本文選題：結(jié)構(gòu)計(jì)算 + 多參考組態(tài)相互作用　； 參考：《中國(guó)科學(xué)技術(shù)大學(xué)》2017年博士論文

【摘要】：隨著先進(jìn)光源技術(shù)進(jìn)步,原子分子物理實(shí)驗(yàn)和理論研究都取得了快速發(fā)展。例如,基于第三代同步輻射技術(shù)發(fā)展的X射線散射方法,可以精確測(cè)量出原子動(dòng)力學(xué)參數(shù);利用自由電子激光技術(shù),可以在飛秒甚至更快的時(shí)間尺度上對(duì)原子分子動(dòng)力學(xué)過程進(jìn)行調(diào)控。前者可以提供精確的形狀因子平方(Squared Form Factor,SFF),該參數(shù)可以很好地表征原子分子基態(tài)和激發(fā)態(tài)波函數(shù)在不同空間尺度區(qū)域的行為;后者可以用于研究原子分子亞穩(wěn)態(tài)的動(dòng)力學(xué)行為,并且新發(fā)現(xiàn)了諸如原子間庫(kù)倫衰變(interatomic coloumb decay,ICD)這種有趣的現(xiàn)象。原則上,一階Born近似下原子分子動(dòng)力學(xué)參數(shù)的計(jì)算精度,僅僅取決于結(jié)構(gòu)計(jì)算的精度。以往的實(shí)驗(yàn)證明,X射線和原子體系(He、Ne、Ar)的散射中,一階Born近似成立。然而對(duì)于X射線和分子體系的散射,一階Born近似的成立情況尚不清楚。同時(shí),基于玻恩-奧本海默近似計(jì)算的分子結(jié)構(gòu)精度,也有待進(jìn)一步的檢驗(yàn)。因此,有必要開展X射線和分子的散射實(shí)驗(yàn),以及相關(guān)的理論計(jì)算,來(lái)驗(yàn)證一階Born近似的成立性,并評(píng)估分子結(jié)構(gòu)計(jì)算方法的精確度。對(duì)于共振態(tài),由于其波函數(shù)具有一定的局域特性,可以采用一些特殊手段,利用束縛態(tài)計(jì)算方法進(jìn)行研究。分子結(jié)構(gòu)的計(jì)算方法眾多,在本文中采用基于變分原理的"多參考單雙激發(fā)的組態(tài)相互作用方法(multi-reference single and double excitation configuration interaction,MRSDCI/MRCI)"來(lái)計(jì)算束縛態(tài)的結(jié)構(gòu),并將該方法拓展至復(fù)數(shù)區(qū)域,結(jié)合復(fù)坐標(biāo)旋轉(zhuǎn)方法(complex coordinate rotation method,CRM)以及復(fù)吸收勢(shì)法(complex absorption potential,CAP),用于原子分子的共振態(tài)以及ICD態(tài)的計(jì)算。本論文的具體工作如下:(1)采用MRCI方法計(jì)算了 H_2以及N_2的電子態(tài)結(jié)構(gòu),并結(jié)合一階Born近似計(jì)算了相應(yīng)的彈性以及非彈性的動(dòng)力學(xué)結(jié)構(gòu)參數(shù),同時(shí)采用非彈性X射線散射方法測(cè)量了 N_2在12-13.3eV激發(fā)能區(qū)振動(dòng)分辨的動(dòng)力學(xué)參數(shù)。對(duì)于簡(jiǎn)單的體系H_2,非相對(duì)論的漸進(jìn)能量計(jì)算精度很高,且動(dòng)力學(xué)參數(shù)的計(jì)算結(jié)果和X射線散射實(shí)驗(yàn)結(jié)果符合很好。對(duì)于較復(fù)雜的體系N_2,動(dòng)力學(xué)參數(shù)的計(jì)算結(jié)果和實(shí)驗(yàn)結(jié)果也符合很好,同時(shí)發(fā)現(xiàn)對(duì)于部分態(tài),中能和高能電子能量損失譜方法未能達(dá)到一階Born近似。以上結(jié)果成功證實(shí)了 X射線和分子體系散射中一階Born近似的成立性,拓展了X射線散射方法作為實(shí)驗(yàn)基準(zhǔn)數(shù)據(jù)的評(píng)估范圍。另一方面,H_2動(dòng)力學(xué)參數(shù)的計(jì)算結(jié)果和X射線散射實(shí)驗(yàn)結(jié)果的差異似乎較為反常,其背后可能有值得考慮的物理機(jī)制;(2)發(fā)展了計(jì)算一維分子振轉(zhuǎn)共振態(tài)的CRM/CAP+DVR方法,可以精確計(jì)算雙原子分子振轉(zhuǎn)亞穩(wěn)態(tài)的共振能級(jí)和自解離速率。利用該方法計(jì)算了 Cu_2和LiH~-分子的振轉(zhuǎn)自解離態(tài),對(duì)于CU_2~-的解離速率,采用CRM+DVR方法計(jì)算的結(jié)果和使用WKB近似計(jì)算的結(jié)果差別了近一個(gè)數(shù)量級(jí),說明WKB近似對(duì)于大質(zhì)量的粒子并不適用。LiH-共振能級(jí)和寬度的計(jì)算結(jié)果和分子軌道強(qiáng)耦合方法(QMOCC)的計(jì)算結(jié)果符合很好,兩種方法互相驗(yàn)證了可靠性,而本文的CAP+DVR方法同時(shí)還可以輔助標(biāo)注各個(gè)共振峰對(duì)應(yīng)的振轉(zhuǎn)態(tài)的量子數(shù);(3)成功實(shí)現(xiàn)以CRM+MRCI方法計(jì)算原子分子Feshbach共振態(tài)。通過計(jì)算Nq+(q=2-5)離子的k殼層空穴態(tài)的共振參數(shù),摸索出合適的基組選擇方法,得出了 28個(gè)共振Auger態(tài)的能級(jí)和寬度數(shù)據(jù),計(jì)算結(jié)果與其他理論和實(shí)驗(yàn)值符合很好,并驗(yàn)證了與自旋相關(guān)的Auger速率關(guān)系。成功計(jì)算了He_2~+的ICD態(tài)寬度,相對(duì)于其他方法,本文的CRM+MRCI方法采用更小的基組和計(jì)算量,獲得精度相當(dāng)?shù)挠?jì)算結(jié)果。
[Abstract]:With the advanced light source technology, atomic and molecular physics experiments and theoretical research have achieved rapid development. For example, X ray scattering method of third generation synchrotron radiation based on the development of technology, can accurately measure the atomic dynamics parameters; using free electron laser technology, can even femtosecond faster time scales of atomic and molecular dynamics in the process of regulation. The former can provide accurate square shape factor (Squared Form, Factor, SFF), the parameters can be well characterized molecular and atomic ground state excited state wave function at different spatial scales in the area of behavior; the latter can be used to study the dynamics of metastable atoms and molecules, and the newly discovered atoms such as Kulun decay (interatomic Coloumb decay, ICD) this interesting phenomenon. In principle, calculation of the first order Born approximation in atomic and molecular dynamics parameters of precision, simply In the structure calculation accuracy. The experiment proved that, X rays and atomic system (He, Ne, Ar) scattering in the first order Born approximation is established. However, for X ray scattering and molecular system, the establishment of the first order Born approximation is not clear. At the same time, Born - Oppenheimer in the molecular structure of precision