Modeling Ar and Kr matrix effect on the nu(s) (Cl - H) and nu(l) (Cl - H) of Cl - H center dot center dot center dot NH(3) by the IEF-PCM method

作者：Liu Guoqun^*; Zhao Yaomin; Yang Yu

来源：Structural Chemistry, 2008, 19(4): 659-663.

DOI：10.1007/s11224-008-9342-7

• B3LYP and MP2 calculations
• IEF-PCM
• argon and krypton matrix effect
• anharmonic frequencies
• ammonia-hydrogen chloride complex

Ar and Kr matrix effect on the geometry and Cl-H stretching (nu(s) (Cl-H)) and librational (nu(l) (Cl-H)) frequencies of the hydrogen-bonded complex Cl-H center dot center dot center dot NH(3) are simulated within the framework of polarizable continuum model with integral equation formalism (IEF-PCM) at B3LYP and MP2 levels of theory with the basis set 6-311++G(2df,2pd). Within the framework of B3LYP and IEF-PCM, the simulated gas phase, Ar, and Kr matrix nu(s) (Cl-H) of the complex are 2140, 1684, and 1550 cm(-1), respectively, which deviate from the experimental values (similar to 2200, 1371, and 1218 cm(-1)) by -60, 313, and 332 cm(-1). Within the framework of MP2 and IEF-PCM, the gas phase, Ar, and Kr matrix nu(s) (Cl-H) are calculated as 2366, 2037, and 1957 cm(-1) by the harmonic approximation, and as 2177, 1876, and 1665 cm(-1) by the full-dimensional anharmonic correction. The matrix effect modeling is of greater importance than the anharmonic correction in accounting for the large experimental gas phase to Ar or Kr matrix shift of the nu(s) (Cl-H) (-829 or -982 cm(-1)). Our calculations do not support the assignment of the 733.8 and 736.9 cm(-1) bands to the Ar and Kr matrix nu (l) (Cl-H).

• 出版日期2008-8
• 单位中原工学院