Tuning Two-Photon Absorption in Rhodopsin Chromophore via Backbone Modification: The Story Told by CC2 and TD-DFT,Journal of Chemical Theory and Computation

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Tuning Two-Photon Absorption in Rhodopsin Chromophore via Backbone Modification: The Story Told by CC2 and TD-DFT
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-09-13 , DOI: 10.1021/acs.jctc.4c00675
Saruti Sirimatayanant ₁ , Tadeusz Andruniów ₁

Affiliation

We investigate here a systematic way to tune two-photon transition strengths (δ^2PA) and two-photon absorption (2PA) cross sections (σ^2PA) of the rhodopsin’s chromophore 11-cis-retinal protonated Schiff base (RPSB) via the modulation of the methyl groups pattern along its polyene chain. Our team employed the resolution of identity, coupled cluster approximate second order (RI-CC2) method with Dunning’s aug-cc-pVDZ basis set, to determine the structural impact on δ^2PA, as well as its correlation to both transition dipole moments and permanent electric dipole moments. Seven structures were probed in vacuo, including five-double-bond-conjugated model of the native chromophore, shortened by the β-ionone ring (RPSB5), and its de/methylated analogues: 9-methyl, 13-methyl, planar and twisted models of 9,10-dimethyl and 9,10,13-trimethyl. Our results demonstrate that the magnitude of δ^2PA is dictated by both the position and number of methylated groups attached to its polyene chain as well as the degree of dihedral twist that is introduced due to the de/methylation. In fact, a strong correlation between δ^2PA enhancement and the presence of a C13-methyl group in the planar RPSB5 species is found. Trends in δ^2PA values follow the trends observed in their corresponding changes in the permanent dipole moment upon the S0–S1 excitation nearly exactly. The assessment of four DFT functionals, i.e., M11, MN15, CAM-B3LYP, and BHandHLYP, previously found most successful in predicting 2PA properties in biological chromophores, points to a long-range-corrected hybrid meta-GGA M11 as the top-performing functional, albeit still delivering underestimated δ^2PA and σ^2PA values by a factor of 3.3–5.3 with respect to the CC2 results. In the case of global-hybrid meta-NGA (MN15), as well as CAM-B3LYP and BHandHLYP functionals, this factor deteriorates significantly to 6.7–20.9 and is mostly related to significantly lower quality of the ground- and excited-state dipole moments.

中文翻译：

通过主链修饰调节视紫红质发色团中的双光子吸收：CC2 和 TD-DFT 讲述的故事

我们在这里研究了一种通过调节视紫红质发色团 11-顺式-视网膜质子化希夫碱 (RPSB) 的双光子跃迁强度 (δ ^2PA ) 和双光子吸收 (2PA) 截面 (σ ^2PA ) 的系统方法甲基沿着其多烯链排列。我们的团队采用身份解析、耦合簇近似二阶 (RI-CC2) 方法和 Dunning 的 aug-cc-pVDZ 基组来确定对 δ ^{2PA 的}结构影响，以及它与过渡偶极矩和永久偶极矩的相关性电偶极矩。在真空中探测了七种结构，包括天然发色团的五双键共轭模型，由 β-紫罗兰酮环 (RPSB5) 缩短，及其去/甲基化类似物：9-甲基、13-甲基、平面和扭曲9,10-二甲基和9,10,13-三甲基的模型。我们的结果表明，δ ^2PA的大小由连接到其多烯链的甲基化基团的位置和数量以及由于去/甲基化引入的二面体扭曲程度决定。事实上，我们发现 δ ^2PA增强与平面 RPSB5 物种中 C13-甲基的存在之间存在很强的相关性。 δ ^2PA值的趋势几乎完全遵循 S0-S1 激励时永久偶极矩相应变化所观察到的趋势。四个 DFT 泛函的评估，即、M11、MN15、CAM-B3LYP 和 BHandHLYP 先前发现在预测生物发色团中的 2PA 特性方面最成功，指出长程校正的混合元 GGA M11 是性能最佳的功能，尽管仍然提供低估的 δ ^2PA σ ^2PA值相对于 CC2 结果增加了 3.3–5.3 倍。在全局混合元 NGA (MN15) 以及 CAM-B3LYP 和 BHandHLYP 泛函的情况下，该因子显着恶化至 6.7–20.9，并且主要与基态和激发态偶极矩质量显着降低有关。

更新日期：2024-09-13

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