Ab Initio Study of the Effect of Solvation on the Electronic Spectra of Formamide and N-Methylacetamide

Nicholas A. Besley; Jonathan D. Hirst

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Ab Initio Study of the Effect of Solvation on the Electronic Spectra of Formamide and N-Methylacetamide

机译：从头开始研究溶剂化对甲酰胺和N-甲基乙酰胺电子光谱的影响

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Calculations on the electronic spectra of formamide and N-methylacetamide in solution are presented. Solvents are modeled by macroscopic continua characterized by their dielectric constant and refractive index. The complete-active-space self-consistent-field model implemented within a self-consistent reaction field model is used. Dynamical correlation is accounted for using multiconfigurational perturbation theory. The Rydberg states are shown to be destabilized by the Pauli repulsion of the solvent. An advantageous side effect of this destabilization is the reduction of mixing between valence and Rydberg states encountered in gas-phase calculations on amides. A red-shift of 0.5-1.0 eV relative to comparable gas-phase calculation is seen for the ππ~* transitions. For formamide in cyclohexane, nπ~* and ππ~* vertical transitions are computed to lie at 5.56 eV (oscillator strength f = 0.0006) and 6.94 eV (F = 0.274). For N-methylacetamide, the corresponding transitions are found at 5.55 eV (f = 0.001) and 6.59 eV (f = 0.256). In addition, higher energy excitations have been studied, including excitations from the lower-lying oxygen lone-pair orbital. Good agreement with available experimental data is achieved throughout, indicating the method used provides an accurate treatment of valence excited states in solution.

机译：给出了溶液中甲酰胺和N-甲基乙酰胺电子光谱的计算。通过宏观连续性对溶剂进行建模，宏观连续性的特征在于其介电常数和折射率。使用在自洽反应场模型中实现的完全活动空间自洽场模型。动态相关性是使用多配置摄动理论来说明的。里德堡状态显示出由于溶剂的保利排斥而不稳定。这种去稳定作用的有利副作用是减少了在酰胺上进行气相计算时所遇到的化合价和里德堡态之间的混合。对于ππ*跃迁，相对于可比较的气相计算而言，红移为0.5-1.0 eV。对于环己烷中的甲酰胺，计算出nπ〜*和ππ〜*的垂直跃迁位于5.56 eV（振荡器强度f = 0.0006）和6.94 eV（F = 0.274）处。对于N-甲基乙酰胺，在5.55 eV（f = 0.001）和6.59 eV（f = 0.256）处发现了相应的跃迁。另外，已经研究了较高能量的激发，包括来自较低氧孤对轨道的激发。整个实验过程中，与可用的实验数据取得了很好的一致性，这表明所使用的方法可以准确处理溶液中的价态激发态。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |1998年第52期|共7页
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Nicholas A. Besley; Jonathan D. Hirst;
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中图分类物理化学（理论化学）、化学物理学;
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1. Ab Initio Study of the Effect of Solvation on the Electronic Spectra of Formamide and N-Methylacetamide [J] . Nicholas A. Besley, Jonathan D. Hirst The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 1998,第52期

机译：从头开始研究溶剂化对甲酰胺和N-甲基乙酰胺电子光谱的影响
2. Specific Solvation Effects on the Structures and Properties of Neutral and One-Electron Oxidized Formamidine-Formamide Complexes. A Theoretical ab Initio Study [J] . Nurbosyn U. Zhanpeisov, Jerzy Leszczynski The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 1999,第41期

机译：对中性和一电子氧化的甲One-甲酰胺配合物的结构和性能的特定溶剂作用。从头算的理论研究
3. Liquid Structure, Infrared and Isotropic/Anisotropic Raman Noncoincidence of the Amide I Band, and Low-Wavenumber Vibrational Spectra of Liquid Formamide: Molecular Dynamics and ab Initio Molecular Orbital Studies [J] . Hajime Torii, Mitsuo Tasumi The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical . 1998,第1期

机译：酰胺I带的液体结构，红外和各向同性/各向异性拉曼光谱不一致以及液体甲酰胺的低波振动光谱：分子动力学和从头算分子轨道研究
4. Ab-Initio Calculations for the Electronic Spectra of Cubic and Hexagonal Boron Nitride [C] . Guido Satta, Giancarlo Cappellini, Valerio Olevano, Symposium on Progress in Compound Semiconductor Materials-Electronic and Optoelectonic Applications . 2005

机译：立方和六边形氮化物的电子光谱的AB-Initio计算
5. Ab initio studies on the solvation, electronic structures and intracluster reactions in M(+)L(n), with M(+)=magnesium and calcium singly-charged ions, L=water, methanol, ammonia, and n=1-6, and the elimination of a hydrogen atom in H atom in hydrated sodium clusters [D] . Chan, Ka Wai 2008

机译：从头开始研究M（+）L（n）中的溶剂化，电子结构和簇内反应，其中M（+）=镁和钙的单电荷离子，L =水，甲醇，氨和n = 1-6以及消除水合钠簇中H原子中的氢原子
6. Electronic Absorption Spectra from MM and ab initio QM/MM Molecular Dynamics: Environmental Effects on the Absorption Spectrum of Photoactive Yellow Protein [O] . Christine M. Isborn, Andreas W. Götz, Matthew A. Clark, -1

机译：电子吸收光谱从mm和从头Qm / mm分子动力学：对光敏蛋白黄色的吸收光谱环境影响
7. Ab Initio Study of the Effect of Solvation on the Electronic Spectra of Formamide and N-Methylacetamide [O] . Nicholas A. Besley, Jonathan D. Hirst 1998

机译：溶剂化对甲酰胺和N-甲基乙酰胺电子光谱影响的从头算研究
8. Ab Initio Study of the Internal Rotation Barrier of Formamide and the Formamide-H2O Complex. (Reannouncement with New Availability Information) [R] . Wang, X. C., Facelli, J. C., Simons, J. 1993

机译：甲酰胺和甲酰胺 - H2O复合物内旋转阻隔的从头算研究。（重新公布新的可用性信息）

Ab Initio Study of the Effect of Solvation on the Electronic Spectra of Formamide and N-Methylacetamide

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