Vibrational energy transfer was a key property of chemical reactions that remains deeply understood. In this work, the detail information of vibrational energy transfer in aniline, N,N-dimethylaniline (DMA) and N,N-diethylaniline (DEA) were studied by femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy, respectively. Low frequency modes of aniline, DMA and DEA were collectively excited, the beats arising from vibrational couplings among these modes were described. With analysis of vibrational coupling, energy transfer flow from one mode to another was visualized. An investigation into the molecular structure and vibrational couplings can be found that vibrational energy transfer is related to vibrational mode symmetry. In addition, substituent groups play an important role in vibrational coupling and energy transfer of aniline, DMA and DEA. A decrease of the number of substituent vibrational modes involved in coupling and energy transfer efficiency with the increase of the amount of relative molecular mass ratio was found out.
Graphical abstract
振动能量转移是化学反应的一个关键特性,但人们对这一特性的理解仍然很深。本研究利用飞秒时间分辨相干反斯托克斯拉曼散射(CARS)光谱分别研究了苯胺、N,N-二甲基苯胺(DMA)和N,N-二乙基苯胺(DEA)中振动能量传递的详细信息。对苯胺、DMA 和 DEA 的低频模式进行了集体激发,并描述了这些模式之间振动耦合产生的节拍。通过分析振动耦合,可以直观地看到能量从一个模式传递到另一个模式。通过对分子结构和振动耦合的研究可以发现,振动能量的传递与振动模式的对称性有关。此外,取代基团在苯胺、DMA 和 DEA 的振动耦合和能量传递中起着重要作用。研究发现,随着相对分子质量比的增加,参与耦合和能量传递效率的取代基振动模式数量减少。
{"title":"Studying substituent number effects on vibrational energy transfer by time−resolved CARS spectroscopy","authors":"Xiaosong Liu, Qingxiao Zou, Hui Li, Weilong Liu, Feng Hu, Yanqiang Yang","doi":"10.1140/epjd/s10053-024-00830-w","DOIUrl":"10.1140/epjd/s10053-024-00830-w","url":null,"abstract":"<div><p>Vibrational energy transfer was a key property of chemical reactions that remains deeply understood. In this work, the detail information of vibrational energy transfer in aniline, N,N-dimethylaniline (DMA) and N,N-diethylaniline (DEA) were studied by femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy, respectively. Low frequency modes of aniline, DMA and DEA were collectively excited, the beats arising from vibrational couplings among these modes were described. With analysis of vibrational coupling, energy transfer flow from one mode to another was visualized. An investigation into the molecular structure and vibrational couplings can be found that vibrational energy transfer is related to vibrational mode symmetry. In addition, substituent groups play an important role in vibrational coupling and energy transfer of aniline, DMA and DEA. A decrease of the number of substituent vibrational modes involved in coupling and energy transfer efficiency with the increase of the amount of relative molecular mass ratio was found out.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":789,"journal":{"name":"The European Physical Journal D","volume":null,"pages":null},"PeriodicalIF":1.5,"publicationDate":"2024-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140596660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-04DOI: 10.1140/epjd/s10053-024-00831-9
Rajnandan Choudhury Das, Samir Khan, Thilagaraj Ravi, Kanhaiya Pandey
The 5S(rightarrow )6P transition in rubidium (Rb) at 420 nm offers the advantage of narrow linewidth and diverse applications in quantum technologies. However, the direct spectroscopy at this transition is challenging due to its weak transition strength. In this paper, we have discussed the saturated absorption spectroscopy (SAS) of Rb using the narrow-line transition at 420 nm. We have studied the effect of the temperature of the Rb cell, control beam power, and beam size on the SAS dip heights and their linewidths. Additionally, our study offers a comprehensive examination, encompassing all eight error signals of Rb for the 5 S(rightarrow )6P transition at 420 nm and 421 nm. These findings contribute valuable insights to the field of laser frequency stabilization of Rb at blue transition and can be useful in quantum technologies based on this transition.
Direct spectroscopy of Rubidium at blue transition.
