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亚乙基硫脲分子键伸缩模式与全耦合模式键极化率的对比及其拉曼激发虚态的相关研究

陈艳荣 王培杰 方炎

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亚乙基硫脲分子键伸缩模式与全耦合模式键极化率的对比及其拉曼激发虚态的相关研究

陈艳荣, 王培杰, 方炎

The comparison of temporal bond polarizabilities of the nonresonant Raman excited virtual state of ethylene thiourea by two different algorithms

Chen Yan-Rong, Wang Pei-Jie, Fang Yan
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  • 从拉曼峰强着手,得到了键伸缩模式与全耦合模式两种不同计算条件下,亚乙基硫脲(ethylene thiourea,ETU)分子的键极化率,并比较分析了两种计算结果的异同.研究表明:在键伸缩模式的算法中,仅考虑势能分布中键对称伸缩比重相对较大的部分拉曼峰参与极化率计算,显然忽略了键伸缩与键弯曲间的相互耦合,造成了与弯曲振动耦合较强的部分键伸缩极化率值存在一定误差.因此,此方法虽能使问题简化,但却丢失了一些信息.而全耦合模式算法考虑了所有振动模式(键伸缩与键弯曲)相互影响的情况,能更全面的反映键电荷的分布情况,
    We studied the temporal bond polarizabilities of ethylene thiourea (ETU) from the Raman intensities by two different algorithms. One algorithm includes only the bond stretching modes and the other includes all bond modes. Our analysis shows that, the algorithm using bond stretching modes, in which only the part of Raman peaks whose vibrational modes have relatively larger proportion in the bond stretching are considered, may have larger errors in certain situations where the stretching and bending modes have significant coupling. Otherwise, this algorithm is just suitable, although it may lose certain physical information. The bond polarizabilities provide much information concerning the electronic distribution of nonresonant Raman excited virtual state. At the initial moment of the 514.5 nm excitation, the tendency of the excited electrons is to spread to the molecular periphery. Meanwhile, the relaxation process of the bond polarizability and the characteristic times for these two models are almost the same.
    • 基金项目: 北京市自然科学基金(批准号:2082006)资助的课题.
    [1]

    Liu Z J 2006 Ph.D. Dissertation (Tsinghua University) (in Chinese)[刘照军 2006 博士学位论文 (清华大学)]

    [2]

    Fang C, Liu Z J, Wu G Z 2008 J.Mol.Struct. 885 168

    [3]

    Fang C, Wu G Z 2009 J. Raman Spectrosc. 40 308

    [4]

    Fang C, Wu G Z 2007 J. Raman Spectrosc. 38 1416

    [5]

    Wu G Z 2007 Raman Spectroscopy: A Intensity Approach (Beijing: Science Press) p70-84 (in Chinese)[吴国祯 2007 拉曼谱学-峰强中的信息.(北京:科学出版社)第70—84页]

    [6]

    Zhong F P, Wu G Z 1993 J.Mol.Struct. 298 55

    [7]

    Wang P J, Wu G Z 2004 Chem.Phys.Lett. 385 96

    [8]

    Huang Y, Wu G Z 1990 Spectrochimica Acta A 46 377

    [9]

    Liu Z J, Wu G Z 2004 Chem.Phys.Lett. 389 298

    [10]

    Liu Z J, Wu G Z 2006 Acta.Phys.Sin. 55 6315(in Chinese)[刘照军、吴国祯 2006 物理学报 55 6315]

    [11]

    Fang C, Wu G Z 2009 Acta.Phys.Sin. 58 2345(in Chinese)[房 超、吴国祯 2009 物理学报 58 2345]

    [12]

    Wang H, Wu G Z 2006 Chem.Phys.Lett. 421 460

    [13]

    Chantry G W 1971 Polarizability Theory for the Raman Effect (New York: Marcel Dekker)

    [14]

    Yoshino T, Bernstein H J 1959 Spectrochim.Acta 14 127

  • [1]

    Liu Z J 2006 Ph.D. Dissertation (Tsinghua University) (in Chinese)[刘照军 2006 博士学位论文 (清华大学)]

    [2]

    Fang C, Liu Z J, Wu G Z 2008 J.Mol.Struct. 885 168

    [3]

    Fang C, Wu G Z 2009 J. Raman Spectrosc. 40 308

    [4]

    Fang C, Wu G Z 2007 J. Raman Spectrosc. 38 1416

    [5]

    Wu G Z 2007 Raman Spectroscopy: A Intensity Approach (Beijing: Science Press) p70-84 (in Chinese)[吴国祯 2007 拉曼谱学-峰强中的信息.(北京:科学出版社)第70—84页]

    [6]

    Zhong F P, Wu G Z 1993 J.Mol.Struct. 298 55

    [7]

    Wang P J, Wu G Z 2004 Chem.Phys.Lett. 385 96

    [8]

    Huang Y, Wu G Z 1990 Spectrochimica Acta A 46 377

    [9]

    Liu Z J, Wu G Z 2004 Chem.Phys.Lett. 389 298

    [10]

    Liu Z J, Wu G Z 2006 Acta.Phys.Sin. 55 6315(in Chinese)[刘照军、吴国祯 2006 物理学报 55 6315]

    [11]

    Fang C, Wu G Z 2009 Acta.Phys.Sin. 58 2345(in Chinese)[房 超、吴国祯 2009 物理学报 58 2345]

    [12]

    Wang H, Wu G Z 2006 Chem.Phys.Lett. 421 460

    [13]

    Chantry G W 1971 Polarizability Theory for the Raman Effect (New York: Marcel Dekker)

    [14]

    Yoshino T, Bernstein H J 1959 Spectrochim.Acta 14 127

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  • 文章访问数:  7435
  • PDF下载量:  698
  • 被引次数: 0
出版历程
  • 收稿日期:  2009-08-24
  • 修回日期:  2009-12-03
  • 刊出日期:  2010-09-15

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