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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical investigation of the (hyper) polarizabilities of pyrrole homologues C4H4XH (X = N, P, As, Sb, Bi). A coupled-cluster and density functional theory study
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Theoretical investigation of the (hyper) polarizabilities of pyrrole homologues C4H4XH (X = N, P, As, Sb, Bi). A coupled-cluster and density functional theory study

机译：吡咯同系物C4H4XH（X = N，P，As，Sb，Bi）的（超）极化率的理论研究。聚类与密度泛函理论的研究

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Geometries, inversion barriers, static and dynamic electronic and vibrational dipole polarizability (R), and first (beta) and second (gamma) hyperpolarizability of the pyrrole homologues C4H4XH (X = N, P, As, Sb, Bi) have been calculated by Hartree-Fock, Moller-Plesset second-order perturbation theory, coupled-cluster theory accounting for singles, doubles, and noniterative triple excitations methods, as well as density functional theory using B3LYP and PBE1PBE functionals and Sadlej's Pol and 6-311G** basis sets. Relativistic effects on the heavier homologues stibole and bismole have been taken into account within effective core potential approximation. The results show that the electronic (hyper) polarizabilities monotonically increase with the atomic number of the heteroatom, consistent with the decrease in the molecular hardness. Ring planarization reduces the carbon-carbon bond length alternation of the cis-butadienic unit, enhancing the electronic polarizability values () by 4-12% and the (hyper) polarizability values (beta(e)(vec) and ) by 30-90%. Pure vibrational and zero-point vibrational average contributions to the (hyper) polarizabilities have been determined within the clamped nucleus approach. In the static limit, the pure vibrational hyperpolarizabilities have a major contribution. Anharmonic corrections dominate the pure vibrational hyperpolarizabilities of pyrrole, while they are less important for the heavier homologues. Static and dynamic electronic response properties of the pyrrole homologues are comparable to or larger than the corresponding properties of the furan and cyclopentadiene homologue series.
机译：吡咯同系物C4H4XH（X = N，P，As，Sb，Bi）的几何形状，反垒，静态和动态电子及振动偶极极化率（R）以及第一（beta）和第二（γ）超极化率Hartree-Fock，Moller-Plesset二阶摄动理论，耦合群理论解释了单，双和非迭代三重激发方法，以及使用B3LYP和PBE1PBE泛函以及Sadlej的Pol和6-311G **基础的密度泛函理论套。在有效的核心电势近似值范围内，已考虑到对较重的同种异味甾烷和双胍的相对论效应。结果表明，电子（超）极化率随杂原子的原子数单调增加，与分子硬度的降低一致。环平面化减少了顺丁二烯单元的碳-碳键长交替，将电子极化率值（α（e））提高了4-12％，并且将（超）极化率值（beta（e）（vec））提高了和）30-90％。在固定核方法中已经确定了对（超）极化率的纯振动和零点振动平均贡献。在静态极限中，纯振动超极化率起主要作用。非谐校正主导了吡咯的纯振动超极化，而对于重同源物则不那么重要。吡咯同系物的静态和动态电子响应特性与呋喃和环戊二烯同系物系列的相应特性相当或更大。

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