optical loss) at the target device鈥檚 operating wavelength.
Therefore, we have surveyed a large variety of common methods for computing the properties of modern high-performance chromophores and compared these results with prior experimental hyper-Rayleigh scattering (HRS) and absorbance data. We focused on hybrid DFT methods, supplemented by more computationally intensive M酶ller鈥揚lesset (MP2) calculations, to determine the relative accuracy of these methods. Our work compares computed hyperpolarizabilities in chloroform relative to standard chromophore EZ-FTC against HRS data versus the same reference.
We categorized DFT methods used by the amount of Hartree鈥揊ock (HF) exchange energy incorporated into each functional. Our results suggest that the relationship between percentage of long-range HF exchange and both 尾HRS and 位max is nearly linear, decreasing as the fraction of long-range HF exchange increases. Mild hybrid DFT methods are satisfactory for prediction of 位max. However, mild hybrid methods provided qualitatively incorrect predictions of the relative hyperpolarizabilities of three high-performance chromophores. DFT methods with approximately 50% HF exchange, and especially the Truhlar M062X functional, provide superior predictions of relative 尾HRS values but poorer predictions of 位max. The observed trends for these functionals, as well as range-separated hybrids, are similar to MP2, though predicting smaller absolute magnitudes for 尾HRS.
Frequency dependence for 尾HRS can be calculated using time-dependent DFT and HF methods. However, calculation quality is sensitive not only to a method鈥檚 ability to predict static hyperpolarizability but also to its prediction of optical resonances. Due to the apparent trade-off in accuracy of prediction of these two properties and the need to use static finite-field methods for MP2 and higher-level hyperpolarizability calculations in most codes, we suggest that composite methods could greatly improve the accuracy of calculations of 尾 and 位max.