Theoretical Insights into Intermolecular Hydrogen-Bonding Strengthening in Fluorenone-Methanol Complexes Induced by Electronic Excitation and Bulk Solvent Effect (cited: 1)

This work presents a theoretical insight into the variation of the site-specific intermolecular hydrogen-bonding (HB), formed between C=O group of fluorenone (FN) and O?H groups of methanol (MeOL) molecules, induced by both the electronic excitation and the bulk solvent effect. Through the calculation of molecular ground- and excited-state properties, we not only demonstrate the characters of HB strengthening induced by electronic excitation and the bulk solvent effect but also reveal the underlying physical mechanism which leads to the HB variation. The strengthening of the intermolecular HB in electronically excited states and in liquid solution is characterized by the reduced HB bond-lengths and the red-shift IR spectra accompanied by the increasing intensities of IR absorption corresponding to the characteristic vibrational modes of the O-H and C=O stretching. The HB strengthening in the excited electronic states and in solution mainly arises from the charge redistribution of the FN molecule induced by the electronic excitation and bulk solvent instead of the intermolecular charge transfer. The charge redistribution of the solute molecule increases the partial dipole moment of FN molecule and the FN-MeOL intermolecular interaction, which subsequently leads to the HB strengthening. With the bulk solvent effect getting involved, the theoretical IR spectra of HBed FN-MeOL complexes agree much better with the experiments than those of gas-phase FN-MeOL dimer. All the calculations are carried out based on our developed analytical approaches for the first and second energy derivatives of excited electronic state within the time-dependent density functional theory.     

Hydrogen Bonding Effects on the Photophysical Properties of 2,3-dihydro-3-keto-1H-pyrido[3,2,1-kl]phenothiazine

Time-dependent density functional theory (TDDFT) and femtosecond transient absorption spectroscopy were used to investigate the photophysical properties of 2,3-dihydro-3-keto-1H-pyrido[3,2,1-kl]phenothiazine (PTZ4) and 3-keto-1H-pyrido[3,2,1-kl]phenothiazine (PTZ5). The calculated results obtained from TDDFT suggest that the red-shifts of the absorption spectra of these two fluorophores in methanol are due to the formation of hydrogen-bonded complexes at the ground state. Four conformers of PTZ4 were obtained by TDDFT. The two fluorescence peaks of PTZ4 in tetrahydrofuran (THF) came from the ICT states of the four conformers. The fluorescence of PTZ4 in THF showed a dependence on the excitation wavelength because of butterfly bending. The excited state dynamics of PTZ4 in THF and methanol were obtained by transient absorption spectroscopy. The lifetime of the excited PTZ4 in methanol was 53.8 ps, and its relaxation from the LE state to the ICT state was completed within several picoseconds. The short lifetime of excited PTZ4 in methanol was due to the formation of out-of-plane model hydrogen bonds between PTZ4 and methanol at the excited state.     

具有延长共轭的绿色发光蛋白生色团的反向溶剂化斯托克斯(Stokes)位移

Chromophore structures inspired by natural green fluorescent protein (GFP) play an important role in the field of bio-imaging. In this work, photochemical properties of a new class of GFP-like chromophores are investigated using computational approaches. Thermodynamically stable isomers are identified in vacuum and in solvent. Spectral Stokes shifts are computed and compared to experiments. An inverted solvatochromic shift between absorption and emission emerging in this new class of GFP-like chromophores is observed, and attributed to the stabilized charge transfer and inhibited rotational structural reorganization in solvent.     

飞秒激光脉宽对三态阶跃型分子波包运动的影响研究

用含时波包法研究了三态阶跃型K2分子在强飞秒泵浦-探测激光场中脉宽对波包动力学过程的影响.研究表明激光场强较弱或者脉宽较短都可能不出现Autler-Townes分裂.波包的振荡周期随脉宽增长而增大,而振荡幅度随脉宽增长而减小. 脉宽影响Rabi振荡,而Rabi振荡的变化又导致了基态和激发态布居数周期性变化．首次量化了脉宽对激发态布居数的影响,表明变化频率随着泵浦场强的增强而增大．研究表明调节激光脉宽可实现对态布居数的选择性分布,可以为实验上实现分子的光控制提供重要参考．     

飞秒激光脉宽对非绝热耦合分子波包运动的影响研究

利用含时波包法研究了强飞秒泵浦-探测激光场中激光脉宽对非绝热耦合NaI分子波包运动的影响.发现波包的振荡周期随脉宽增长而增大,而振荡幅度随脉宽增长而减小.非绝热效应引起的波包在交叉区域的分裂情况影响各态布居.脉宽增长,NaI分子的激发概率增大,而解离概率减小.研究表明调节激光场脉宽可实现对波包运动的控制从而控制态布居的选择性分布.研究结果可以为实验上实现分子的光控制以及量子调控过程提供一定的参考.     