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Pub Date : 2024-04-04DOI: 10.1140/epjd/s10053-024-00829-3
Johannes Fiedler, Bodil Holst
Atom and, of late, molecule interferometers find application in both the crucible of fundamental research and industrial pursuits. A prevalent methodology in the construction of atom interferometers involves the utilisation of gratings fashioned from laser beams. While this approach imparts commendable precision, it is hampered by its incapacity to attain exceedingly short wavelengths and its dependence on intricate laser systems for operational efficacy. All applications require the control of matter waves, particularly the particle’s velocity. In this manuscript, we propose a continuous beam monochromator scheme reaching enormously high velocity purification with speed ratios in the order of (10^3) based on atom-surface diffraction. Beyond these high purifications, the proposed scheme simplifies the application by reducing the degree of freedom to a single angle, selecting the wanted particle’s velocity.
{"title":"A continuous beam monochromator for matter waves","authors":"Johannes Fiedler, Bodil Holst","doi":"10.1140/epjd/s10053-024-00829-3","DOIUrl":"10.1140/epjd/s10053-024-00829-3","url":null,"abstract":"<p>Atom and, of late, molecule interferometers find application in both the crucible of fundamental research and industrial pursuits. A prevalent methodology in the construction of atom interferometers involves the utilisation of gratings fashioned from laser beams. While this approach imparts commendable precision, it is hampered by its incapacity to attain exceedingly short wavelengths and its dependence on intricate laser systems for operational efficacy. All applications require the control of matter waves, particularly the particle’s velocity. In this manuscript, we propose a continuous beam monochromator scheme reaching enormously high velocity purification with speed ratios in the order of <span>(10^3)</span> based on atom-surface diffraction. Beyond these high purifications, the proposed scheme simplifies the application by reducing the degree of freedom to a single angle, selecting the wanted particle’s velocity.</p>","PeriodicalId":789,"journal":{"name":"The European Physical Journal D","volume":null,"pages":null},"PeriodicalIF":1.5,"publicationDate":"2024-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1140/epjd/s10053-024-00829-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140596773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-03DOI: 10.1140/epjd/s10053-024-00828-4
Peter Uylings, Ton Raassen
Orthogonal operators are a next step in the semi-empirical description of complex spectra. Orthogonality yields optimal independence and thus least correlation between the operators. The increased stability of the fitting process is used to include higher-order many-body as well as fully relativistic effects. The calculated eigenvalues are frequently an order of magnitude more accurate with respect to a conventional semi-empirical approach. The resulting eigenvectors may not only be put to use to calculate transition probabilities and g-factors, but also to calculate hyperfine structure A and B constants. We illustrate our first steps in this field with two examples of first spectra of the iron group elements. The results are compared to current experimental hyperfine structure A-values while strong and weak points of the method are discussed. In particular to be able to deal with lanthanides and actinides, the orthogonal operator method is completed with the definition of operators for equivalent p- and f-electrons.
摘要 正交算子是复杂光谱半经验描述的下一步。正交性产生了最佳的独立性,从而使算子之间的相关性最小。拟合过程稳定性的提高可用于包含高阶多体效应和完全相对论效应。与传统的半经验方法相比,计算出的特征值通常要精确一个数量级。由此得到的特征向量不仅可以用来计算转变概率和 g 因子,还可以用来计算超细结构 A 常量和 B 常量。我们以两个铁族元素的第一光谱为例,说明我们在这一领域迈出的第一步。我们将结果与当前的实验超正弦结构 A 值进行了比较,同时讨论了该方法的强项和弱项。特别是为了能够处理镧系元素和锕系元素,通过定义等效 p 电子和 f 电子的算子完成了正交算子方法。 图形摘要
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Pub Date : 2024-04-03DOI: 10.1140/epjd/s10053-024-00820-y
Alexander Kramida
The present article discusses some recent advances in methods of critical evaluation of experimental data on wavelengths of spectral lines and theoretical data on transition probabilities and oscillator strengths for atoms and atomic ions. In particular, recently developed new statistical approaches to estimation of uncertainties of weighted means of multiple measurements are described, and a numerical toolbox implementing these new approaches is presented. There are also some new developments in estimation of uncertainties of theoretical transition probabilities. A short review of literature implementing these new procedures is provided, including a description of the methodology.
