Theoretical and experimental studies of optical nonlinearities of haloforms CHX3, X=F, Cl, Br, I
Theoretical and experimental studies of optical nonlinearities of haloforms CHX3, X=F, Cl, Br, I
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卤仿CHX3、X=F、Cl、Br、I光学非线性的理论与实验研究
DOI：
10.1063/1.458227
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发表时间：
1990
影响因子：
4.4
通讯作者：
P. Prasad
中科院分区：
文献类型：
--
作者：
S. Karna;M. Dupuis;E. Perrin;P. Prasad
本文用有效核势方法从头算计算了卤型系列CHX_3的静态极化率α、静态第一超极化率β和静态第二超极化率γ，其中X=F、Cl、Br和I。微观光学非线性系数α，β和γ是能量对电场的导数，能量由自洽场方法确定，非线性系数由耦合微扰哈特里-福克公式计算。为了检验ECP方法引入的近似，对CHF3和CHCl3系列中较轻的成员的非线性光学响应与全电子计算进行了比较。研究了基组大小和d、f型扩散函数和偏振函数的包含对计算结果的影响。然后使用ECP技术计算CHBr3和CHI3的光学非线性。虽然计算的极化率与实验的极化率之间有很好的一致性。
In this paper, we present ab initio calculations of static polarizability α and static first and second hyperpolarizabilities β and γ for the haloform series CHX3, where X=F, Cl, Br, and I using the effective core potential (ECP) approach. The microscopic optical nonlinearities α, β, and γ are calculated as the derivatives of the energy with respect to the electric field, with the energy determined by means of the self‐consistent‐field approach (SCF), and nonlinearities calculated by means of the coupled perturbed Hartree–Fock (CPHF) formalism. To test the approximation introduced by the ECP method, nonlinear optical responses for the lighter members of the series CHF3 and CHCl3 are compared with all electron calculations. The effects due to basis set size and inclusion of diffuse and polarization functions of d and f type are examined. The ECP technique is then used to calculate optical nonlinearities for CHBr3 and CHI3. Although very good agreement is found between calculated and experimental polarizabi...