An ab initio prediction of the extraordinary static first hyperpolarizability for the electron-solvated cluster (FH)(2){e}(HF)

作者：Li Y; Li ZR^*; Wu D; Li RY; Hao XY; Sun CC

来源：Journal of Physical Chemistry B, 2004, 108(10): 3145-3148.

DOI：10.1021/jp036808u

A theoretical prediction of the nonlinear optical (NLO) properties of the hydrogen fluoride trimer anion (FH)(2){e}(HF) reveals that this electron-solvated cluster possesses exceptionally large static first hyperpolarizability. Using the d-aug-cc-pVDZ basis set supplemented with diffusive bond functions (BF), we obtained the mean static first hyperpolarizability (beta(0)) for (FH)(2){e}(HF) and its neutral core (HF)(2){e}(HF) at the CISD level of theory. The beta(0) is 8.1 x 10(6) au for (FH)(2){e}(HF) and 5.1 au for (HF)(2){}(HF). Obviously, the excess electron is the key factor in bringing to (FH)(2){e}(HF) the significantly large NLO response. The other properties of (FH)(2){e}(HF) are also much larger than those of its neutral core. The values of the static dipole moment, mean polarizability, and anisotropy of the polarizability are, respectively, mu = 1.5764 au, alpha(0) = 654.67 au, and Deltaalpha = 224.71 au for the anion, and mu = 0.9351 au, alpha(0) = 17.34 au, Deltaalpha = 5.40 an for the neutral core. In addition, the field dependences of the polarizability and first hyperpolarizability are obtained at the MP2/ d-aug-ce-pVDZ+BF level of theory. And the influence of the secondary interaction, H-bond-excess electron attracting, on the static first hyperpolarizability of (HF)(2){e}(HF) is also explored.

• 出版日期2004-3-11
• 单位吉林大学