{"title":"Evaluation of uncertainties in atomic data on spectral lines and transition probabilities","authors":"Alexander Kramida","doi":"10.1140/epjd/s10053-024-00820-y","DOIUrl":"10.1140/epjd/s10053-024-00820-y","url":null,"abstract":"<p>The present article discusses some recent advances in methods of critical evaluation of experimental data on wavelengths of spectral lines and theoretical data on transition probabilities and oscillator strengths for atoms and atomic ions. In particular, recently developed new statistical approaches to estimation of uncertainties of weighted means of multiple measurements are described, and a numerical toolbox implementing these new approaches is presented. There are also some new developments in estimation of uncertainties of theoretical transition probabilities. A short review of literature implementing these new procedures is provided, including a description of the methodology.</p>","PeriodicalId":789,"journal":{"name":"The European Physical Journal D","volume":null,"pages":null},"PeriodicalIF":1.5,"publicationDate":"2024-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1140/epjd/s10053-024-00820-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140596804","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-03DOI: 10.1140/epjd/s10053-024-00810-0
Jaroslav Hofierka, Brian Cunningham, Dermot G. Green
Positron bound state properties in hydrogen cyanide are studied via many-body theory calculations that account for strong positron-electron correlations including positron-induced polarization, screening of the electron–positron Coulomb interaction, virtual-positronium formation and positron–hole repulsion. Specifically, the Dyson equation is solved using a Gaussian basis, with the positron self-energy in the field of the molecule calculated using the Bethe–Salpeter equations for the two-particle and particle–hole propagators. The present results suggest near cancellation of screening corrections to the bare polarization, and the non-negligible role of the positron–hole interaction. There are no existing measurements to compare to for HCN. Previous configuration interaction (CI) and fixed-node diffusion Monte Carlo (FN-DMC) calculations give positron binding energies in the range 35–44 meV, most of which used a single even-tempered basis centred near the nitrogen atom. Using a similar single-centre positron basis we calculate a positron binding energy of 41 meV, in good agreement. However, we find that including additional basis centres gives an improved description of the positron wave function near the nuclei, and results in a converged binding energy in the range 63–73 meV (depending on geometry and approximation to the positron–molecule correlation potential used).
{"title":"Many-body theory calculations of positron binding to hydrogen cyanide","authors":"Jaroslav Hofierka, Brian Cunningham, Dermot G. Green","doi":"10.1140/epjd/s10053-024-00810-0","DOIUrl":"10.1140/epjd/s10053-024-00810-0","url":null,"abstract":"<p>Positron bound state properties in hydrogen cyanide are studied via many-body theory calculations that account for strong positron-electron correlations including positron-induced polarization, screening of the electron–positron Coulomb interaction, virtual-positronium formation and positron–hole repulsion. Specifically, the Dyson equation is solved using a Gaussian basis, with the positron self-energy in the field of the molecule calculated using the Bethe–Salpeter equations for the two-particle and particle–hole propagators. The present results suggest near cancellation of screening corrections to the bare polarization, and the non-negligible role of the positron–hole interaction. There are no existing measurements to compare to for HCN. Previous configuration interaction (CI) and fixed-node diffusion Monte Carlo (FN-DMC) calculations give positron binding energies in the range 35–44 meV, most of which used a single even-tempered basis centred near the nitrogen atom. Using a similar single-centre positron basis we calculate a positron binding energy of 41 meV, in good agreement. However, we find that including additional basis centres gives an improved description of the positron wave function near the nuclei, and results in a converged binding energy in the range 63–73 meV (depending on geometry and approximation to the positron–molecule correlation potential used).</p>","PeriodicalId":789,"journal":{"name":"The European Physical Journal D","volume":null,"pages":null},"PeriodicalIF":1.5,"publicationDate":"2024-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1140/epjd/s10053-024-00810-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140596914","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-04-02DOI: 10.1140/epjd/s10053-024-00819-5
Li Dai, Shuo Shi, Zhipeng Huang, Xianbiao Li
Zr:Ho:LiNbO3 crystals with different concentrations of Zr4+ were prepared by Czochralski method. The internal structure changes and the occupancy of doped ions were analyzed by X-ray diffraction (XRD). The effective segregation coefficient was analyzed by inductively coupled plasma atomic emission spectrometer (ICP-AES), and the optical homogeneity was analyzed by birefringence gradient method. The experimental results show that doping does not change the inherent structure of the crystal, the threshold concentration of Zr4+ is 1 mol%, and the occupation of Zr4+ changes before and after the threshold concentration. The effective separation coefficient of Zr4+ and Ho3+ decreases with the increase of ZrO2 concentration. The optical homogeneity of the crystal will increase with the increase of ZrO2 concentration, and the optical homogeneity of the crystal is strongest when the concentration of ZrO2 reaches the maximum (4 mol%).