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Excited States of Methylene, Polyenes, and Ozone from Heat-Bath Configuration Interaction
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-02-23 00:00:00 , DOI: 10.1021/acs.jpca.8b01554 Alan D. Chien 1 , Adam A. Holmes 2, 3 , Matthew Otten 3 , C. J. Umrigar 3 , Sandeep Sharma 2 , Paul M. Zimmerman 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-02-23 00:00:00 , DOI: 10.1021/acs.jpca.8b01554 Alan D. Chien 1 , Adam A. Holmes 2, 3 , Matthew Otten 3 , C. J. Umrigar 3 , Sandeep Sharma 2 , Paul M. Zimmerman 1
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The electronically excited states of methylene (CH2), ethylene (C2H4), butadiene (C4H6), hexatriene (C6H8), and ozone (O3) have long proven challenging due to their complex mixtures of static and dynamic correlations. The semistochastic heat-bath configuration interaction (SHCI) algorithm, which efficiently and systematically approaches the full configuration interaction (FCI) limit, is used to provide close approximations to the FCI energies in these systems. This article presents the largest FCI-level calculation to date on hexatriene, using a polarized double-ζ basis (ANO-L-pVDZ), which gives rise to a Hilbert space containing more than 1038 determinants. These calculations give vertical excitation energies of 5.58 and 5.59 eV, respectively, for the 21Ag and 11Bu states, showing that they are nearly degenerate. The same excitation energies in butadiene/ANO-L-pVDZ were found to be 6.58 and 6.45 eV. In addition to these benchmarks, our calculations strongly support the presence of a previously hypothesized ring-minimum species of ozone that lies 1.3 eV higher than the open-ring-minimum energy structure and is separated from it by a barrier of 1.11 eV.
中文翻译：
亚甲基，多烯和臭氧在热浴构型相互作用中的激发态
亚甲基（CH 2），乙烯（C 2 H 4），丁二烯（C 4 H 6），己三烯（C 6 H 8）和臭氧（O 3）的电子激发态）由于静态和动态相关性的复杂混合，长期以来一直被证明具有挑战性。半随机热浴配置相互作用（SHCI）算法有效而系统地接近了完全配置相互作用（FCI）极限，用于提供这些系统中FCI能量的近似值。本文使用极化双ζ基（ANO-L-pVDZ）提出了迄今为止最大的六三烯FCI级计算，这产生了包含10个以上38个行列式的希尔伯特空间。这些计算对于2 1 A g和1 1 B u分别给出了5.58和5.59 eV的垂直激发能。状态，表明它们几乎退化了。发现在丁二烯/ ANO-L-pVDZ中相同的激发能为6.58和6.45 eV。除了这些基准，我们的计算还强烈支持先前假设的最小环臭氧物种的存在，该物种比最小开环能量结构高1.3 eV，并被1.11 eV的势垒隔开。
更新日期：2018-02-23
中文翻译：
亚甲基，多烯和臭氧在热浴构型相互作用中的激发态
亚甲基（CH 2），乙烯（C 2 H 4），丁二烯（C 4 H 6），己三烯（C 6 H 8）和臭氧（O 3）的电子激发态）由于静态和动态相关性的复杂混合，长期以来一直被证明具有挑战性。半随机热浴配置相互作用（SHCI）算法有效而系统地接近了完全配置相互作用（FCI）极限，用于提供这些系统中FCI能量的近似值。本文使用极化双ζ基（ANO-L-pVDZ）提出了迄今为止最大的六三烯FCI级计算，这产生了包含10个以上38个行列式的希尔伯特空间。这些计算对于2 1 A g和1 1 B u分别给出了5.58和5.59 eV的垂直激发能。状态，表明它们几乎退化了。发现在丁二烯/ ANO-L-pVDZ中相同的激发能为6.58和6.45 eV。除了这些基准，我们的计算还强烈支持先前假设的最小环臭氧物种的存在，该物种比最小开环能量结构高1.3 eV，并被1.11 eV的势垒隔开。
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