based on calculation, also needs to be further tested. Therefore, it is necessary to carry out X X-ray scattering experiments and molecular computation, and the related theories, to verify the validity of the first order Born approximation, and the calculation method of molecular structure accuracy. For resonance due to the wave function with local characteristics, we can use some special means, use bound calculation methods were studied. Many calculation methods of molecular structure, the multireference single and double excitation configuration interaction method based on the variational principle "in this paper (multi-reference single and Dou Ble excitation configuration interaction, MRSDCI/MRCI) "to calculate the structure of the bound state, and this method is extended to complex area, combined with the complex coordinate rotation method (complex coordinate rotation method, CRM) and the complex absorption potential (complex absorption potential, CAP method), used in atomic and molecular resonances and calculation of ICD state. The specific work this paper is as follows: (1) using MRCI H_2 method and electronic structure of N_2 is calculated, and combined with the first-order Born corresponding elastic and inelastic dynamic structural parameters were calculated using non elastic approximation and X ray scattering method N_2 kinetic parameters of vibration excitation in 12-13.3eV resolution measurement system for H_2. Simple, non relativistic asymptotic energy has very high calculation precision, calculation results and kinetic parameters of X and X-ray scattering is consistent with the experimental results. For more complex body. Department of N_2, the calculation results of kinetic parameters and experimental results are in good agreement, also found that for part of the state, and in high energy electron energy loss spectroscopy method can meet the first order Born approximation. The above results confirmed the successful establishment of the first order Born approximation in X ray system and molecular scattering, extended X ray scattering method as the experimental reference data to assess the scope. On the other hand, the difference calculation results of kinetic parameters of H_2 and X ray scattering of experimental results is likely to be abnormal, which might be behind a physical mechanism worthy of consideration; (2) the development of the CRM/CAP+DVR method in the calculation of one-dimensional molecular vibrational resonances. The resonance level can be accurately calculated for diatomic molecules rovibrational metastable and self dissociation rate. Cu_2 and LiH~- molecular rovibrational self dissociation is calculated by using the method, the dissociation rate of CU_2~-, and the results calculated by CRM+DVR method Using the WKB approximate calculation results differ by nearly an order of magnitude, indicating that WKB approximate calculation results for large mass particles is not suitable for.LiH- and the width of the resonance level and the molecular orbital coupling method (QMOCC) calculation results are in good agreement with each other, the two methods to verify the reliability of the CAP+DVR method in this paper, and at the same time you can also assist marked quantum number of each resonance peak corresponds to the rovibrational states; (3) the successful implementation of the CRM+MRCI method in the calculation of atomic and molecular resonances. Through the calculation of Nq+ Feshbach (q=2-5) k resonance parameters of shell holes ions, find out suitable basis set selection method, the level and width of data 28 Auger resonance state, the calculated results are compared with other theoretical and experimental values are in good agreement, and verify the Auger rate relationship with spin dependent. The success of the He_2~+ ICD state width was calculated and compared with other methods, this paper CRM+MRCI The method uses the smaller base group and the amount of calculation to obtain the accurate calculation results.

【學(xué)位授予單位】：中國(guó)科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O561

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