几个荧光蛋白发色团双光子吸收性质的理论研究

实验测得的荧光蛋白的单、双光子吸收光谱在低频和高频区域都表现出明显不同的特征。为了揭示这些不同点的起源和研究荧光蛋白的构–效关系,我们详细研究了三种荧光蛋白发色团(一种增强型蓝绿色荧光蛋白的中性发色团和两种红色荧光蛋白的阴离子发色团)的单、双光子吸收特性,分别计算了纯的和振动分辨的电子谱。计算结果表明：光谱线形与计算采用的交换相关密度泛函及谱截面计算所采用的近似关系密切;如果在计算光谱截面时,我们利用长程修正的交换相关泛函CAM-B3LYP来计算几何和电子结构参数,然后把Franck-Condon (FC)效应和包含Herzberg-Teller (HT)效果的电-声耦合效应都考虑进去,理论计算的光谱与实验测定的光谱可以很好地符合;对于两种离子态的发色团,HT电-声耦合效应使得对应于基态到第一激发态跃迁的双光子吸收最强峰相对于单光子吸收的最强峰发生了蓝移,但HT电-声耦合效应对高频的双光子吸收谱没有太大的影响;分子内电荷转移是导致高频区的双光子吸收明显强于单光子吸收的主要原因。     

最优化“调控”区间分离密度泛函理论的研究进展

发展精确、高效的交换-关联泛函一直是密度泛函理论工作者所追求的神圣目标。传统密度泛函被证实在计算原子或分子体系的某些基态和激发态性能时存在困难,而且预测不具有普适性;另一方面,一些高水平方法如耦合簇（CC）理论和基于格林函数（G）和屏蔽库仑作用（W）近似的多体微扰理论（MBPT）,尽管相对精确但往往需要消耗昂贵的计算成本,因而其研究体系的尺寸和实用性受到了很大的限制。近年来,“最优化”调控区间分离泛函的发展在一定程度上使得上述问题得到改善,尤其是在消耗较少的计算成本前提下能够达到与高水平方法相媲美的预测精度,引起了越来越多的关注。本文首先简要回顾了密度泛函领域的理论背景,在区间分离密度泛函理论的基础上,重点介绍了最优化“调控”的概念;并且结合近期的理论工作对其在实际计算时的表现进行评价;最后,就最优化“调控”方法的前景和应用进行了展望。     

黄芩素激发态分子内质子转移耦合电荷转移反应的实验和理论研究

通过稳态光谱实验和量子化学计算相结合,研究了黄芩素激发态质子转移耦合电荷转移的反应. 实验和计算中S₁态吸收峰的缺失表明S₁态是暗态. S₁暗态导致在实验中观察不到黄芩素在乙醇溶液中的荧光峰,且固体的荧光峰很弱. 黄芩素分子的前线分子轨道和电荷差异密度表明S₁态是电荷转移态,然而S₂态是局域激发态. 计算的黄芩素分子的势能曲线在激发态只有一个稳定点,这表明了黄芩素激发态分子内质子转移的过程是一个无     

氢键效应对2,3-二氢-3-酮基-1H-吡啶并[3,2,1-kl]吩噻嗪光物理性质的影响

利用含时密度泛函理论(TDDFT)方法和飞秒时间分辨的瞬态吸收光谱技术对2,3-二氢-3-酮基-1H-吡啶并[3,2,1-kl]吩噻嗪(PTZ4)和3-酮基-1H-吡啶并[3,2,1-kl]吩噻嗪(PTZ5)这两种荧光探针分子的光物理性质进行了研究. TDDFT结果表明PTZ4和PTZ5在甲醇溶液形成了氢键络合物导致它们吸收峰的红移. PTZ4分子在基态有四种稳定构型,其在四氢呋喃溶液中的双荧光峰正是来自于四种构型下的内部电荷转移态. PTZ4分子在四氢呋喃和甲醇溶液中的瞬态吸收光谱表明,从局域态到转移态的弛豫时间常数在四氢呋喃中为16.0 ps,在甲醇中为7.5 ps;PTZ4分子在甲醇中的激发态寿命为53.8 ps,而这种超短的寿命可能是由于PTZ4分子在激发态时形成的面外型氢键络合物导致的.     

硫脲21A激发态扭曲几何结构的共振拉曼光谱和理论研究

获得了硫脲在水和乙腈溶液中A吸收带的共振拉曼光谱,通过B3LYP/6-311++G(3df,3pd)和RCIS/6-311++G(3df,3pd)分别对硫脲的电子跃迁和2¹A 激发态鞍点结构进行了研究．对共振拉曼光谱进行了归属,并通过含时波包理论对吸收光谱和共振拉曼光谱进行拟合,结果表明硫脲动态结构特征主要沿着：C=S伸缩振动ν₆(|△|=0.95)、H₅N₃H₆+H₈N₄H₇弯曲振动ν₅(|△|=0.19)、NCN对称伸缩振动+C=S伸缩振动+N₃H₆+H₈N₄弯曲振动ν₄(|△|=0.18)．ν₁₅倍频2ν₁₅和4ν₁₅强度主要归因于ν₁₅激发态频率的改变而不是简正模位移量的变化．对S=CN₂面外变形振动ν₁₅倍频出现的机理进行了探究,结果表明Franck-Condon区域势能面鞍点是标准A项共振拉曼散射里的二次声子机制的驱动力,导致碳原子中心的锥形化,并使硫脲在2¹A激发态发生几何结构扭曲.