Molecular ionization energies and ground- and ionic-state properties using a non-Dyson electron propagator approach.
Molecular ionization energies and ground- and ionic-state properties using a non-Dyson electron propagator approach.
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使用非戴森电子传播器方法的分子电离能以及基态和离子态特性。
DOI：
10.1063/1.2047550
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发表时间：
2005
期刊：
影响因子：
--
通讯作者：
J. Schirmer
中科院分区：
文献类型：
--
作者：
A. Trofimov;J. Schirmer
早期提出的传播分子电离的治疗方法进行了测试，在第一个应用程序。被称为电子传播子的非Dyson三阶代数图解构造[nD-ADC（3）]近似的方法代表了现有Dyson ADC（3）方法在计算上有前途的替代方案。nD-ADC（3）方案的优点是单粒子绿色函数的（N+/-1）电子部分相互解耦，相应的方程可以单独求解。为了验证该方法的有效性，将C（2）H（4），CO，CS，F（2），H（2）CO，H（2）O，HF，N（2），Ne垂直电离跃迁的nD-ADC（3）计算结果与已有的实验和理论数据（包括全组态相互作用（FCI）和耦合团簇计算结果）进行了比较。nD-ADC（3）电离能相对于实验和FCI结果的平均误差约为0.2 eV。nD-ADC（3）方法，随着轨道的数目按n（5）缩放，需要解决相对简单的厄米特本征值问题。该方法呈现访问基态属性，如偶极矩。此外，由于nD-ADC方法的特定中间态表示（ISR）公式，现在还可以研究（N+/-1）电子态的单电子性质。给出了相应的二阶ISR方程。
An earlier proposed propagator method for the treatment of molecular ionization is tested in first applications. The method referred to as the non-Dyson third-order algebraic-diagrammatic construction [nD-ADC(3)] approximation for the electron propagator represents a computationally promising alternative to the existing Dyson ADC(3) method. The advantage of the nD-ADC(3) scheme is that the (N+/-1)-electronic parts of the one-particle Green's function are decoupled from each other and the corresponding equations can be solved separately. For a test of the method the nD-ADC(3) results for the vertical ionization transitions in C(2)H(4), CO, CS, F(2), H(2)CO, H(2)O, HF, N(2), and Ne are compared with available experimental and theoretical data including results of full configuration interaction (FCI) and coupled cluster computations. The mean error of the nD-ADC(3) ionization energies relative to the experimental and FCI results is about 0.2 eV. The nD-ADC(3) method, scaling as n(5) with the number of orbitals, requires the solution of a relatively simple Hermitian eigenvalue problem. The method renders access to ground-state properties such as dipole moments. Moreover, also one-electron properties of (N+/-1) electron states can now be studied as a consequence of a specific intermediate-state representation (ISR) formulation of the nD-ADC approach. Corresponding second-order ISR equations are presented.