R型半胱氨酸体系电荷转移百分数的理论计算
|
摘要
采用密度泛函理论中的CAM-B3LYP方法,在6-31G(d)基组水平上优化气相条件下R型半胱氨酸(R-Cys)分子的几何构型,理论研究电子激发过程中R-Cys体系片段间的电荷转移特征,并基于弛豫与非弛豫激发态密度计算片段间的电荷转移百分数.结果表明:对于SH片段,S0到S3的电荷转移百分数为57.96%;对于COOH片段,S0到S1～S5各激发态的电荷转移百分数均为负值,二者电荷转移的定性结果一致;对于NH_2片段,S0到S1和S4的电荷转移百分数分别为6.98%和31.45%.
Using the CAM-B3LYP method of density functional theory,we optimized the geometric configuration of R-Cysteine(R-Cys)molecule in gas phase at 6-31 G(d)basis set,theoretically studied the charge transfer characteristics between fragments of R-Cys system during the electron excitation,and calculated the charge transfer percentage between fragments based on the excited state density of relaxation and non-relaxation.The results show that for SH fragment,the charge transfer percentage from S0 to S3 is 57.96%.For COOH fragment,the charge transfer percentages of the excited states from S0 to S1—S5 are negative,and the qualitative results of charge transfer are consistent.For NH_2 fragments,the charge transfer percentages from S0 to S1 and S4 are 6.98%and 31.45%,respectively.
Using the CAM-B3LYP method of density functional theory,we optimized the geometric configuration of R-Cysteine(R-Cys)molecule in gas phase at 6-31 G(d)basis set,theoretically studied the charge transfer characteristics between fragments of R-Cys system during the electron excitation,and calculated the charge transfer percentage between fragments based on the excited state density of relaxation and non-relaxation.The results show that for SH fragment,the charge transfer percentage from S0 to S3 is 57.96%.For COOH fragment,the charge transfer percentages of the excited states from S0 to S1—S5 are negative,and the qualitative results of charge transfer are consistent.For NH_2 fragments,the charge transfer percentages from S0 to S1 and S4 are 6.98%and 31.45%,respectively.
引文
[1]张小玲,黎星术,谢如刚.两类新型含硫手性大环配体的合成[J].高等学校化学学报,1998,19(8):1262-1266.(ZHANG Xiaoling,LI Xingshu,XIE Rugang.The Synthesis of Two Series Novel Sulfur-Containing Chiral Macrocyclic Ligands[J].Chemical Journal of Chinese Universities,1998,19(8):1262-1266.)
[2]段静静,彭佳敏,曹美荣,等.柱前衍生化高效液相色谱法测定酶法拆分的DL-半胱氨酸含量[J].南开大学学报(自然科学版),2012,45(1):46-51.(DUAN Jingjing,PENG Jiamin,CAO Meirong,et al.Quantity Determination of Enzymatic Chiral Resolution of DL-Cysteine Using Precolumn Derivatization High Performance Liquid Chromatography[J].Acta Scientiarum Naturalium Universitatis Nankaiensis,2012,45(1):46-51.)
[3]洪传敏,王海水.D-半胱氨酸自组装膜对D-或L-天冬氨酸结晶行为的影响[J].化学学报,2014,72:739-742.(HONG Chuanmin,WANG Haishui.Effect of D-Cysteine Self-assembled Monolayers on the Crystallization and Growth of D-or L-Aspartic Acid[J].Acta Chimica Sinica,2014,72:739-742.)
[4]姚金水,李弘,何炳林.2-(2-吡啶基)-4-羧基-1,3-噻唑烷的合成及其在不对称硅氢化反应中的应用[J].山东轻工业学院学报,1997,11(4):5-7.(YAO Jinshui,LI Hong,HE Binglin.Synthesis of 2-(2-Pyridyl)-4-carboxy-1,3-thiazolidine and Its Application in Catalytic Asymmetric Hydrosilation[J].Journal of Shandong Institute of Light Industry,1997,11(4):5-7.)
[5]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 16,Revision A.03[CP/CD].Pittsburgh,PA:Gaussian Inc,2016.
[6]LU Tian,CHEN Feiwu.Multiwfn:A Multifunctional Wavefunction Analyzer[J].Journal of Computational Chemistry,2012,33(5):580-592.
[7]LU Tian,CHEN Feiwu.Quantitative Analysis of Molecular Surface Based on Improved Marching Tetrahedra Algorithm[J].Journal of Molecular Graphics and Modelling,2012,38(9):314-323.
[8]肖萌,卢天.广义化的电荷分解分析(GCDA)方法[J].物理化学进展,2015,4(4):111-124.(XIAO Meng,LU Tian.Generalized Charge Decomposition Analysis(GCDA)Method[J].Journal of Advances in Physical Chemistry,2015,4(4):111-124.)
[2]段静静,彭佳敏,曹美荣,等.柱前衍生化高效液相色谱法测定酶法拆分的DL-半胱氨酸含量[J].南开大学学报(自然科学版),2012,45(1):46-51.(DUAN Jingjing,PENG Jiamin,CAO Meirong,et al.Quantity Determination of Enzymatic Chiral Resolution of DL-Cysteine Using Precolumn Derivatization High Performance Liquid Chromatography[J].Acta Scientiarum Naturalium Universitatis Nankaiensis,2012,45(1):46-51.)
[3]洪传敏,王海水.D-半胱氨酸自组装膜对D-或L-天冬氨酸结晶行为的影响[J].化学学报,2014,72:739-742.(HONG Chuanmin,WANG Haishui.Effect of D-Cysteine Self-assembled Monolayers on the Crystallization and Growth of D-or L-Aspartic Acid[J].Acta Chimica Sinica,2014,72:739-742.)
[4]姚金水,李弘,何炳林.2-(2-吡啶基)-4-羧基-1,3-噻唑烷的合成及其在不对称硅氢化反应中的应用[J].山东轻工业学院学报,1997,11(4):5-7.(YAO Jinshui,LI Hong,HE Binglin.Synthesis of 2-(2-Pyridyl)-4-carboxy-1,3-thiazolidine and Its Application in Catalytic Asymmetric Hydrosilation[J].Journal of Shandong Institute of Light Industry,1997,11(4):5-7.)
[5]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 16,Revision A.03[CP/CD].Pittsburgh,PA:Gaussian Inc,2016.
[6]LU Tian,CHEN Feiwu.Multiwfn:A Multifunctional Wavefunction Analyzer[J].Journal of Computational Chemistry,2012,33(5):580-592.
[7]LU Tian,CHEN Feiwu.Quantitative Analysis of Molecular Surface Based on Improved Marching Tetrahedra Algorithm[J].Journal of Molecular Graphics and Modelling,2012,38(9):314-323.
[8]肖萌,卢天.广义化的电荷分解分析(GCDA)方法[J].物理化学进展,2015,4(4):111-124.(XIAO Meng,LU Tian.Generalized Charge Decomposition Analysis(GCDA)Method[J].Journal of Advances in Physical Chemistry,2015,4(4):111-124.)